KR830000230B1 - Manufacturing method of hard butter by continuous fractional crystallization - Google Patents

Abstract

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Description

Manufacturing method of hard butter by continuous fractional crystallization

TECHNICAL FIELD The present invention relates to a method for preparing a fat composition, and more particularly, to a special hard butter added to cocoa butter or cocoa butter and butterfat, or such a special hard butter.

In recent years, the price of chocolate liquor and cocoa butter has increased, so there is a great need for a replacement for cocoa butter, and in particular, the need to pursue economic feasibility for the final composition by mixing cocoa butter or cocoa butter and fats with these substitutes. It is becoming. The direction of research on these hybrid alternatives takes two basic directions. One direction is to find the chemical structure of triglycerides, the main ingredient in cocoa butter, and fats that can be naturally or approximately converted. This approach often requires the use of foreign-derived fats such as oil, mango oil and shea butter. Clearly, lauric oil, ie, those rich in lauric triglycerides such as palm kernel oil, coconut oil, duck colander, parquet, etc., are not logically applicable. The other direction is a fat, oil, and C ₁₆ - ₁₈ of triglycerides are many things that create acid fat, soybean oil, for example, cottonseed oil, corn oil, coconut oil, lard oil, safflower oil (紅花油), sunflower oil, rice bran oil, A mixture of olive oil and rapeseed oil with a small amount of erucic acid is used to separate products that are close to hard and glossy cocoa butter. In general, in this case, investigating compatible substitutes separates the fats derived from these oils or mixtures, which are chemically different from cocoa butter. For example, it contains fatty acids that produce a substantial portion of unsaturated fats in a high melting trans configuration that is distinct from a low melting cis configuration. Among the cocoa butter there is no or substantially no acid in these trans systems.

Known ones that the inventors know most relevant are US Pat. No. 2,972,541 to Cochran et al. According to this patent, a triglyceride hard butter having a certain amount of saturated fatty acid and unsaturated fatty acid produced from non-lauric oil is trans coordination. These products are prepared by selectively hydrogenating the starting fat to remove at least most of the polyethenically unsaturations and to obtain monoethene unsaturations which are in the ratio of trans to desired cis. After the hydrogenation reaction, fats are dissolved in acetone, other keto or 2-nitropropane, and then fractionated and crystallized successively to make high melting point crystals such as stearin and crystalline hard butter components belonging to the type intended in the present invention. To separate.

In the present invention, various fats can be used. These include soybeans, cottonseeds, safflowers, palms, peanuts, sunflowers, rapeseeds with low erucic acid, corn, rice bran, sesame seeds, citrus seeds, common liquid components of pork oil, fat of chicken, or mixtures thereof. There is oil from the back. In view of efficiency and economics, it is generally advantageous to use oil from a single material. Frequently used in the present invention is a hard butter made by systematic continuous fractional crystallization of cottonseed oil having a large content of a trans-system selectively hydrogenated from an organic solvent. Furthermore, in the present invention, an oil mixture in which corn, soybean, safflower oil, etc. are rearranged together with palm oil and fractionated and crystallized with sodium methylate may be used.

A large amount of triglyceride structures are also readily found in selectively hydrogenated single oils, such as cottonseed oil and soybean oil. C ₁₆ - ₁₈ in the unsaturated fatty acids and saturated and cis and epoch Chemistry lipogenesis with a trans-form acid addition location is the complex makes the various triglycerides to glycerol molecule attaches. If these fats are regularized, the glyceride coordination of certain natural products is much higher than others. In any case, there are combinations of glycerides in the fats for substances of overall unpredictable and unknown low boiling point and near eutectic melting point due to coordination and concentration, some of which are 90 ° and 80 ° And it may have a required hardness at 92 ° F and may also exhibit the required hard butter properties by melting even at a temperature of the degree of mouth of the human body. Separation from dense esters of good fats, not only with good hard butter properties but also as a substitute for cocoa butter (particularly with a composition containing fats and oils mixed with chocolate), is experimental and adventurous. It is particularly difficult to be a chocolate liquid mixed with fats and oils for milk chocolate production, or even the chocolate liquid itself to be satisfactorily mixed with a large amount of fat other than cocoa butter to become a fat having required strength and gloss.

Such cocoa butter content and replaceable fat are referred to in the present invention as replacement fat. The present invention has made a breakthrough discovery for such alternative fats.

Hard butters are widely used in confectionery and other food systems because they do not melt well at 50-70 ° F and melt extremely rapidly above this temperature, and they dissolve well at the body's temperature. to be. In practice, hard butters typically have a melting point of 90 ° -105 ° F and sometimes above 105 ° F (higher melting points above 103 ° F are generally regarded as poor cocoa butter substitutes). There is no smell, and the taste of hard butter is usually in the mouth. These fats should be brittle at temperatures up to about 75 ° F. This brittleness is sometimes called snap. At this temperature, the liquid must be maintained on the surface of the film without any liquid phenomena. When these hard butters are mixed with cocoa and sugar, coated and aged, the final product should be free from gloss changes. Often, this change in surface appearance is accelerated by alternating heating and cooling of the coated product several times.

One characteristic of the present invention is about 15-40 parts of cocoa butter, about 0-25 parts of fats and oils (in this case, the total amount of cocoa butter and fats is not more than about 40 parts), hard butter for confectionery. It is in the composition using about 60-85 parts.

Hard butter characteristics;

A) C ₁₆ - ₁₈ triglycerides is a minimum of 96% and a cis-coordination as will be approximately 20% of the acid to produce the unsaturated fat.

B) Solids Fat Index (SFI) is 78-85% at 50 ° F and 70 ° F, 70-80% at 80 ° F, 31-45% at 92 ° F, up to 3% at 100 ° F, and at 110 ° F. 0.

C) The Mettler Dropping Point (MDP>) should be about 36 ° to about 39 ° C.

Another feature of the present invention lies in the provision of such hard butters and, since the melting point is higher than that of cocoa butter, it is surprising that at least cocoa butter, especially cocoa butter and fats and oils, result in an excellent product.

A further feature of the present invention is that the lipogenic acid contains about 35-60% of unsaturated triglycerides in trans coordination and is substantially free of polyunsaturated triglycerides (i.e. up to about 5% by weight) and saturated triglycerides of about 35- Solid, which is a mixture of saturated and unsaturated triglycerides containing 45%, is continuously fractionated and crystallized from a solvent to give at least one solid-rich component rich in saturated triglycerides and a hard-buttered solid that has a small saturated triglyceride but has a trans coordination. It is an improvement on how to make ingredients. The improvement according to the present invention provides a solid component having a small saturated triglyceride as described above.

A) dissolved in a solvent to form a new solution,

B) fractional crystallization to crystallize about 75-95% of the solute fat from the fresh solution,

C) after the local crystals have been recovered

D) stripping the solvent from the recovered crystals.

Solid-state anti-water index (also known as SFI, or Solids Content Indux) is measured by the expansion method for the solid phase that coexists with the liquid phase of fat at a given temperature. Measured according to the Official Test Method cd 10-57. Fat experts are advised that SFI and METTLE dropping temperatures (which may be lower than the Wiley melting point, but much more reproducible) are available in the mid-range and ultimately in the complete melting of various commercial hard butters, especially transcoordinates. It will be noted that the acid producing unsaturated fats is higher than that of many hard butters and also high in comparison with the following cases. In other words,

A) for cocoa butter itself, or

B) It refers to the case where the milk solids are mixed with cocoa butter when they are cocoa butters of various levels.

Willie melting point measurement is based on AOCS Official Test Method Cc 2-38. Interestingly, the inventors have confirmed that these hard butters are structurally different from cocoa butters except that their chemical structure is similar, but this butter is mixed well with cocoa butter (especially with a mixture of cocoa butter and fats and oils). It should be somewhat hard. Otherwise, the resulting mixture is too soft to be considered as a substitute for fat. Therefore, in order to make a compound for the coating for candy, etc. by combining the chocolate liquid (in this case, the chocolate liquid has about 48% cocoa fiber and cocoa butter about 52%), and the chocolate liquid is a normal content of sucrose, lecithin, vanillin. And when mixed with fats from milk solids, this hard butter can be used as a complete replacement for the cocoa butter added to this mixture.

The use of these alternatives does not produce any apparent defects, nor does it affect the organoleptic quality or taste. Selective hydrogenation conditions, usually using molecular hydrogen sesame seeds, virtually eliminate all of the highly reactive polyethenic unsaturations in fats or fat mixtures (up to about 5% of unsaturated fats) while remaining unsaturated fatty acids. By eliminating a large portion of them, the trans content is high (eg 35-60% of the total weight of the combined acid).

As used herein, "elliidation" refers to the conversion of one or more olefinic double bonds of an acid-producing acid group into a trans coordination other than the cis coordination. This hydrogenation reaction temperature can range from about 250 ° F. to 460 ° F., which is generally advantageously started at 270 ° F. to 400-425 ° F.

The pressure required for this hydrogenation reaction is at least about 5 psig, typically in the range of about 5-80 psig, but may be in the range of about 5-60 psig. The hydrogenation time is usually about 2 hours or more, often 4-7 hours or more. In general, hydrogenation stops when the fat iodine value is about 50-70, usually around 50-60. The most effective catalysts known to the present inventors that can be used for such a hydrogenation reaction are hydrogenated catalysts supported by nicks previously used, for example, two to four times for the hydrogen reduction of fats. It is somewhat toxic due to previous use. These catalysts can also be mixed with the new Nickel-based fat hydrogenation catalysts, which use about 0.01-0.2% of Nickel for fat and generally around 0.07%. Other catalysts that can be used include a nickel sulfide catalyst and a catalyst according to US Patent Application No. 815,158 to John Hasman. Barium oxide-chromite copper in the latter case is used in the first step in hydrogenation. In the second step, a conventional Nickel catalyst is used.

As described above, basic materials that can be used to prepare hard butter include cottonseed oil having an iodine value of about 50-60 and having the following typical analyses, which are alkali purified and optionally hydrogenated.

Willie Melting Point (WMP), ℉ 111.0

METTLER LOADING TEMPERATURE, DEG C 43.8

(The above unsaturated acids are in the form or configuration of cis and trans)

Iodine 56.5

Transacid 41.7

(% Of total binder acid)

Free fatty acid,% 0.2

This base material dissolves a solvent such as 2-nitropropane as shown in Examples 1,2 and 3, and acetone can be used as a good solvent.

The solvent used for the purpose of the present invention is a solvent capable of dissolving at least 10 g of fat per 100 cc at a temperature of about 50 ° C. or lower, and this solvent is used to reduce the solution temperature with respect to fat, especially a saturated portion of the fat. Solubility is also reduced, almost completely from fat at 5-60 minutes under temperatures and times that do not cause significant lipolysis (e.g., extremely low absolute pressures (1 mmHg or less) and temperatures do not exceed about 500 ° F). Typical solvents having this property include neutral solvents, for example nitropropane, especially ketones such as 2-nitropropane, acetone and 2-butanol, and liquid lower paraffins such as hexane. Propane, acetamide, carbon tetrachloride, chloroform; benzene, dimethylformamide, tetrahydrofuran, dimethylsulfone, hexamethylphosphor There is such midfield.

Fractional crystallization of dissolved fats, as described in US Pat. No. 2,972,541, starts systematically with slowly decreasing the temperature of the solution and finally a high melting point crystal is obtained. The crystallization is usually done using a cooling vessel and indirectly cooling the solution and the resulting slurry using a refrigerant such as direct expansion ammonia. It is effective to use 6-10 parts of solvent for 1 part of solute fat.

When the temperature at which primary components with high saturated triglycerides appear, ie, the typical temperature reaches 59 ^° ± 2 ° F., the resulting slurry is filtered and the resulting cake is washed with a lower temperature solvent. Secondary crystals are taken from the mother liquor according to U.S. Pat.No. 2,972,541 (the mother liquor is usually diluted with primary cake wash liquor) and slowly cooled to 27 ^o ± 2 ° F at an average rate of about 1 ° F per minute. Get the tea crystals. This process is called "B component" or hard butter component and it is an excellent starting material used to prepare special hard butter according to the present invention. When various other fats or fat mixtures or displaced fats are used, the above-described elements are changed to some extent so that the raw material components suitable for the purpose of the present invention are produced. Similarly, various other fats will also require some hydrogenation. It is almost impossible to replace the hydrogenation reaction with an elliidation reaction by mixing fat mixtures or displaced fats in the correct proportion of unsaturated to acid producing saturated bound fats and other fats. In this example, the hydrogen does not need to be chemically bonded to the fat or the atmosphere is extremely degraded even if there is no molecular hydrogen or molecular hydrogen without departing from the concept of the present invention only if an optional hydrogenation catalyst is used. do.

METTLER DELTA TEMP MEASUREMENTS The METTLER DELTA electronic control FP5 unit is a METTLER heating furnace FP53 with a very gentle heating rate and a Willie melting point plate and other accessories. . The accessory contains at least one sample cup, which fits snugly in the cartridge and alternates in the sleeve. The sample cup has a bottom hole with a diameter of 2.8 mm and these cups fit into the hole in the Willie melting point plate. After melting the sample fat and cooling the cup in advance, the cup is dipped into the cup while being filled in the hole of the Willie measuring plate. At this time, the position of the measurement plate is in a dish containing dry ice (solid carbon dioxide). It is not necessary to flatten the top of the cup and allow at least 10 minutes to cool the sample. The temperature is set to 5 ° C below the expected melting point as the starting temperature in the furnace control unit, where the heating rate is programmed to 1 ° C per minute. When the temperature of the furnace matches the indicator on the control unit, use the top of the cartridge to remove the cooled drip cup from the dry ice dish and attach the drip catch sleeve. The device is inserted perpendicular to the furnace column and rotated to keep the cartridge in place. After 2 minutes at this stage, the cup is equilibrated with the minimum temperature of the furnace, which is then heated with the heating rate automatically adjusted. The dropping temperature is usually recorded in degrees Celsius using this device. The dropping temperature is close to the will melting point and much more reproducible. It also eliminates the subjectivity of the operator, which is inherent in Willie melting point measurements.

The prescription of a baker can be seen from the following examples. These examples illustrate, but do not limit, the present invention or methods in which the present invention can be practiced. The amounts added herein are all parts by weight but are percentages and temperatures are given in degrees Fahrenheit unless otherwise specified.

Used in this invention, "fatty acid" means the C ₁₂ - ₂₆ saturated fatty acid is. In addition, "an acid which produces other fats" means unsaturated fatty acids having the same chain length.

[Examples 1,2,3]

As a starting material, so-called "B" component is used, which is the result of systematic fractionation of selectively hydrogenated cottonseed oil with high trans content.

Analysis values of the starting material having a B component used in this Example are as follows.

In each of the above examples, 1 part of a hard butter starting material of component B is used. This material is dissolved using the respective parts (parts) of 2-nitropropane at 120 ° F. In each example, the solution is cooled to the corresponding final slurry temperature at an average rate of about 1 ° F. per minute. As the refrigerant to be used, liquid ethylene glycol is used on the double wall side of the heat exchanger. The cake produced by vacuum filtration of each slurry was disassembled using 175 parts of 2-nitropropane at about 24 ° F. and then re-filtered under vacuum. The resulting washing cake was stripped with 2-nitropropane and deodorized at 240 ° C. and 1 mmHg absolute pressure for 60 minutes using steam to produce a hard butter according to the present invention. These products contain 14-15% of the combined acid in the cis coordination, compared to 17% of light butter as starting material.

The amount of solvent used in Example 3 is much higher than in the two examples, but the separation effect is very large. But all the products are extremely satisfactory. The characteristics of each product are as follows.

Product of Example 1

Product of Example 2

Product of Example 3

A combination of the novel hard butters according to Example 3 is used to make several representative confectionery coatings, in which case the chocolate liquid, whole milk powder, the hard butter according to the present invention, sucrose, 0.05% vanilla flavor. , 0.1% salt and 1.2% lecithin are used. These coatings have the following lipid composition as a component of the total fat contained. Three fats (cocoa butter made from chocolate liquor, milk fat made from powdered milk and hard butter according to Example 3) and 1.2% lecithin as a percentage of these three fats were added to make up all the lipid composition of the coating. In this case, the coating amount should be about 32%, and broadly about 30-35%.

The hard butter used here is a substitute for all of the cocoa butter added to commonly used chocolate blends. All samples were sensory, hard and shiny, almost identical to similar combinations (except in this case no hard butter was used instead of cocoa butter). These products have good hardness and gloss, and have more sensory properties than other compositions. This is the case when using a hard butter or other widely used hard butter as a starting material. The analytical value and solid fat number of the starting material B component, that is, the hard butter component, are shown above, and the typical constants for these materials are as follows.

Solid Paper Prevention Water

Fractional crystallization similar to Examples 1, 2 and 3, but at actual plant scale, the ratio of solvent to starting fat is 10: 1 and the resulting slurry is cooled down to 20 ° F. The filter cake is washed without dismantling and is steam deodorized for 20 minutes at 475 ° F, 5 mmHg absolute. As a result of this treatment, the hard butter according to the present invention exhibited the following characteristics.

Solid Paper Prevention Water

The following are examples of basic formulations for chocolate flavored coatings, which can of course be altered to suit individual preferences or product needs. The hard butter to be used in the compounding example is the same as that in Example 3.

Dark sweet coating

Percentage (%)

Milk Coating

Percentage (%)

Light milk coatings

Percentage (%)

If special hard butter is used in the coating of confectionery, do as follows.

Processing

Coatings made using the special hard butter shown here are easier to process and handle than chocolate.

You don't have to be tempering or you can simplify it. If tempered hard butters are used, the apparatus and process are similar to those for chocolate coatings. The proper tempering (approximately 2% of seed crystals) is influenced by the formulation of the coating and the ratio of cocoa butter and fat to whole fat.

Typical titling temperature ranges are 94-97 ° F. If a non-tempered hard butter is used, the processing can be simplified and the cooling temperature of the coating should be 100-105 ° F. The functional properties of special hard butter coatings are determined by the amount of cocoa butter and fats and oils contained in the formulation of the coating and the processing conditions.

For best results, follow these processing guidelines.

(A) The total content of cocoa butter and fats derived from chocolate and whole milk powder, respectively, shall be in the range of 30-40% of the total fat in the coating.

(B) For combinations with more than 35% of cocoa butter and fats and oils, use fats from at least 10% to up to 20% of total fat.

(C) In some cases, the best sensory properties can be obtained by tempering.

Representative cocoa butter is as follows.

In addition, the representative analysis of the fat-producing acid is as follows.

None of the above is trans coordinating, and the official Willie melting point is 84-86 ° F. After the same tempering process as for chocolate coatings, the Willie Melting Point (WMP) is 89-93 ° F and METTLER Dropping Temperature is 33-35 ° C (93-95 ° F). Becomes These figures are indicative of the specificity of cocoa butter but are compared with data for hard butters according to the invention (which are higher at 92 ° F. and also higher for METTLER loading). Moreover, the hard butter according to the present invention has only 14-15% of the acid producing fat in the cis coordination (substantially no effect at 15% or more and no more than 20%).

On the other hand, the typical cocoa butter is about 38%, and the values for these acids presented in Kochran et al. Patent No. 2,972,541 are extremely low, but the upper limit is 40% and the lower limit is 15%. will be.

Example 4

As a starting material, so-called "B" component is used, which is produced by the systematic fractionation of selectively hydrogenated soybean oil with a high trans content. The analysis value of this "B" component is as follows.

This material is dissolved using about 10 parts of 120 ° F. 2-nitropropane and then the solution is cooled to a final slurry temperature of about 260 ° F. at an average cooling rate of about 1 ° F. per minute. As the refrigerant to be used, liquid ethylene glycol is used on the double wall side of the heat exchanger. The slurry produced by vacuum filtration of each slurry was dismantled using 175 parts of 2-nitropropane at about 24 ° F. and then filtered again under vacuum. The washing medium thus produced was stripped with 2-nitropropane and deodorized with steam at 240 ° C. and 1 mmHg at absolute pressure for 60 minutes to produce a hard butter according to the present invention. These products have 16-17% combined acid in the cis coordination, while about 18-19% for the starting hard butter. The yield is about 85-87% relative to the starting material.

SFI and other data for the hard butter according to the present invention are as follows.

Solid Paper Prevention Water

The hard butter according to the present invention is used for the coating of the refreshments as in Examples 1, 2 and 3, and is somewhat lower in blueness stability than the hard butter obtained in Examples 1, 2 and 3. Similar results may be obtained using safflower, palm, peanut, sunflower, rapeseed, corn, rice bran, sesame seeds, citrus seeds, liquid components of pig or other animal oils, fat from chicken, or oils thereof. You can get it. When saturated oils such as palm oil are used, these oils must be mixed with unsaturated oils such as cottonseed oil, soybean oil and corn oil before being selectively hydrogenated, with about 10-50 parts by weight of 50 parts unsaturated oil. It is preferable to mix palm oil.

Claims (1)

It uses mainly fats consisting of a mixture of saturated and unsaturated triglycerides of C ₁₆ -C ₁₈ fatty acids with other fatty acid, which contains about 35-60% of unsaturated triglycerides to which the fatty acid is transcoordinated and is substantially multiple. There is no unsaturated triglyceride, and about 35-45% of saturated triglyceride is a solid component rich in at least one saturated triglyceride and less saturated triglyceride from the solvent suitable for the fat, but the fatty acid is a solid component in trans coordination. In the hard butter manufacturing method of crystallization, a saturated solid solution containing less triglycerides is dissolved in a solvent to make a new solution, and fractionated crystallization of about 75% to 95% of the solute fat from the new solution is made into a crystal, and a fat crystal From the recovered crystals Method for producing a hard butter, characterized in that for stripping the solvent.