阅读说明：本技术 制备焦糖色素的方法、焦糖色素及其应用 (Method for preparing caramel pigment, caramel pigment and application thereof ) 是由 张美玲 张新峰 陈志锋 黄永志 于 2021-09-29 设计创作，主要内容包括：本发明属于食品添加剂领域,具体涉及一种制备焦糖色素的方法,包括：将糖溶液与酸性助剂混合,在0.03～0.5MPa条件下反应,反应温度高于100℃但不超过200℃,得到反应产物；将反应产物的pH值调至3.5～7.5,冷却,得到焦糖色素；本发明还涉及制得的焦糖色素及其应用。本发明方法制备的焦糖色素粘度高、树脂化时间长、稳定性好、货架寿命长。(The invention belongs to the field of food additives, and particularly relates to a method for preparing caramel pigment, which comprises the following steps: mixing the sugar solution with an acidic auxiliary agent, and reacting under the condition of 0.03-0.5 MPa, wherein the reaction temperature is higher than 100 ℃ but not higher than 200 ℃, so as to obtain a reaction product; adjusting the pH value of the reaction product to 3.5-7.5, and cooling to obtain caramel pigment; the invention also relates to the prepared caramel pigment and application thereof. The caramel pigment prepared by the method has high viscosity, long resinification time, good stability and long shelf life.)

1. A method of preparing a caramel color comprising the steps of:

(1) mixing the sugar solution with an acidic auxiliary agent, and reacting under the condition of 0.03-0.5 MPa, wherein the reaction temperature is higher than 100 ℃ but not higher than 200 ℃, so as to obtain a reaction product;

(2) adjusting the pH value of the reaction product to 3.5-7.5, and cooling to obtain caramel pigment;

wherein, the cooling program comprises the following nine stages in sequence:

the method comprises the following steps: reducing the reaction temperature to 96-100 ℃ at the speed of 0.2-0.8 ℃/min;

stage two: keeping the temperature at 96-100 ℃ for 5-15 minutes;

stage III: reducing the temperature from 96 ℃ to 100 ℃ to 86 ℃ to 94 ℃ at the speed of 0.2-0.8 ℃/min;

stage IV: keeping the temperature at 86-94 ℃ for 5-15 minutes;

stage five: reducing the temperature from 86-94 ℃ to 77-84 ℃ at the speed of 0.1-0.6 ℃/min;

stage (II): keeping the temperature at 77-84 ℃ for 5-15 minutes;

stage (c): reducing the temperature from 77-84 ℃ to 65-75 ℃ at the speed of 0.05-0.2 ℃/min;

stage (v): keeping the temperature at 65-75 ℃ for 5-15 minutes;

stage ninthly: quickly cooling from 65-75 deg.C to below 63 deg.C.

2. The method according to claim 1, wherein in the step (1), the reaction is carried out under the condition of 0.05-0.3 MPa.

3. The method according to claim 1 or 2, wherein in the step (1), the reaction lasts for 30 to 200 minutes.

4. The method according to any one of claims 1 to 3, wherein in the step (1), the reaction is carried out under stirring conditions, and the rotation speed of the stirring is 20-200 r/min.

5. The process according to any one of claims 1 to 4, wherein in step (2), the cooling is carried out under 0 MPa.

6. The method according to any one of claims 1 to 5, wherein, in the step (2), the pH value of the reaction product is adjusted with an alkaline reagent;

preferably, the alkaline reagent is selected from one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium bicarbonate, calcium hydroxide, sodium carbonate and potassium carbonate.

7. The method according to any one of claims 1 to 6, wherein in step (1), the weight of the acidic adjuvant is 0.1-1% of the weight of the solids in the sugar solution.

8. The method according to any one of claims 1 to 7, characterized by one or more of the following:

A. in the step (1), the sugar solution is selected from one or more aqueous solutions of corn syrup, sucrose, glucose, fructose, invert sugar, high fructose syrup, maltose syrup and starch hydrolysate;

B. in the step (1), the solid content of the sugar solution is 40-90% by weight;

C. in the step (1), the DE value of the sugar solution is 40-80%;

D. in the step (1), the acidic auxiliary agent is selected from one or more aqueous solutions of sulfuric acid, hydrochloric acid, nitric acid, citric acid, tartaric acid, lactic acid and acetic acid;

E. in the step (1), the concentration of the acid additive is 10-30 wt%;

F. in the step (2), cooling and filtering, and collecting filtrate to obtain caramel pigment;

G. the caramel pigment is a common caramel pigment.

9. A caramel color made by the process of any one of claims 1 to 8;

preferably, the viscosity of the caramel pigment is 10000-23000 cP measured at 25 ℃ by adopting a viscometer;

preferably, the resinification time of the caramel pigment is more than 22 hours.

10. Use of the caramel color of claim 9 in a food product.

Technical Field

The invention belongs to the field of food additives, and particularly relates to a method for preparing a caramel pigment, the prepared caramel pigment and application of the caramel pigment in food.

Background

Caramel Color (carame Color) is one of the oldest and most widely used food colors to enhance naturally occurring colors, correct natural changes in Color, and protect colors that may be lost by light degradation during food processing and storage. The caramel pigment has the characteristics of good water solubility, coloring capability, stability, safety and the like, so that the caramel pigment is the edible pigment which is most widely applied and has the largest output and sale quantity all over the world, and occupies more than 90 percent of the using amount of the edible pigment in developed countries in Europe and America and China.

Important parameters of caramel color include, but are not limited to, viscosity, hue index, resinification, density, alcohol solubility, salt stability, and beer testing. Wherein, the viscosity is an important parameter of the caramel color, generally reflects the quality and the shelf life of the caramel color, and directly influences the conveying, stirring, mixing and the like of the caramel color. In actual application, the quality of the caramel pigment product is influenced by too high or too low viscosity; the viscosity is too high, the pumping transportation is not facilitated, the resinification is easy, and the stability is poor; the liquid seasoning has low viscosity, slow resinification and long shelf life, but has a common effect of improving the body state and the wall-hanging property of the liquid seasoning. The caramel pigment prepared by the common method has the characteristics of high red-yellow pigment index, ruddy color, high safety and the like, is more in line with the consumption concept and environment of safety, greenness, nature and health, and is widely applied to alcohol, seasonings (particularly Asia markets) and baking industries. Caramel pigment is added into liquid seasonings such as sauce oil, so that the color is improved, the batch change is reduced, the color adhesion of meat and noodles is improved, and the product taste is improved, therefore, the common caramel pigment for soy sauce needs to keep higher viscosity and have higher stability, but the common caramel pigment of the type is not provided in the prior art.

Therefore, the demand for obtaining the common caramel pigment with high viscosity, good stability and long shelf life is high.

Disclosure of Invention

One of the purposes of the invention is to provide a method for preparing caramel pigment, wherein the prepared caramel pigment has high viscosity, long resinification time, good stability and long shelf life; the invention also aims to provide the caramel pigment and application thereof.

To achieve the above object, a first aspect of the present invention relates to a method for preparing caramel color, comprising the steps of:

(1) mixing the sugar solution with an acidic auxiliary agent, and reacting under the condition of 0.03-0.5 MPa at the reaction temperature of more than 100 ℃ but not more than 200 ℃ (preferably 110-180 ℃, such as 130 ℃, 150 ℃ and 180 ℃) to obtain a reaction product;

(2) adjusting the pH value of the reaction product to 3.5-7.5 (such as 4.0, 5.0, 6.0, 6.5, 7.0 and 7.2), and cooling to obtain caramel pigment;

wherein, the cooling program comprises the following nine stages in sequence:

the method comprises the following steps: reducing the reaction temperature to 96-100 ℃ (for example, 98 ℃ and 100 ℃) at the speed of 0.2-0.8 ℃/min (for example, 0.5 ℃/min and 0.6 ℃/min);

stage two: maintaining at 96-100 deg.C (such as 98 deg.C and 100 deg.C) for 5-15 min (such as 10 min);

stage III: reducing the temperature from 96-100 ℃ (e.g., 98 ℃, 100 ℃) to 86-94 ℃ (e.g., 88 ℃, 90 ℃, 92 ℃) at a rate of 0.2-0.8 ℃/min (e.g., 0.5 ℃/min, 0.6 ℃/min);

stage IV: maintaining at 86-94 deg.C (e.g. 88 deg.C, 90 deg.C, 92 deg.C) for 5-15 min (e.g. 10 min);

stage five: reducing the temperature from 86-94 ℃ (e.g., 88 ℃, 90 ℃, 92 ℃) to 77-84 ℃ (e.g., 78 ℃, 80 ℃, 82 ℃) at a rate of 0.1-0.6 ℃/min (e.g., 0.3 ℃/min, 0.4 ℃/min);

stage (II): maintaining at 77-84 deg.C (such as 78 deg.C, 80 deg.C, 82 deg.C) for 5-15 min (such as 10 min);

stage (c): reducing the temperature from 77-84 ℃ (e.g., 78 ℃, 80 ℃, 82 ℃) to 65-75 ℃ (e.g., 68 ℃, 70 ℃, 72 ℃) at a rate of 0.05-0.2 ℃/min (e.g., 0.1 ℃/min, 0.15 ℃/min);

stage (v): maintaining at 65-75 deg.C (such as 68 deg.C, 70 deg.C, 72 deg.C) for 5-15 min (such as 10 min);

stage ninthly: rapidly cooling from 65-75 deg.C (such as 68 deg.C, 70 deg.C, 72 deg.C) to below 63 deg.C (such as below 60 deg.C).

In any embodiment of the first aspect of the present invention, in the step (1), the reaction is performed under a pressure of 0.05 to 0.3MPa (preferably 0.05 to 0.2 MPa).

In any embodiment of the first aspect of the present invention, in the step (1), the reaction is continued for 30 to 200 minutes, preferably 30 to 180 minutes, for example, 80 minutes, 100 minutes, 150 minutes, 180 minutes.

In any embodiment of the first aspect of the present invention, in the step (1), the reaction is performed under stirring conditions, and the stirring speed is 20 to 200r/min, preferably 20 to 100r/min, such as 30r/min, 50r/min, and 70 r/min.

In any embodiment of the first aspect of the present invention, in step (2), the cooling is performed under 0 MPa.

In any embodiment of the first aspect of the present invention, in step (2), the pH of the reaction product is adjusted with an alkaline reagent.

In any embodiment of the first aspect of the present invention, the alkaline agent is selected from an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, calcium hydroxide, sodium carbonate and potassium carbonate.

In any embodiment of the first aspect of the present invention, in step (1), the weight of the acidic adjuvant is 0.1% to 1% of the weight of the solids in the sugar solution, for example, 0.2%, 0.22%, 0.248%, 0.25%, 0.37%, 0.5%, 0.561%, 0.7%.

In any embodiment of the first aspect of the present invention, in step (1), the sugar solution is selected from an aqueous solution of one or more of corn syrup, sucrose, glucose, fructose, invert sugar, high fructose syrup, maltose syrup, and starch hydrolysate.

In any embodiment of the first aspect of the present invention, in step (1), the sugar solution has a solid content of 40% to 90%, preferably 60% to 90%, for example 70% to 80% by weight.

In any embodiment of the first aspect of the present invention, in step (1), the DE value of the sugar solution is from 40% to 80%, for example from 50% to 70%.

In any embodiment of the first aspect of the present invention, in step (1), the acidic adjuvant is selected from an aqueous solution of one or more of sulfuric acid, hydrochloric acid, nitric acid, citric acid, tartaric acid, lactic acid and acetic acid.

In any embodiment of the first aspect of the present invention, in step (1), the concentration of the acidic adjuvant is 10 wt% to 30 wt%, for example 15 wt%, 20 wt%, 25 wt%.

In any embodiment of the first aspect of the present invention, in the step (2), the caramel pigment is obtained by cooling, filtering and collecting filtrate.

In any embodiment of the first aspect of the present invention, the caramel color is a plain caramel color.

In a second aspect, the invention relates to a caramel color produced by the method of the first aspect of the invention.

In any embodiment of the second aspect of the present invention, the viscosity of the caramel color is 10000 to 23000cP, preferably 10000 to 20000cP, and more preferably 12000 to 19000cP measured at 25 ℃ with a viscometer.

In any embodiment of the second aspect of the present invention, the time for resinating the caramel color is 22 hours or more, preferably 22 to 50 hours, and more preferably 22 to 40 hours or 25 to 40 hours.

In any embodiment of the second aspect of the present invention, the method for measuring the resinification time of the caramel color comprises: and a small amount of samples are sealed in a glass tube, the glass tube is placed in an oven at about 100 ℃ for starting timing, the oven temperature is kept at about 100 ℃ until the samples are observed to have no fluidity, and the timing is finished to obtain the resinification time.

A third aspect of the invention relates to the use of the caramel color of the second aspect of the invention in a food product.

In the present invention, unless otherwise specified, wherein:

the term "solids of the sugar solution" refers to the dry matter of the sugar solution after removal of water;

the term "invert sugar" refers to a mixture of glucose and fructose containing equivalent amounts of material obtained after the action of dilute acids or enzymes on sucrose;

the term "DE value" is an abbreviation for Dextrose Equivalent, and refers to the percentage of reducing sugars (in glucose) in the solids of the sugar solution;

the term "starch hydrolysate" refers to products after starch hydrolysis, such as sugar alcohols, dextrins, starch sugars and the like, wherein starch sugars include maltose, oligosaccharides and the like.

The invention has the following beneficial effects:

the caramel pigment prepared by the method has high viscosity, long resinification time, good stability and long shelf life, and realizes the controllable regulation of the rheological behavior of the caramel pigment.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which

FIG. 1 is a flow chart of the process for preparing caramel color of examples 1-3.

Detailed Description

Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying examples, in which some, but not all embodiments of the invention are shown. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

As shown in figure 1, a high-pressure reaction kettle with the volume of 25L is selected, 15kg of high fructose corn syrup with the DE value of 50-70% and the solid content of 70-80% by weight is metered into the reaction kettle and is stirred uniformly for standby; adding 28.68g of citric acid solution (2.48 per mill of the weight of solid matters in the raw material sugar) with the concentration of 30 wt% into a high-pressure reaction kettle, and stirring to prepare reaction liquid; the reaction solution was reacted under the following conditions: the reaction temperature is 130 ℃, the positive pressure is 0.05-0.20MPa, the reaction time is 180min, and the rotating speed of the stirrer is 50 r/min; after the reaction was completed, the pH of the reaction product was adjusted to 6.5 with 20 wt% aqueous sodium hydroxide solution, and then the temperature was reduced under 0MPa according to the following procedure:

firstly, reducing the reaction temperature from 130 ℃ to 100 ℃ at the cooling rate of 0.5 ℃/min;

② keeping the temperature at 100 ℃ for 10 minutes;

thirdly, reducing the temperature from 100 ℃ to 90 ℃ at the rate of 0.5 ℃/min;

fourthly, keeping the temperature at 90 ℃ for 10 minutes;

the temperature is reduced from 90 ℃ to 80 ℃ at the rate of 0.3 ℃/min;

sixthly, keeping the temperature at 80 ℃ for 10 minutes;

seventhly, reducing the temperature from 80 ℃ to 70 ℃ at the speed of 0.15 ℃/min;

maintaining at 70 deg.c for 10 min;

ninthly, quickly cooling from 70 ℃ to below 60 ℃;

and after the process is finished, filtering to obtain the common caramel pigment liquid product 1.

Example 2

As shown in figure 1, a high-pressure reaction kettle with the volume of 25L is selected, and the high fructose corn syrup with the 15kgDE value of 50-70% and the solid content of 70-80% by weight is metered into the reaction kettle and stirred uniformly for standby; adding 28.68g of citric acid solution (2.48 per mill of the weight of solid matters in the raw material sugar) with the concentration of 30 wt% into a high-pressure reaction kettle, and stirring to prepare reaction liquid; the reaction solution was reacted under the following conditions: the reaction temperature is 150 ℃, the positive pressure is 0.05-0.20MPa, the reaction time is 150min, and the rotating speed of the stirrer is 50 r/min; after the reaction is finished, adjusting the pH value of the reaction product to 7.2 by using a 20 wt% sodium hydroxide aqueous solution; then cooling under the condition of 0MPa according to the procedure in the embodiment 1, and filtering to obtain the common caramel pigment liquid product 2.

Example 3

As shown in figure 1, a high-pressure reaction kettle with the volume of 25L is selected, and the high fructose corn syrup with the 15kgDE value of 50-70% and the solid content of 70-80% by weight is metered into the reaction kettle and stirred uniformly for standby; adding 28.68g of citric acid solution (2.48 per mill of the weight of solid matters in the raw material sugar) with the concentration of 30 wt% into a high-pressure reaction kettle, and stirring to prepare reaction liquid; the reaction solution was reacted under the following conditions: the reaction temperature is 180 ℃, the positive pressure is 0.05-0.20MPa, the reaction time is 100min, and the rotating speed of the stirrer is 50 r/min; after the reaction is finished, adjusting the pH value of the reaction product to 4.0 by adopting a 20 wt% sodium hydroxide aqueous solution; then cooling under the condition of 0MPa according to the procedure in the embodiment 1, and filtering to obtain the common caramel pigment liquid product 3.

Comparative example 1 reaction No pressure, reaction temperature and time were not synergistically controlled

The reaction solution was prepared as in example 2; the reaction solution was reacted under the following conditions: the reaction temperature is 180 ℃, the pressure is 0MPa, the reaction time is 150min, and the rotating speed of the stirrer is 50 r/min; the operation after the reaction was completed was the same as in example 2 to obtain a liquid product A of a conventional caramel color.

Comparative example 2 the pH of the reaction product was not adjusted

Omitting the operation of adjusting the pH value after the reaction is finished, directly cooling the reaction product under the condition of 0MPa according to the procedure in the embodiment 1, and obtaining the common caramel pigment liquid product B by the rest operations in the same way as the embodiment 2.

Comparative example 3 No temperature reduction procedure

(1) Adjusting the pH value of the reaction product to 7.2, immediately cooling to below 60 ℃ under the condition of 0MPa, and performing the other operations in the same way as in the example 2 to obtain a liquid product C1 of the caramel pigment;

(2) and (3) adjusting the pH value of the reaction product to 7.2, slowly cooling to below 60 ℃ at the speed of 0.15-0.5 ℃/min, and obtaining the common caramel pigment liquid product C2 by the rest operations in the same way as the example 2.

Comparative example 4 pH adjustment after Cooling

The preparation and reaction process of the reaction solution are the same as those of example 2; after the reaction is finished, the temperature of the reaction product is reduced under the condition of 0MPa according to the procedure in the example 1, then the pH value of the reaction product is adjusted to 7.2 by adopting 20 wt% of sodium hydroxide aqueous solution, and a liquid product D of the caramel pigment is obtained after filtration.

Test example

Color ratio: measured according to the method specified in appendix A of GB1886.64-2015 national food safety Standard food additive caramel pigment;

viscosity: measuring with DV-ll + Pro model viscometer of BROOKFIELD, USA, at 25 deg.C;

density: measuring by adopting a density balance method;

resinification time: and a small amount of samples are sealed in a glass tube, the glass tube is placed in a high-temperature oven at about 100 ℃ for starting timing, the temperature of the oven is kept at about 100 ℃ until the samples are observed to have no fluidity, and the timing is finished to obtain the resinification time.

The measurement of the parameters of the liquid products of caramel color 1-3 and the liquid products of caramel color A-B, C1, C2 and D is carried out according to the above method, and the results are shown in Table 1. It is worth to be noted that the viscosity difference of different samples at different temperatures is large, and temperature control is needed during measurement.

TABLE 1

As can be seen from Table 1, the viscosity of the present caramel color product is greater than that of the conventional caramel color products B, C1, C2, D; compared with the common caramel pigment products B, C1, C2 and D, the common caramel pigment product has longer resinification time, better stability and longer shelf life; although the viscosity of the conventional caramel color product A is greater than the caramel color product of the present invention, the excessive viscosity results in too short a resinification time, poor stability, and short life of the conventional caramel color product A; in addition, the color ratio of the common caramel pigment product B is lower; therefore, the caramel pigment product of the common caramel has higher viscosity, longer resinification time, good stability and long shelf life.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.