阅读说明：本技术 用肉桂油精馏釜底产物生产食品级苯甲醛的方法 (Method for producing food-grade benzaldehyde by using cinnamon oil rectifying still bottom product ) 是由 李伟光 粟桂娇 刘雄民 辛永超 张笮晦 陈耿 于 2021-08-16 设计创作，主要内容包括：本发明公开了一种用肉桂油精馏釜底产物生产食品级苯甲醛的方法,将桂油精馏尾油和溶剂混合,放入气液反应器中通入臭氧进行臭氧化反应；反应结束后回收溶剂,桂油精馏尾油臭氧化物加水加热分解同时水蒸气蒸馏带出粗苯甲醛,粗苯甲醛经真空精馏提纯,即得。由于肉桂油精馏釜底产物中含有少量肉桂醛及沸点较高的肉桂酸和肉桂醛聚合物,采用本发明经过臭氧化、分解和分离提纯,可以得到食品级苯甲醛。因此,应用本发明可以提高精馏尾油利用率,并实现废液的资源化处理,以求达到最大程度地提高肉桂油制备食品级苯甲醛得率和减少副产物处置。(The invention discloses a method for producing food-grade benzaldehyde by using a cinnamon oil rectifying still bottom product, wherein cinnamon oil rectifying tail oil and a solvent are mixed, and the mixture is placed into a gas-liquid reactor and is introduced with ozone for ozonization reaction; and (3) recovering the solvent after the reaction is finished, adding water into the cassia oil rectification tail oil ozonide for heating decomposition, simultaneously carrying out steam distillation to carry out crude benzaldehyde, and carrying out vacuum rectification and purification on the crude benzaldehyde to obtain the compound. Because the bottom product of the cassia oil rectifying still contains a small amount of cinnamic aldehyde and cinnamic acid and cinnamic aldehyde polymers with higher boiling points, the invention can obtain food-grade benzaldehyde through ozonization, decomposition, separation and purification. Therefore, the invention can improve the utilization rate of the rectification tail oil and realize the resource treatment of the waste liquid so as to improve the yield of the food-grade benzaldehyde prepared from the cinnamon oil to the maximum extent and reduce the disposal of byproducts.)

1. A method for producing food-grade benzaldehyde by using cinnamon oil rectifying still bottom products is characterized in that cinnamon oil rectifying tail oil and a solvent are mixed, and the mixture is placed into a gas-liquid reactor and ozone is introduced into the gas-liquid reactor for ozonization reaction; and (3) recovering the solvent after the reaction is finished, adding water into the cassia oil rectification tail oil ozonide for heating decomposition, simultaneously carrying out steam distillation to carry out crude benzaldehyde, and carrying out vacuum rectification and purification on the crude benzaldehyde to obtain the compound.

2. The method of claim 1, wherein: and mixing the cassia oil rectification tail oil and the solvent according to the weight-volume ratio of 1:2-1: 20.

3. The method of claim 3, wherein: the solvent is one or mixture of food grade anhydrous alcohol, food grade 95% ethanol, food grade ethyl acetate and food grade extraction oil.

4. The method of claim 1, wherein: the reaction temperature of the gas-liquid reactor is-5-25 ℃.

5. The method of claim 1, wherein: when the tail gas obviously discolors the potassium iodide test paper after the reaction is finished.

6. The method of claim 1, wherein: the solvent recovery is carried out by putting the reaction liquid after ozonization reaction into a heavy volatile oil extraction and distillation device and vacuumizing.

7. The method of claim 1, wherein: the water adding amount of the ozonide added with water for heating is one third of the capacity of the distillation flask, and the ozonide is heated to boiling.

Technical Field

The invention belongs to the technical field of fine and deep processing of agricultural and forestry chemical products, and particularly relates to a method for producing food-grade benzaldehyde by using a cinnamon oil rectifying still bottom product.

Background

The cinnamon oil mainly contains trans-cinnamaldehyde which can be used as a raw material for producing food-grade benzaldehyde equivalent to natural products [ GB-28320-2012-food safety national standard-food additive-benzaldehyde; research on the synthesis method of natural benzaldehyde is advanced-Chenhongyan, fine chemical engineering, No. 6 of 2010, page 579-583; the research progress of deep processing of natural cinnamon oil-how small English, Chinese seasoning, No. 10 of 2015, page 120-124 ]. In order to fully utilize each component in cinnamon oil, a large number of multipurpose rectification methods are used for separating and purifying the cinnamaldehyde by an industrial production method [ the process research of the cinnamon oil for purifying the cinnamaldehyde is Zhang Chang Yong, forest chemical and industry, No. 6 in 2009, pages 65-68, the process of separating high-purity cinnamaldehyde and cinnamyl acetate from the cinnamon oil, LieGuiqing, Western forestry science, No. 6 in 2016, page 104 and 107 in 107 ], a product at the bottom of a kettle after the cinnamon oil rectification is called as cassia oil rectification tail oil for short, the cassia oil rectification tail oil is brown oily liquid, and the cassia oil rectification tail oil can only be treated as viscous liquid at present, and no method report of recovery treatment is seen.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for producing food-grade benzaldehyde by using a cinnamon oil rectifying still bottom product, so that the yield of food-grade benzaldehyde prepared from cinnamon oil is improved, and byproducts are reduced.

In order to solve the technical problems, the invention adopts the following technical scheme:

a method for producing food-grade benzaldehyde from cassia oil rectifying still bottom products comprises mixing cassia oil rectifying tail oil and a solvent, placing into a gas-liquid reactor, and introducing ozone for ozonization reaction; and (3) recovering the solvent after the reaction is finished, adding water into the cassia oil rectification tail oil ozonide for heating decomposition, simultaneously carrying out steam distillation to carry out crude benzaldehyde, and carrying out vacuum rectification and purification on the crude benzaldehyde to obtain the compound.

Mixing the cassia oil rectification tail oil and the solvent according to the weight-volume ratio of 1:2-1: 20.

The solvent is one or mixture of food grade anhydrous alcohol, food grade 95% ethanol, food grade ethyl acetate, and food grade extraction oil.

The reaction temperature of the gas-liquid reactor is-5-25 ℃.

When the tail gas after the reaction obviously changes the color of the potassium iodide test paper.

The solvent recovery is carried out by putting the reaction liquid after ozonization reaction into a heavy volatile oil extraction and distillation device and vacuumizing.

The water adding amount of the ozonide added with water for heating is one third of the capacity of the distillation flask, and the ozonide is heated to boiling.

Aiming at the problem that the tank bottom product is not recycled after the cassia oil is rectified at present, the inventor establishes a method for producing food-grade benzaldehyde by using the tank bottom product of the cassia oil rectification, wherein the cassia oil rectification tail oil and a solvent are mixed and are placed into a gas-liquid reactor to be introduced with ozone for ozonization reaction; and (3) recovering the solvent after the reaction is finished, adding water into the cassia oil rectification tail oil ozonide for heating decomposition, simultaneously carrying out steam distillation to carry out crude benzaldehyde, and carrying out vacuum rectification and purification on the crude benzaldehyde to obtain the compound. Because the bottom product of the cassia oil rectifying still contains a small amount of cinnamic aldehyde and cinnamic acid and cinnamic aldehyde polymers with higher boiling points, the invention can obtain food-grade benzaldehyde through ozonization, decomposition, separation and purification. Therefore, the invention can improve the utilization rate of the rectification tail oil and realize the resource treatment of the waste liquid so as to improve the yield of the food-grade benzaldehyde prepared from the cinnamon oil to the maximum extent and reduce the disposal of byproducts.

Detailed Description

First, the process route

Mixing oil rectification tail oil and a solvent according to a certain proportion, putting the mixture into a gas-liquid reactor (Meng wash bottle), putting the gas-liquid reactor into a low-temperature bath at the temperature of-5 to 25 ℃, introducing ozone to carry out gas-liquid reaction, monitoring the tail gas by using a moist potassium iodide test paper, and stopping introducing the ozone to stop the reaction when the potassium iodide test paper obviously discolors; 2, putting the reaction solution into a heavy volatile oil extraction and distillation device, vacuumizing the solvent for recycling, and stopping vacuumizing when the solvent is not much left; 3 adding water into the reaction liquid after solvent recovery until the reaction liquid is heated to boiling by one third of the capacity of the distillation flask, decomposing ozonides while carrying out steam distillation to remove crude benzaldehyde, stopping heating when no oil exists in the fraction, standing the fraction for a period of time, and separating lower-layer crude benzaldehyde when the oil and the water are separated into layers. Separating unreacted water-insoluble distillation tail oil residual liquid at the bottom of the bottle, wherein the residual liquid amount is about 45% of the fed material, and the resource rate of cassia oil distillation tail oil reaches 55%; 4, vacuum rectifying and purifying the crude benzaldehyde to more than 98%, wherein the highest food-grade benzaldehyde yield can reach 10.6%.

Second, application example

Example 1

Weighing 20g of rectified tail oil, adding 200mL of absolute ethyl alcohol for dissolution, adding a dissolved solution into a bubble reactor, placing the bubble reactor into a low-temperature bath tank (-5 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing and recovering ethanol, stopping vacuumizing when residual liquid is about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is obtained, separating a lower oil layer after a distillate oil water layer is separated, and performing vacuum rectification under the conditions of 2000Pa and 100 ℃ oil bath.

As a result: the yield of 99% benzaldehyde is 10.2%; and unreacted rectification tail oil residue which is insoluble in water is separated out from the bottom of the bottle, and the recycling rate of the cassia oil rectification tail oil is 54 percent.

Example 2

Weighing 20g of rectified tail oil, adding 200mL of 95% ethanol for dissolution, adding a dissolved solution into a bubble reactor, placing the bubble reactor into a low-temperature bath (0 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing to recover ethanol, stopping vacuumizing when residual liquid is about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is discharged, separating a lower oil layer after distillate oil water is layered, and performing vacuum rectification at 2000Pa and oil bath 100 ℃.

As a result: the yield of 99% benzaldehyde was 9.8%; and unreacted water-insoluble distillation tail oil residual liquid is separated from the bottom of the bottle, and the recycling rate of the cassia oil distillation tail oil is 51 percent.

Example 3

Weighing 20g of rectified tail oil, adding 200mL of ethyl acetate for dissolving, adding a dissolving solution into a bubble reactor, placing the bubble reactor into a low-temperature bath (0 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing and recovering ethanol, stopping vacuumizing when residual liquid is left to be about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is obtained, separating a lower-layer oil layer after a distillate oil water layer is separated, and performing vacuum rectification under the conditions of 2000Pa and 100 ℃ oil bath.

As a result: the yield of 99% benzaldehyde was 8.9%; and unreacted water-insoluble distillation tail oil residual liquid is separated from the bottom of the bottle, and the recycling rate of the cassia oil distillation tail oil is 52 percent.

Example 4

Weighing 20g of rectified tail oil, adding 300mL of extraction oil No. 6 for dissolution, adding a dissolved solution into a bubble reactor, placing the bubble reactor into a low-temperature bath (0 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing and recovering ethanol, stopping vacuumizing when residual liquid is about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is obtained, separating a lower-layer oil layer after distillate oil water is layered, and performing vacuum rectification under the conditions of 2000Pa and oil bath 100 ℃.

As a result: the yield of 99% benzaldehyde is 6.6%; and unreacted rectification tail oil residue which is insoluble in water is separated out from the bottom of the bottle, and the recycling rate of the cassia oil rectification tail oil is 48 percent.

Example 5

Weighing 20g of rectification tail oil, adding 120mL of absolute ethyl alcohol and 80mL of extraction oil No. 6 for dissolution, adding a dissolved solution into a bubbling reactor, placing the bubbling reactor into a low-temperature bath (0 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing to recover ethyl alcohol, recovering residual liquid to be about 30mL, stopping vacuumizing, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is discharged, separating a lower oil layer after a distillate oil water layer is separated, and performing vacuum rectification at 2000Pa and an oil bath temperature of 100 ℃.

As a result: the yield of 99% benzaldehyde is 10.6%; and unreacted water-insoluble distillation tail oil residual liquid is separated from the bottom of the bottle, and the recycling rate of the cassia oil distillation tail oil is 55 percent.

Example 6

Weighing 20g of rectification tail oil, adding 100mL of absolute ethyl alcohol and 100mL of ethyl acetate for dissolving, adding a dissolved solution into a bubble reactor, placing the bubble reactor into a low-temperature bath (0 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing and recovering ethanol, stopping vacuumizing when residual liquid is about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is discharged, separating a lower oil layer after distillate oil water is layered, and performing vacuum rectification under the conditions of 2000Pa and oil bath 100 ℃.

As a result: the yield of 99% benzaldehyde is 10.3%; and unreacted rectification tail oil residue which is insoluble in water is separated out from the bottom of the bottle, and the recycling rate of the cassia oil rectification tail oil is 54 percent.

Example 7

Weighing 20g of rectification tail oil, adding 150mL of absolute ethyl alcohol and 50mL of extraction oil No. 6 for dissolution, adding a dissolved solution into a bubbling reactor, placing the bubbling reactor into a low-temperature bath (20 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing to recover ethyl alcohol, recovering residual liquid to be about 30mL, stopping vacuumizing, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is discharged, separating a lower oil layer after a distillate oil water layer is separated, and performing vacuum rectification at 2000Pa and an oil bath temperature of 100 ℃.

As a result: the yield of 99% benzaldehyde is 7.2%; and unreacted rectification tail oil residue which is insoluble in water is separated out from the bottom of the bottle, and the resource rate of the cassia oil rectification tail oil is 49.8 percent.

Example 8

Weighing 20g of rectified tail oil, adding 200mL of absolute ethyl alcohol for dissolution, adding a dissolved solution into a bubbling reactor, placing the bubbling reactor into a low-temperature bath (25 ℃), introducing ozone for reaction, stopping introducing ozone when potassium iodide test paper in tail gas is obviously discolored, placing a reaction solution into a 500mL heavy oil extraction device flask, vacuumizing and recovering ethanol, stopping vacuumizing when residual liquid is about 30mL, adding 250mL of distilled water, distilling with steam to evaporate volatile oil, stopping heating after no oil is obtained, separating a lower oil layer after a distillate oil water layer is separated, and performing vacuum rectification under the conditions of 2000Pa and 100 ℃ oil bath.

As a result: the yield of 99% benzaldehyde is 8.7%; and unreacted water-insoluble distillation tail oil residual liquid is separated from the bottom of the bottle, and the recycling rate of the cassia oil distillation tail oil is 47 percent.

The benzaldehyde obtained in the embodiment is detected according to the standard [ GB _ 28320-.