Method for removing coumarin from natural perfume

Abstract

The invention provides a method for removing coumarin in natural perfume. The method comprises the following steps: dissolving the natural perfume by using a solvent, adding an alkaline substance to adjust the pH value, carrying out a heating reflux reaction, concentrating after the reaction, extracting a concentrate by using an organic solvent, and carrying out reduced pressure distillation on extract liquor to remove the organic solvent, thereby obtaining the coumarin-removed natural perfume. By adopting the method for removing the coumarin in the natural perfume, the coumarin in the natural perfume such as hierochloe odorata extract, sweet clover extract, grain rain grass extract, cassia oil, pyrola calliantha extract and fenugreek tincture can be effectively removed, the coumarin content of the obtained coumarin-removed natural perfume product is less than 0.5 mu g / g, and the safety and application range of the product are greatly improved. The preparation method is simple in operation process, low in cost and very suitable for industrial production.

Description

Technical Field

[0001] The invention relates to a process for removing coumarin from natural spices, belonging to the technical field of spice fine processing. Background Art

[0002] Grass extract, sweet osmanthus extract, guyu grass extract, cinnamon oil, deer tongue grass extract, black tonk bean tincture, etc. are all traditional tobacco fragrance raw materials, which have been widely used in the ingredients and flavoring of various tobacco products. These spices can inhibit the irritation of tobacco, improve the taste of tobacco, and enhance the aroma of tobacco. Their flavoring effect is very significant and is deeply loved by perfumers. In recent years, the use of these spices in the tobacco fragrance industry has dropped significantly, and some have even been banned. The reason is that these spices contain a common ingredient-coumarin.

[0003] Coumarin, also known as benzo-α-pyrone, is a bicyclic compound synthesized by a benzene ring and an oxygen heterocycle. Coumarin compounds are a class of aromatic compounds widely found in nature, distributed in many plants and spices, including higher plants such as Rutaceae, Asteraceae, Leguminosae, Thymelaeaceae, and Solanaceae. Coumarin can be divided into free coumarin (simple coumarin), furanocoumarin, pyranocoumarin, isocoumarin and other coumarins according to its structure. In the past, coumarin was widely used in food as a flavor additive because of its ability to fix and enhance aroma. With the continuous advancement of scientific and technological means, people have been increasingly studying the toxicity of coumarin. Studies have shown that coumarin substances can easily induce the production of oxygen free radicals in the body, damage the body, and produce moderate toxicity to the liver and kidneys, thereby endangering human health. Many countries, regions and relevant agencies have begun to regulate the content of coumarin in food. The U.S. Food and Drug Administration (FDA), the British Food Standards Committee, China, India and other organizations and countries have banned the direct addition of coumarin to various foods; the European Food Safety Authority (EFSA) stipulates that the limit in desserts, breakfast cereals and bread is 5-50 mg / kg; Australia stipulates that the limit of coumarin in alcoholic beverages is 10 mg / kg; the German Tobacco Law stipulates that coumarin is prohibited in tobacco products; China stipulates that coumarin shall not be added directly to tobacco products, and the detection limit of coumarin in tobacco flavors is 100 mg / kg.

[0004] The patent "A method for removing furanocoumarins from essential oils" (patent number: CN201310058217.3) discloses a method for removing furanocoumarins from essential oils. The method is to contact the furanocoumarin-containing essential oil with a DNA-solid phase support under UVA band ultraviolet light. Under the action of gravity and pump pressure, the furanocoumarin-containing essential oil passes through the DNA-solid phase support, and the furanocoumarins are captured on the DNA-solid phase support to obtain the essential oil with furanocoumarins removed. The method used in this patent requires the use of a DNA-solid phase support. The preparation and purification of the DNA-solid phase support itself is a very complex technology, the process is cumbersome, and the preparation cost is also high. In addition, this technology cannot achieve the separation of coumarins in non-essential oil products.

[0005] At present, there is no literature report on the removal of coumarin from natural spices such as cyperus rotundus extract, sweet osmanthus extract, cyperus rotundus extract, cinnamon oil, leontopodium glutamate extract, and black tonka bean tincture in China. The spice industry has not yet found a removal method that meets industrial production and has economic application value. How to economically and effectively remove coumarin from these natural spices to improve their safety and expand their application range has become an issue that needs to be solved urgently. Summary of the invention

[0006] Aiming at the current situation that there is no method for separating coumarin from natural spices such as cyperus rotundus extract, sweet osmanthus extract, cyperus rotundus extract, cinnamon oil, leontopodium glutamate extract and tonka bean tincture in China, the present invention provides a method for industrially removing coumarin from natural spices.

[0007] The technical scheme adopted by the present invention is a method for removing coumarin from natural spices, specifically, the spices are first dissolved by a solvent, an alkaline substance is added to the dissolved solution to adjust the pH value to a certain range, and then the solution is placed in a heating reflux device for heating and reflux, and the addition of reflux is stopped after a certain period of time, and the solution is transferred to a concentrator for concentration, and a part of the solvent is removed to obtain a concentrate, and then the concentrate is extracted with an organic solvent, and the extract is concentrated to remove the solvent to obtain a natural spice without coumarin. The coumarin content of the finally obtained spice product is less than 0.5 μg / g.

[0008] The specific steps of this method are as follows: (1) mixing a natural flavor containing coumarin with a solvent in a certain proportion, and mechanically stirring to dissolve the mixture to obtain a solution; (2) adding an alkaline substance to the solution obtained in step (1) to adjust the pH value to a certain range; (3) placing the solution after pH adjustment in step (2) in a heating reflux device and heating and refluxing for a certain period of time; (4) transferring the solution after the heating and reflux reaction in step (3) into a vacuum concentrator to remove part of the solvent and obtain a concentrate; (5) extracting the concentrate obtained in step (4) with a certain amount of organic solvent, and concentrating the extract under reduced pressure until there is no solvent, thereby obtaining the final product: natural flavoring except coumarin.

[0009] In step (1), the solvent is water to 70% ethanol solution; the mass ratio of natural flavor to solvent is 1:1 to 1:5; In step (2), the alkaline substance is one or a combination of potassium hydroxide, sodium carbonate, sodium bicarbonate, and sodium hydroxide; The pH value in step (2) is in the range of 10 to 12; The heating reflux reaction time in step (3) is 3 to 10 hours; In step (5), the organic solvent is one or a combination of 95% ethanol, ethyl acetate, petroleum ether, and n-hexane; The mass ratio of the organic solvent in step (5) to the concentrate obtained in step (4) is 2:1 to 10:1 The method for removing coumarin from natural spices of the present invention can effectively remove coumarin from natural spices such as cyperus rotundus extract, sweet clover extract, cyperus rotundus extract, cinnamon oil, leontopodium glutamate extract, and tonka bean tincture, thereby obtaining natural spices without coumarin. The method of the present invention has simple process and low cost, and is very suitable for industrial production. The coumarin content in the final product is less than <0.5 μg / g, and the safety and application range are greatly improved. Implementation

[0010] The following examples are provided to further describe the present invention. Example

[0011] (1) mixing the herba spatholobi extract with a 20% ethanol solution in a mass ratio of 1:2, and mechanically stirring to uniformly dissolve; (2) adding sodium carbonate and potassium hydroxide to the solution obtained in step (1) in a mass ratio of sodium carbonate / potassium hydroxide = 2 / 1, and adjusting the pH value to 10; (3) placing the solution after pH adjustment in step (2) in a heating reflux device and heating under reflux for 10 hours; (4) transferring the solution after the heating and reflux reaction in step (3) into a vacuum concentrator to remove part of the solvent and obtain a concentrate; (5) extracting the concentrate obtained in step (4) with ethyl acetate, wherein the mass ratio of ethyl acetate to concentrate is 3:1, and concentrating the extract under reduced pressure until there is no solvent, thereby obtaining the final product: coumarin-free hyssop extract. Example

[0012] (1) mixing the extract of Cyperus rotundus with a 50% ethanol solution in a mass ratio of 1:3, and mechanically stirring to dissolve the mixture uniformly; (2) adding sodium bicarbonate, sodium hydroxide and sodium carbonate to the solution obtained in step (1) in a mass ratio of sodium bicarbonate / sodium hydroxide / sodium carbonate = 1 / 1 / 1, and adjusting the pH value to 11; (3) placing the solution after pH adjustment in step (2) in a heating reflux device and heating under reflux for 4 hours; (4) transferring the solution after the heating and reflux reaction in step (3) into a vacuum concentrator to remove part of the solvent and obtain a concentrate; (5) extracting the concentrate obtained in step (4) with a mixed solvent of ethyl acetate and 95% ethanol, wherein the mass ratio of ethyl acetate to 95% ethanol is 1:2, and the mass ratio of the mixed solvent to the concentrate is 5:1, and concentrating the extract under reduced pressure until there is no solvent, thereby obtaining the final product: coumarin-free cyperus rotundus extract. Example

[0013] (1) Mixing black tomatillo tincture with 70% ethanol solution in a mass ratio of 1:1, and mechanically stirring to dissolve evenly; (2) adding potassium hydroxide to the solution obtained in step (1) to adjust the pH value to 12; (3) placing the solution after pH adjustment in step (2) in a heating reflux device and heating under reflux for 3 hours; (4) transferring the solution after the heating and reflux reaction in step (3) into a vacuum concentrator to remove part of the solvent and obtain a concentrate; (5) extracting the concentrate obtained in step (4) with 95% ethanol, and concentrating the extract under reduced pressure until there is no solvent, thereby obtaining the final product: coumarin-free black tonkotsu tincture.

[0014] Table 1. Content and recovery of coumarin in spice samples

[0015] As can be seen from Table 1 above, no coumarin was detected in the treated flavors and spices, indicating that Examples 1 to 3 can effectively remove coumarin in the spices.

Claims

1. A method for removing coumarin from natural spices, Features: (1) mixing a natural flavor containing coumarin with a solvent in a certain proportion, and mechanically stirring to dissolve the mixture to obtain a solution; (2) adding an alkaline substance to the solution obtained in step (1) to adjust the pH value to a certain range; (3) placing the solution after pH adjustment in step (2) in a heating reflux device, and heating and refluxing for a certain period of time; (4) transferring the solution after the heating and reflux reaction in step (3) into a vacuum concentrator for concentration, removing part of the solvent, and obtaining a concentrate; (5) extracting the concentrate obtained in step (4) with a certain amount of organic solvent, and concentrating the extract under reduced pressure until there is no solvent, thereby obtaining the final product: natural flavoring except coumarin.

2. The method for removing coumarin from natural spices according to claim 1, Features: The natural coumarin-containing spices in step (1) include cyperus rotundus extract, sweet osmanthus extract, cyperus rotundus extract, cinnamon oil, leontopodium glutamate extract, tonka bean tincture and other similar natural coumarin-containing spices. In step (1), the solvent is water to 70% ethanol solution; the mass ratio of natural flavor to solvent is 1:1 to 1:

5.

3. The method for removing coumarin from natural spices according to claim 1, Features: In step (2), the alkaline substance is one or a combination of potassium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide. The pH value range in step (2) is 10 to 12.

4. The method for removing coumarin from natural spices according to claim 1, Features: The heating reflux reaction time in step (3) is 3 to 10 hours.

5. The method for removing coumarin from natural spices according to claim 1, Features: The organic solvent in step (5) is one or a combination of 95% ethanol, ethyl acetate, petroleum ether, and n-hexane.

6. The method for removing coumarin from natural spices according to claim 1, Features: The mass ratio of the organic solvent in step (5) to the concentrate obtained in step (4) is 2:1 to 10:1.

Images