High-quality peach aldehyde composition as well as preparation method and application thereof

Abstract

The invention discloses a high-quality peach aldehyde composition as well as a preparation method and application thereof. The composition comprises peach aldehyde, n-caprylic alcohol, a component A and a component B, the content of the peach aldehyde is greater than or equal to 99 wt%, the content of the n-caprylic alcohol is less than or equal to 800 ppm, the content of the component A is 2000-3000 ppm, and the content of the component B is less than or equal to 100 ppm, based on the total mass of the high-quality peach aldehyde composition. The composition has rich and stable fragrance, and a conventional fragrance retreatment step in the industry is not needed. The odor of the peach aldehyde is stabilized by limiting the impurity content, the problem that the odor of peach aldehyde products in the market is not uniform is solved, and more convenience is provided for application of downstream formula products.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a high-quality peach aldehyde composition and a preparation method and application thereof. Background Art

[0002] Peach aldehyde, also known as γ-undecalactone, is a colorless, viscous, transparent liquid with the aroma of peach and almond. It is a component of floral flavors such as lilac and osmanthus, fantasy flavors, and fruit flavors such as peach, cherry, and straw.

[0003] The current method for synthesizing peach aldehyde includes using ω-undecenoic acid as a raw material to obtain γ-undecalactone through esterification, isomerization, and lactonization reactions; however, the disadvantages of this method are low reaction yield, difficulty in obtaining raw materials, and difficulty in industrialization.

[0004] Patent CN112275234A discloses a peach aldehyde production system and production method. First, n-octanol, acrylic acid, and di-tert-butyl peroxide are uniformly mixed in a raw material tank in proportion, n-octanol and catalyst boric acid are pre-added in a reactor, and the raw materials are added dropwise after heating to 140-180°C for 6-12 hours. After the addition is completed, the reaction is continued for 1-2 hours. During the addition, protective gas needs to be introduced to reduce the raw material addition temperature to reduce the occurrence of side reactions. This method is intermittently operated and the addition of boric acid causes the product to have an impure odor.

[0005] Patent CN103030614A discloses a method for extracting synthetic peach aldehyde, which comprises premixing octanol, acrylic acid and peroxide, adding octanol and a catalyst into a reactor, heating the mixture to 140-190°C and then dripping the premix into the reactor within 4-10 hours. After the reaction is completed, pure peach aldehyde is obtained through distillation, and the yield of peach aldehyde is 73%. The pure peach aldehyde needs to undergo a special aroma treatment for 1-6 hours. This method has the disadvantages of long reaction time, complicated intermittent operation, low yield and long post-processing time.

[0006] Peach aldehyde, as a flavor and fragrance, is mainly used in daily products such as perfumes, toiletries, beverages, and feed, which puts higher requirements on the stability of aroma quality. The current industry's peach aldehyde production technology is relatively mature, but the odors of products from different manufacturers or different batches of the same manufacturer on the market are uneven. Peach aldehydes of the same purity have different tastes, which may be strong or weak, or mixed with some peculiar smells. Current peach aldehyde research focuses on purity and yield, and there has been no research report on the odor stability of peach aldehyde. Summary of the invention

[0007] In view of the above problems existing in the prior art, the object of the present invention is to provide a high-quality peach aldehyde composition having a strong and stable aroma without the need for conventional aroma reprocessing steps in the industry.

[0008] The present invention also aims to provide a method for preparing the above-mentioned high-quality peach aldehyde composition, by adjusting the synthesis process and the separation method to limit the impurity content to stabilize the peach aldehyde odor, thereby obtaining a peach aldehyde composition with excellent quality, solving the problem of uneven odor of peach aldehyde products on the market, and providing more convenience for the application of downstream formulated products.

[0009] The present invention also provides the use of the high-quality peach aldehyde composition as flavors and fragrances, feed additives, and daily chemical additives.

[0010] To achieve the above object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a high-quality peach aldehyde composition, the composition comprising peach aldehyde, n-octanol, component A, and component B;

[0012]

[0013] Wherein, the peach aldehyde content is ≥99wt%, for example, 99wt%, 99.2wt%, 99.4wt%, 99.6wt%, 99.8wt%, the n-octanol content is ≤800ppm, for example, 800ppm, 700ppm, 600ppm, 500ppm, 400ppm, 300ppm, 200ppm, 100ppm, 10ppm, 0ppm, component A content is 2000-3000ppm, for example, 2000ppm, 2100ppm, 2200ppm, 2300ppm, 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, component B content is ≤100ppm, for example, 100ppm, 90ppm, 80ppm, 70ppm, 60ppm, 50ppm, 40ppm, 30ppm, 20ppm, 10ppm, 0ppm, based on the total mass of the high-quality peach aldehyde composition.

[0014] In the high-quality peach aldehyde composition of the present invention, the aroma is mainly provided by peach aldehyde, but the inventor unexpectedly discovered during the research process that there are three other important components that play a key synergistic and antagonistic role, the three components are n-octanol, component A, and component B;

[0015] Structural characterization of component A, NMR data: H 1 NMR (400 Hz CDCl 3 )δ0.88-0.96(6H,t),1.25(4H,m),1.29-1.31(4H,m),1.53(2H,m),2.26(1H,m),2.38(2H,d),4.28(1H,m);

[0016] Structural characterization of component B, NMR data: H 1 NMR (400 Hz CDCl 3 )δ0.88(3H,t),

[0017] 1.25(4H,m),1.29(6H,m),1.31(2H,m),1.44(2H,m),2.54(1H,m),

[0018] 2.29 (2H, d), 3.7 (3H, s);

[0019] Among them, n-octanol is a spice with a lower threshold value. When its content in the peach aldehyde composition exceeds 800ppm, the product will produce a plastic taste, affecting the quality of peach aldehyde; component A is an isomer of peach aldehyde, with a milky flavor. When its content is controlled at 2000-3000ppm, it will make the peach aldehyde fragrance more intense, play an auxiliary role in enhancing the fragrance, and have the effect of stabilizing the fragrance of the product; component B is a reaction intermediate of peach aldehyde, containing a sour and rotten taste. When its content exceeds 100ppm, it will affect the aroma quality of peach aldehyde and make its taste sour. The present invention is based on this discovery, and by controlling n-octanol and components A and B within a specific content range, a high-quality peach aldehyde composition can be obtained, and the composition has an improved fragrance and good stability.

[0020] In the second aspect, the present invention provides a method for preparing the above-mentioned high-quality peach aldehyde composition. It should be understood by those skilled in the art that the following preparation method is only an exemplary description of the source mode of the peach aldehyde composition product with the above-mentioned characteristics of the present invention, but does not constitute any limitation. The peach aldehyde composition of the present invention is also not limited to the preparation method listed below, for example, based on the existing peach aldehyde product, by directly adding or adopting a conventional separation and purification method, the content of n-octanol and components A and B in the peach aldehyde composition is regulated to within a certain range.

[0021] The present invention exemplarily provides a method for preparing the high-quality peach aldehyde composition, which uses n-octanol and methyl acrylate as raw materials, initiates a reaction with di-tert-butyl peroxide, and obtains a peach aldehyde reaction solution, and the reaction formula is as follows:

[0022]

[0023] The reaction liquid is then subjected to conventional post-treatment operations such as flash evaporation and distillation to adjust the contents of n-octanol and component A and component B, thereby obtaining a high-quality peach aldehyde product with a strong and stable aroma.

[0024] In a preferred embodiment, a method for preparing a high-quality peach aldehyde composition comprises the following steps:

[0025] S1: using n-octanol and methyl acrylate as raw materials, initiated by di-tert-butyl peroxide, reacting at a certain temperature to obtain peach aldehyde reaction liquid;

[0026] S2: the peach aldehyde reaction liquid is subjected to a flash evaporator to remove n-octanol, and the flash evaporation process controls the content of n-octanol in the reaction liquid to be reduced to 1000-30000ppm, for example, 1000ppm, 5000ppm, 10000ppm, 15000ppm, 20000ppm, 25000ppm, 30000ppm;

[0027] S3: then removing light components through a first distillation tower, wherein the first distillation process controls the content of n-octanol in the reaction solution to not exceed 800 ppm, for example, 800 ppm, 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 10 ppm, or 0 ppm;

[0028] S4: The heavy components are removed by the second distillation tower, and the content of component A in the reaction solution is controlled to be reduced to 2000-3000ppm, for example, 2000ppm, 2100ppm, 2200ppm, 2300ppm, 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, and the content of component B is no more than 100ppm, for example, 100ppm, 90ppm, 80ppm, 70ppm, 60ppm, 50ppm, 40ppm, 30ppm, 20ppm, 10ppm, 0ppm, to obtain a high quality peach aldehyde composition.

[0029] In the present invention, there is no particular limitation on the reaction conditions involved in step S1, and technicians can screen them according to existing published methods as needed. For example, the molar ratio of n-octanol to methyl acrylate is 3-12:1, such as 3:1, 5:1, 7:1, 9:1, 12:1, preferably 5-10:1; the mass ratio of methyl acrylate to di-tert-butyl peroxide is 10-20:1, such as 10:1, 13:1, 15:1, 17:1, 20:1, preferably 10-15:1, such as 10:1, 12:1, 14:1, 15:1; the reaction temperature is 50-200°C, such as 50°C, 100°C, 150°C, 200°C, and the reaction time is 2-10h, such as 2h, 4h, 6h, 8h, 10h.

[0030] In the present invention, the flash kettle in step S2 has a flash temperature of 50-150°C, for example, 50°C, 80°C, 110°C, 150°C, preferably 60-110°C, an operating vacuum of 1-10KPa, for example, 1KPa, 3KPa, 5KPa, 7KPa, 10KPa, preferably 5-10KPa, and a kettle residence time of 5-60min, for example, 5min, 20min, 40min, 60min.

[0031] In the present invention, the separation conditions of the first distillation tower in step S3 are: the operating vacuum degree is 0.1-5KPa, for example, 0.1KPa, 0.5KPa, 1KPa, 3KPa, 5KPa, the tower bottom operating temperature is 50-150°C, for example, 50°C, 80°C, 110°C, 150°C, the tower bottom residence time is 5-30min, for example, 5min, 10min, 20min, 30min, the tower top reflux ratio is 1-5:1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, the number of tower plates is 10-50, for example, 10, 20, 30, 40, 50, and the tower is fed;

[0032] Preferably, the key point of controlling the content of n-octanol is that in the operation of removing light components in the first distillation tower, the separation conditions are strictly controlled, preferably the operating vacuum degree is 1-4 KPa, the tower bottom operating temperature is 60-100° C., the tower bottom residence time is 5-20 min, the tower top reflux ratio is 1-5:1, and the number of tower plates is 10-45.

[0033] In the present invention, the separation conditions of the second distillation tower in step S4 are: the operating vacuum degree is 0.01-5KPa, for example, 0.01KPa, 0.1KPa, 1KPa, 3KPa, 5KPa, the operating temperature of the tower bottom is 100-180°C, for example, 100°C, 130°C, 160°C, 180°C, the time is 1-20min, for example, 1min, 5min, 10min, 15min, 20min, the top reflux ratio is 0.1-3:1, for example, 0.1:1, 1:1, 2:1, 3:1, the number of plates is 10-50, for example, 10, 20, 30, 40, 50, and the feed is in the tower;

[0034] Preferably, the key point of controlling the content of component A and component B is that in the operation of removing the heavy components in the second distillation tower, the separation conditions are strictly controlled, preferably the operating vacuum degree is 0.01-3KPa, the tower bottom operating temperature is 120-180°C, the time is 1-15min, the top reflux ratio is 0.1-2:1, and the number of tower plates is 20-50.

[0035] As a preferred solution, the key point of controlling the content of component A and component B is that the temperature is gradually increased during the reaction of step S1, specifically, the preformulation of n-octanol, di-tert-butyl peroxide and methyl acrylate is first added dropwise at 50-80°C, such as 50°C, 60°C, 70°C, and 80°C, and the addition time is 1-4h, such as 1h, 2h, 3h, and 4h, and then the temperature is increased to 100-200°C, such as 100°C, 130°C, 160°C, 180°C, and 200°C at a rate of 0.5-5°C / min, such as 0.5°C / min, 1°C / min, 2°C / min, 3°C / min, 4°C / min, and 5°C / min, and the temperature is kept for 1-3h, such as 1h, 2h, and 3h. During the gradient temperature increase, part of the peach aldehyde intermediate of component B will be converted into the peach aldehyde isomer of component A. If the temperature is increased too quickly, the content of component A will be too low;

[0036] Preferably, the n-octanol is added in two parts. Specifically, one part is added as a base before the reaction, and the remaining part is mixed with di-tert-butyl peroxide and methyl acrylate as a pre-formulated material. The mass ratio of the two parts is 1:0.1-1, for example, 1:0.1, 1:0.3, 1:0.6, 1:0.8, 1:1.

[0037] In a third aspect, the present invention provides a use of the above-mentioned high-quality peach aldehyde composition, wherein the high-quality peach aldehyde composition is suitable for the fields of flavors and fragrances, feed additives, and daily chemical additives, and is particularly suitable for the fields of feed and daily chemical products.

[0038] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0039] (1) The present invention limits the content of peach aldehyde to ≥99%, the content of n-octanol to ≤800ppm, the content of isomers of peach aldehyde in component A to 2000-3000ppm, and the content of peach aldehyde reaction intermediates in component B to ≤100ppm, so that the product has a strong and stable aroma, does not require the conventional aroma reprocessing steps in the industry, simplifies the process flow, has low cost, and has a high yield.

[0040] (2) The present invention studies the odor of impurities, identifies the components that have a greater impact on the odor of peach aldehyde, and limits their content in the peach aldehyde product, thereby stabilizing the odor of the product and solving the pain point of the uneven odor of peach aldehyde products on the market, thereby providing convenience for the application of downstream flavor and fragrance formula products. DETAILED DESCRIPTION

[0041] The present invention is further described below in conjunction with specific examples. These examples are only for illustrating the present invention and are not to be construed as limiting the scope of the present invention or the method for implementing the present invention.

[0042] The sources of the main raw materials in the examples and comparative examples of the present invention are as follows. Other sources are obtained from common commercial channels unless otherwise specified:

[0043] n-Octanol: Corning, Thailand;

[0044] Di-tert-butyl peroxide: Aladdin Reagent Company;

[0045] Methyl acrylate: Yantai Wanhua.

[0046] The performance test parameters and corresponding test methods used in various embodiments of the present invention are as follows:

[0047] Aroma: sensory evaluation by experienced perfumers;

[0048] The purity of the product was detected by gas chromatograph, and the specific analysis conditions were as follows: instrument: Agilent gas chromatograph 8890, chromatographic column: Agilent DB-5, column box temperature: 80°C; inlet temperature: 300°C; detector temperature: 310°C; split ratio 10:1; carrier gas flow rate: 1mL / min; heating program: maintain at 80°C for 0 min, increase to 200°C at a rate of 8°C / min, maintain for 5 min, continue to increase to 300°C at a rate of 30°C / min, and maintain for 7 min.

[0049] Example 1

[0050] The steps of preparing a high-quality peach aldehyde composition are as follows:

[0051] S1: Add 700g (5.385mol) of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 80g (0.615mol) of n-octanol, 8g of di-tert-butyl peroxide, and 86g (1.024mol) of methyl acrylate to a mixing bottle in order to obtain a pre-formulated material. When the internal temperature reaches 60°C, the pre-formulated material is pumped into the three-necked flask with a peristaltic pump, and the mixture is added dropwise for 3h. After the addition is completed, the temperature is raised to 140°C at a rate of 1°C / min, and the mixture is reacted for 2h to obtain a peach aldehyde reaction solution.

[0052] S2: The peach aldehyde reaction liquid enters the flash kettle, at 100°C, vacuum degree 10KPa, to remove n-octanol, the residence time is 20min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 15000ppm.

[0053] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 4KPa, tower bottom temperature 90℃, reflux ratio 2:1, tower plate number 40, residence time 20min, control the content of n-octanol in the reaction liquid to reduce to 650ppm.

[0054] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 0.5 KPa, the tower bottom temperature is 120 ° C, the reflux ratio is 2: 1, the number of plates is 45, the residence time is 15 min, and the content of component A in the reaction liquid is controlled to be reduced to 2350ppm, and the content of component B is reduced to 80ppm. A high-quality peach aldehyde product composition is obtained from the top of the tower, which has a pleasant smell rich in fruity peach flavor.

[0055] Gas phase analysis results: based on methyl acrylate, peach aldehyde content is 99.3wt%, n-octanol content is 650ppm, component A content is 2350ppm, component B content is 80ppm; the total yield is 74%.

[0056] Example 2

[0057] The steps of preparing a high-quality peach aldehyde composition are as follows:

[0058] S1: Add 700g (5.385mol) of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 100g (0.769mol) of n-octanol, 10g of di-tert-butyl peroxide, and 86g (1.024mol) of methyl acrylate to a mixing bottle in sequence to obtain a pre-mixed material. When the internal temperature reaches 80°C, the pre-mixed material is pumped into the three-necked flask with a peristaltic pump, and the mixture is added dropwise for 2h. After the addition is completed, the temperature is raised to 130°C at a rate of 0.5°C / min, and the mixture is reacted for 2h to obtain a peach aldehyde reaction solution.

[0059] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 8KPa, to remove n-octanol, the residence time is 18min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 14000ppm.

[0060] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 3KPa, tower bottom temperature 100℃, reflux ratio 3:1, tower plate number 40, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 500ppm.

[0061] S4: After the light removal is completed, the product enters the second distillation tower for heavy removal, the feed is in the tower, the vacuum degree is 1KPa, the temperature of the tower bottom is 140°C, the reflux ratio is 0.5:1, the number of plates is 50, the residence time is 13min, and the content of component A in the reaction liquid is controlled to be reduced to 2050ppm and the content of component B is reduced to 70ppm. A high-quality peach aldehyde product composition is obtained from the top of the tower, which has a pleasant smell rich in fruity peach flavor.

[0062] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99.0wt%, n-octanol content is 500ppm, component A content is 2050ppm, and component B content is 70ppm; the total yield is 72%.

[0063] Example 3

[0064] The steps of preparing a high-quality peach aldehyde composition are as follows:

[0065] S1: Add 600g (4.615mol) of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 180g (1.385mol) of n-octanol, 10g of di-tert-butyl peroxide, and 86g (1.024mol) of methyl acrylate to a mixing bottle in sequence to obtain a pre-mixed material. When the internal temperature reaches 100°C, the pre-mixed material is pumped into the three-necked flask with a peristaltic pump, and the mixture is added dropwise for 2h. After the addition is completed, the temperature is raised to 120°C at a rate of 0.1°C / min, and the mixture is reacted for 2h to obtain a peach aldehyde reaction solution.

[0066] S2: The peach aldehyde reaction liquid enters the flash kettle, at 100°C, vacuum degree 10KPa, to remove n-octanol, the residence time is 30min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 16000ppm.

[0067] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 0.5KPa, tower bottom temperature 110℃, reflux ratio 1:1, tower plate number 30, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 450ppm.

[0068] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 0.1KPa, the tower bottom temperature is 130°C, the reflux ratio is 1:1, the number of tower plates is 40, the residence time is 10min, and the content of component A in the reaction liquid is controlled to be reduced to 2000ppm and the content of component B is reduced to 70ppm. A high-quality peach aldehyde product composition is obtained from the top of the tower, which has a pleasant smell rich in fruity peach flavor.

[0069] Gas phase analysis results: based on methyl acrylate, peach aldehyde content is 99.1wt%, n-octanol content is 450ppm, component A content is 2000ppm, component B content is 70ppm; the total yield is 68%.

[0070] Example 4

[0071] The steps of preparing a high-quality peach aldehyde composition are as follows:

[0072] S1: Add 6000g (53.85mol) of n-octanol to a 50L glass reactor with a condenser and a water separator to lay the bottom, and add 1000g (7.69mol) of n-octanol, 90g of di-tert-butyl peroxide, and 860g (10.24mol) of methyl acrylate to a mixing bottle in sequence to obtain a pre-formulated material. When the internal temperature reaches 110°C, the pre-formulated material is pumped into a three-necked flask with a peristaltic pump, and the mixture is added dropwise for 4h. After the addition is completed, the temperature is raised to 150°C at a rate of 1°C / min, and the mixture is reacted for 1.5h to obtain a peach aldehyde reaction solution.

[0073] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 6KPa, to remove n-octanol, the residence time is 30min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 18000ppm.

[0074] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 2KPa, tower bottom temperature 100℃, reflux ratio 1:1, tower plate number 45, residence time 10min, control the content of n-octanol in the reaction liquid to reduce to 250ppm.

[0075] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 0.01KPa, the tower bottom temperature is 140°C, the reflux ratio is 3:1, the number of tower plates is 50, the residence time is 11min, and the content of component A in the reaction liquid is controlled to be reduced to 2800ppm and the content of component B is reduced to 20ppm. A high-quality peach aldehyde product composition is obtained from the top of the tower, which has a pleasant smell rich in fruity peach flavor.

[0076] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99.4wt%, n-octanol content is 250ppm, component A content is 2800ppm, and component B content is 20ppm; the total yield is 78%.

[0077] Comparative Example 1

[0078] Preparation of peach aldehyde composition, the steps are:

[0079] Add 600g of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom. Also add 100g of n-octanol, 10g of di-tert-butyl peroxide and 86g of methyl acrylate to a mixing bottle in sequence and mix to obtain a preformulated material. When the internal temperature reaches 150°C, pump the preformulated material into the three-necked flask with a peristaltic pump, and add dropwise for 5 hours while keeping warm to obtain a peach aldehyde reaction solution.

[0080] The peach aldehyde reaction liquid enters the flash kettle, at 100°C, vacuum degree 10KPa, to remove n-octanol, the residence time is 30min, at which time the n-octanol content in the reaction liquid is 21000ppm.

[0081] Then it enters the light removal distillation tower to continue light removal, with a vacuum degree of 8 KPa, a bottom temperature of 90°C, a reflux ratio of 2:1, 40 plates, and a time of 30 minutes. At this time, the content of n-octanol in the reaction liquid is reduced to 800 ppm.

[0082] After the light removal is completed, the reaction mixture enters the heavy removal distillation tower with a vacuum degree of 1 KPa, a bottom temperature of 130 ° C, a reflux ratio of 1:1, 40 plates, and a time of 10 min. The content of component A in the reaction liquid is reduced to 350 ppm, and the content of component B is reduced to 510 ppm. A peach aldehyde composition is obtained at the top of the tower, and the peach aroma is light and sour.

[0083] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99wt%, n-octanol content is 800ppm, component A content is 350ppm, component B content is 510ppm, and the total yield is 50%.

[0084] Comparative Example 2

[0085] Preparation of peach aldehyde composition, the steps are:

[0086] Add 600g of n-octanol to the bottom of a three-necked flask with a condenser and a water separator, and add 180g of n-octanol, 10g of di-tert-butyl peroxide, and 86g of methyl acrylate to a mixing bottle in order to obtain a preformulation. When the internal temperature reaches 80°C, pump the preformulation into the three-necked flask with a peristaltic pump, and add dropwise for 3h. After the addition is completed, heat to 150°C at a rate of 1°C / min, and react for 2h to obtain a peach aldehyde reaction solution.

[0087] The peach aldehyde reaction liquid is intermittently distilled with 45 plates and a vacuum degree of 0.1-10KPa. The temperature of the bottom of the tower is slowly increased, and the peach aldehyde fraction is obtained at the top of the tower. The product has a smell of plastic paste.

[0088] Gas phase analysis results: peach aldehyde content 98.5wt%, n-octanol content 5000ppm, component A content 2700ppm, component B content 400ppm, based on methyl acrylate, the total yield is 48%.

[0089] Comparative Example 3

[0090] Preparation of peach aldehyde composition, the steps are:

[0091] Add 700g of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 100g of n-octanol, 10g of di-tert-butyl peroxide, and 86g of methyl acrylate to a mixing bottle in order to obtain a preformulation. When the internal temperature reaches 80°C, pump the preformulation into the three-necked flask with a peristaltic pump, and add dropwise for 2h. After the addition is completed, heat to 140°C at a rate of 6°C / min, and react for 2h to obtain a peach aldehyde reaction solution.

[0092] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 8KPa, to remove n-octanol, the residence time is 18min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 14000ppm.

[0093] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 3KPa, tower bottom temperature 100℃, reflux ratio 3:1, tower plate number 40, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 500ppm.

[0094] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 1KPa, the tower bottom temperature is 140°C, the reflux ratio is 0.5:1, the number of plates is 50, the residence time is 13min, and the content of component A in the reaction liquid is controlled to be reduced to 1250ppm, and the content of component B is reduced to 70ppm. A peach aldehyde product composition is obtained from the top of the tower, and the fruity aroma is slightly light.

[0095] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99.0wt%, n-octanol content is 500ppm, component A content is 1250ppm, and component B content is 70ppm; the total yield is 70%.

[0096] Comparative Example 4

[0097] Preparation of peach aldehyde composition, the steps are:

[0098] Add 700g of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 100g of n-octanol, 10g of di-tert-butyl peroxide, and 86g of methyl acrylate to a mixing bottle in order to mix to obtain a preformulation. When the internal temperature reaches 80°C, pump the preformulation into the three-necked flask with a peristaltic pump, and add dropwise for 2h. After the addition is completed, heat to 140°C at a rate of 0.1°C / min, and react for 2h to obtain a peach aldehyde reaction solution.

[0099] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 8KPa, to remove n-octanol, the residence time is 18min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 14000ppm.

[0100] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 3KPa, tower bottom temperature 100℃, reflux ratio 3:1, tower plate number 40, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 500ppm.

[0101] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 1KPa, the tower bottom temperature is 140°C, the reflux ratio is 0.5:1, the number of tower plates is 50, the residence time is 13min, and the content of component A in the reaction liquid is controlled to be reduced to 12000ppm and the content of component B is reduced to 70ppm. The peach aldehyde product composition is obtained from the top of the tower, and the milky aroma is too strong, covering up part of the peach aroma.

[0102] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 98.0wt%, n-octanol content is 500ppm, component A content is 12000ppm, and component B content is 70ppm; the total yield is 70%.

[0103] Comparative Example 5

[0104] Preparation of peach aldehyde composition, the steps are:

[0105] S1: Add 700g of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 100g of n-octanol, 10g of di-tert-butyl peroxide, and 86g of methyl acrylate to a mixing bottle in order to obtain a pre-formulated material. When the internal temperature reaches 80°C, pump the pre-formulated material into the three-necked flask with a peristaltic pump, and add dropwise for 2h. After the addition is completed, heat to 130°C at a rate of 0.5°C / min, and react for 2h to obtain a peach aldehyde reaction solution.

[0106] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 15KPa, to remove n-octanol, the residence time is 5min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 34000ppm.

[0107] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 8KPa, tower bottom temperature 90℃, reflux ratio 3:1, tower plate number 40, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 4500ppm.

[0108] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 1KPa, the tower bottom temperature is 140°C, the reflux ratio is 0.5:1, the number of plates is 50, the residence time is 13min, and the content of component A in the reaction liquid is controlled to be reduced to 2050ppm, and the content of component B is reduced to 70ppm. A peach aldehyde product composition is obtained from the top of the tower, and the smell is sour.

[0109] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99.0wt%, n-octanol content is 4500ppm, component A content is 2050ppm, and component B content is 70ppm; the total yield is 69%.

[0110] Comparative Example 6

[0111] Preparation of peach aldehyde composition, the steps are:

[0112] S1: Add 700g of n-octanol to a three-necked flask with a condenser and a water separator to lay the bottom, and add 100g of n-octanol, 10g of di-tert-butyl peroxide, and 86g of methyl acrylate to a mixing bottle in order to obtain a pre-formulated material. When the internal temperature reaches 80°C, pump the pre-formulated material into the three-necked flask with a peristaltic pump, and add dropwise for 2h. After the addition is completed, heat to 130°C at a rate of 0.5°C / min, and react for 2h to obtain a peach aldehyde reaction solution.

[0113] S2: The peach aldehyde reaction liquid enters the flash kettle, at 80°C, vacuum degree 8KPa, to remove n-octanol, the residence time is 18min, and the content of n-octanol in the reaction liquid is controlled to be reduced to 14000ppm.

[0114] S3: Then enter the first distillation tower to remove light, feed into the tower, vacuum degree 3KPa, tower bottom temperature 100℃, reflux ratio 3:1, tower plate number 40, residence time 15min, control the content of n-octanol in the reaction liquid to reduce to 500ppm.

[0115] S4: After the light removal is completed, the second distillation tower is entered for heavy removal, the tower is fed, the vacuum degree is 1KPa, the tower bottom temperature is 190°C, the reflux ratio is 0.5:1, the number of tower plates is 50, the residence time is 25min, and the content of component A in the reaction liquid is controlled to be reduced to 2900ppm, and the content of component B is reduced to 370ppm. A peach aldehyde product composition is obtained from the top of the tower, and the peach fragrance is mixed with sour and rotten taste.

[0116] Gas phase analysis results: based on methyl acrylate, peach aldehyde contains 99.0wt%, n-octanol content is 500ppm, component A content is 2900ppm, and component B content is 370ppm; the total yield is 68%.

Claims

1. A high-quality peach aldehyde composition, It is characterized in that The composition comprises peach aldehyde, n-octanol, component A and component B; Wherein, the peach aldehyde content is ≥99wt%, the n-octanol content is ≤800ppm, the component A content is 2000-3000ppm, and the component B content is ≤100ppm, based on the total mass of the high-quality peach aldehyde composition.

2. A method for preparing the high-quality peach aldehyde composition according to claim 1, It is characterized in that the steps include: S1: using n-octanol and methyl acrylate as raw materials, initiated by di-tert-butyl peroxide, reacting at a certain temperature to obtain peach aldehyde reaction liquid; S2: The peach aldehyde reaction liquid is subjected to a flash evaporator to remove n-octanol, and the content of n-octanol in the reaction liquid is controlled to be reduced to 1000-30000ppm during the flash evaporation process; S3: Then the light components are removed through the first distillation tower, and the content of n-octanol in the reaction solution is controlled not to exceed 800 ppm during the first distillation process; S4: The heavy components are removed by a second distillation tower. The content of component A in the reaction solution is controlled to be reduced to 2000-3000 ppm and the content of component B is not more than 100 ppm during the second distillation process, thereby obtaining a high-quality peach aldehyde composition.

3. The preparation method according to claim 2, It is characterized in that In step S1, the molar ratio of n-octanol to methyl acrylate is 3-12:1, preferably 5-10:1; and / or In step S1, the mass ratio of methyl acrylate to di-tert-butyl peroxide is 10-20:1, preferably 10-15:1; and / or In step S1, the reaction temperature is 50-200°C, and the reaction time is 2-10h.

4. The preparation method according to claim 2, It is characterized in that The flash kettle in step S2 has a flash temperature of 50-150°C, preferably 60-110°C, an operating vacuum of 1-10KPa, preferably 5-10KPa, and a kettle residence time of 5-60min.

5. The preparation method according to claim 2, It is characterized in that The separation conditions of the first distillation tower in step S3 are: operating vacuum degree of 0.1-5 KPa, tower bottom operating temperature of 50-150° C., tower bottom residence time of 5-30 min, tower top reflux ratio of 1-5:1, tower plate number of 10-50, and tower feed.

6. The preparation method according to claim 5, It is characterized in that The separation conditions are: operating vacuum degree 1-4 KPa, tower bottom operating temperature 60-100° C., tower bottom residence time 5-20 min, tower top reflux ratio 1-5:1, and tower plate number 10-45.

7. The preparation method according to claim 2, It is characterized in that In step S4, the separation conditions of the second distillation tower are: operating vacuum degree of 0.01-5KPa, tower bottom operating temperature of 100-180°C, time of 1-20min, top reflux ratio of 0.1-3:1, number of tower plates of 10-50, and feeding in the tower.

8. The preparation method according to claim 7, It is characterized in that The separation conditions are: operating vacuum degree 0.01-3KPa, tower bottom operating temperature 120-180°C, time 1-15min, tower top reflux ratio 0.1-2:1, and tower plate number 20-50.

9. The preparation method according to claim 2, It is characterized in that In step S1, the temperature is increased gradually during the reaction process, specifically, firstly, a pre-mixed mixture of n-octanol, di-tert-butyl peroxide and methyl acrylate is added dropwise at 50-80° C. for 1-4 hours, and then the temperature is increased to 100-200° C. at a rate of 0.5-5° C. / min, and the reaction is kept at this temperature for 1-3 hours; Preferably, the n-octanol is added in two parts, one part is added as a base before the reaction, and the remaining part is mixed with di-tert-butyl peroxide and methyl acrylate as a pre-formulated material; more preferably, the mass ratio of the two parts is 1:0.1-1.

10. Use of the high-quality peach aldehyde composition according to claim 1 or the high-quality peach aldehyde composition prepared by the method according to any one of claims 2 to 9, It is characterized in that It is suitable for the fields of flavors and fragrances, feed additives, and daily chemical additives, especially for the fields of feed and daily chemical products.

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