TW201806915A - System and method for preparing aromatic derivative - Google Patents

Abstract

A system for preparing an aromatic derivative is provided, including: a photo-bromination reaction section for performing a photocatalytic reaction of an aromatic hydrocarbon and a brominating agent to form an aromatic hydrocarbon bromide; a substitution reaction section for performing a substitution reaction of the an aromatic hydrocarbon bromide from the photo-bromination reaction section with an alkali base compound or an alkali carboxylate compound to form an aromatic derivative; and a regeneration unit for reacting an alkali metal bromide formed by the substitution reaction section with an acid to form a hydrobromic acid. The regeneration unit is in fluid communication with the photo-bromination reaction section, such that the hydrobromic acid is recycled to the photo-bromination reaction section. A method for preparing the aromatic derivative is also provided.

Description

Preparation system and preparation method of aromatic derivatives

This disclosure relates to a preparation system and a preparation method for aromatic derivatives.

The direct oxidation of benzyl of aromatic hydrocarbons is an important chemical reaction to provide corresponding aromatic derivatives. However, the metal reagents and wastes generated by the above reactions cannot usually be reused, which causes a large amount of pollution and waste, and also consumes preparation costs. Moreover, in the above reaction, halogen is often used for oxidation, especially the relatively cheap chlorine gas. However, after the chlorine gas forms a chloride, it needs to be converted back to chlorine gas by electrolysis, so it is difficult to recover for repeated use. In addition, in the prior art, aromatic derivatives need to be prepared by two independent processes, which results in complicated process steps and reduced reaction efficiency.

Based on the above problems, the present disclosure provides a new aromatic derivative preparation system and preparation method, which can simplify the process steps and increase the yield, and the waste generated by the reaction can be recycled and reused, thereby reducing the production cost and increasing the production. effectiveness.

According to some embodiments, the present disclosure provides a system for preparing aromatic derivatives, including: a photobromination reaction zone, which performs a photocatalytic reaction between an aromatic hydrocarbon and a brominating agent to form an aromatic hydrocarbon bromide; and replaces the reaction zone, so that the Aromatic hydrocarbon bromide and alkali base compound in the reaction zone Or an alkali carboxylate compound to perform a substitution reaction to form an aromatic derivative; and a regeneration unit that reacts the alkali metal bromide formed in the substitution reaction zone with an acid to form hydrobromic acid, and the regeneration unit is photobrominated The reaction zone is in fluid communication to recover the hydrobromic acid into the photobromination reaction zone. The aromatic derivative is, for example, an aromatic alcohol or an aromatic ester.

According to some embodiments, the present disclosure further provides a preparation system for aromatic derivatives, including: a reaction tank for containing a reaction liquid, the reaction liquid including aromatic hydrocarbons and a brominating agent; a lighting device, so that the aromatic hydrocarbons from the reaction tank and The brominating agent performs a photobromination reaction to form a brominated product stream. The brominated product stream includes a liquid unreacted aromatic hydrocarbon and a solid aromatic bromide; a separation unit enables the solid aromatic bromide and liquid Separation of unreacted aromatic hydrocarbons, wherein the separation unit is in fluid communication with the reaction tank to circulate the liquid unreacted aromatic hydrocarbons into the reaction tank; and instead of the reactor, the solid aromatic bromide and alkali from the separation unit are replaced A basic alkali compound or an alkali carboxylate compound undergoes a substitution reaction to form an aromatic derivative. The aromatic derivative is, for example, an aromatic alcohol or an aromatic ester.

According to some embodiments, the present disclosure further provides a method for preparing an aromatic derivative, including: (a) performing a photobromination reaction of an aromatic hydrocarbon and a brominating agent in a first solvent to form an aromatic hydrocarbon bromide; (b) Substituting an aromatic hydrocarbon bromide with an alkali base compound or an alkali carboxylate compound in a second solvent to form an aromatic derivative, such as an aromatic alcohol or an aromatic ester; and (c) reacting the alkali metal bromide formed by the substitution reaction with an acid to form hydrobromic acid, and recovering the hydrobromic acid for use in step (a).

To enable the above and other objectives, features, and advantages of this disclosure to be further improved Obviously easy to understand, several examples and experimental examples are given below, and will be described in detail with the accompanying drawings, as follows.

100‧‧‧ Preparation System

10‧‧‧Aromatics

11‧‧‧ Brominating agent

11a‧‧‧hydrobromic acid

11b‧‧‧hydrogen peroxide solution

12‧‧‧ Solvent

13‧‧‧ water

14a‧‧‧Alkali alkali metal compounds

14b‧‧‧ alkali metal carboxylate

16‧‧‧Aromatic hydrocarbon bromide

18‧‧‧ reaction mixture

20‧‧‧extraction solvents

22‧‧‧ organic phase

24‧‧‧ water phase

26a‧‧‧Aromatic alcohol

26b‧‧‧Aromatic ester

27‧‧‧ Alkali metal bromide

28‧‧‧ acidic compounds

29‧‧‧ Water

30‧‧‧ concentrated sulfuric acid

32‧‧‧ alkali metal salts

34‧‧‧ basic compounds

300‧‧‧ Preparation System

55‧‧‧ reaction mixture

56‧‧‧ Brominated mixture

58‧‧‧ solid aromatic bromide

60‧‧‧Reaction mixture

64‧‧‧mixture

68‧‧‧ organic phase

R‧‧‧ Reactor

R1‧‧‧ Reactor

R2‧‧‧Reactor

A‧‧‧Photobromination reaction zone

B‧‧‧ Separation Unit

C‧‧‧ replaces the reaction zone

D‧‧‧extraction unit

E‧‧‧purification unit

F‧‧‧Distillation unit

G‧‧‧Regeneration unit

H‧‧‧ Neutralization Unit

I‧‧‧ reaction tank

J‧‧‧lighting device

K‧‧‧ Separation Unit

L‧‧‧ replaces the reactor

M‧‧‧Distillation unit

N‧‧‧ Neutralization Unit

O‧‧‧extraction unit

Q‧‧‧Regeneration unit

P‧‧‧Purification unit

The embodiments of the present disclosure will be described in detail below with the accompanying drawings. It should be noted that the following illustrations are not drawn to scale according to industrial standards. In fact, the size of the components may be arbitrarily enlarged or reduced for clarity. Showing the characteristics of this disclosure. In the description and drawings, unless otherwise specified, the same or similar elements will be represented by similar symbols.

FIG. 1 is a schematic diagram of an aromatic derivative preparation system according to the first embodiment of the present disclosure.

FIG. 2 is a schematic diagram of a preparation system of an aromatic derivative according to a second embodiment of the present disclosure.

FIG. 3 is a schematic diagram of a system for preparing aromatic derivatives according to a third embodiment of the present disclosure.

Even if any one of the embodiments described in the following description discloses a plurality of technical features at the same time, it does not mean that the inventor must implement all the technical features in any one of the embodiments at the same time. In other words, as long as it does not affect the possibility of implementation, those with ordinary knowledge in the technical field can selectively implement some but not all of the technical features according to the disclosure of the present invention and according to requirements or design concepts, thereby increasing the implementation of the present invention. Flexibility.

The disclosed embodiments provide a system and method for preparing aromatic derivatives. By-products produced by the reaction can be recovered and reused. Therefore, the energy consumption of the reaction can be reduced, the production cost can be saved, and the production efficiency can be improved. rate. Furthermore, in some embodiments, the process of forming an aromatic derivative from an aromatic hydrocarbon does not need to go through a recrystallization or distillation purification unit and does not have a step of purifying the intermediate, thereby simplifying the manufacturing process.

In addition, the "mole equivalent" described in this disclosure is based on the molar number of the effective response of one compound, and the ratio of the molar number of the other compound is compared. For example, in one experimental example, 1 mole equivalent of para-xylene is used, and the corresponding hydrogen peroxide compound in the hydrogen peroxide aqueous solution is 2.5 mole equivalents. The following can be deduced by analogy.

FIG. 1 is a schematic diagram of an aromatic derivative preparation system 100 according to the first embodiment of the present disclosure. Referring to FIG. 1, the aromatic derivative preparation system 100 includes at least a photobromination reaction zone A, a substitution reaction zone C, and a regeneration unit G. In this embodiment, the photobromination reaction zone A and the replacement reaction zone C are located in the same reactor R (the reactor is, for example, a commercially available batch reactor provided with a stirring bar), but in another embodiment The photobromination reaction zone A and the substitution reaction zone C may also be located in different reactors.

Referring to FIG. 1, the photobromination reaction zone A is used to perform a photocatalytic reaction between an aromatic hydrocarbon 10 and a brominating agent 11 to form an aromatic hydrocarbon bromide 16. In addition, the substitution reaction zone C is used to perform a substitution reaction between the aromatic hydrocarbon bromide 16 and the alkali base compound 14a or the alkali carboxylate compound 14b from the photobromination reaction zone A. To form an aromatic derivative, this embodiment is an aromatic alcohol 26a or an aromatic ester 26b. In addition, the regeneration unit G is, for example, a redox reaction tank, and is used for reacting the alkali metal bromide 27 and the acid formed from the substitution reaction zone C (this embodiment is concentrated sulfuric acid 30, and in other embodiments may be hydrochloric acid, etc. The acid used according to the design is reacted to form hydrobromic acid 11a. In addition, the regeneration unit G is in fluid communication with the photobromination reaction zone A, and the hydrobromic acid 11a is recovered into the photobromination reaction zone A.

For example, as shown in the following formula (1), the photobromination reaction zone A can be used to perform a photocatalytic reaction between p-xylene and a brominating agent (for example, a combination of hydrobromic acid (HBr) and an aqueous hydrogen peroxide solution) to Α, α'-dibromo-p-xylene is formed. Furthermore, the substitution reaction zone C may be used to perform a substitution reaction of α, α′-dibromo-p-xylene from the photobromination reaction zone A with sodium formate (HCOONa) to form p-xylylene glycol. In addition, the regeneration unit G can be used to react sodium bromide (NaBr) formed by replacing the reaction zone C with sulfuric acid to form hydrobromic acid (HBr), and recover the hydrobromic acid (HBr) into the photobromination reaction zone A. . It should be noted that the compounds used in formula (1) are only examples, and the disclosure is not limited thereto.

Hereinafter, the preparation system 100 and the process steps for preparing aromatic derivatives using the preparation system 100 will be described in more detail and in detail. As shown in FIG. 1, the preparation system 100 may further include an extraction unit D, a purification unit E, a distillation unit F, and a neutralization unit H.

First, as shown in FIG. 1, the photobromination reaction zone A is used to perform a photobromination reaction on the aromatic hydrocarbon 10. Specifically, an aromatic hydrocarbon 10, a brominating agent 11 (a combination of hydrobromic acid (HBr) 11a and an aqueous hydrogen peroxide solution 11b in this embodiment), and a solvent 12 are separately added to the photobromination reaction zone A, and Stir well to obtain a mixture.

In the present disclosure, the aromatic hydrocarbon 10 used is not particularly limited, and is, for example, a monoaromatic hydrocarbon, a biaromatic hydrocarbon or a triaromatic hydrocarbon. In some embodiments, the monoaromatic hydrocarbon may be Wherein R is a linear or branched alkyl group having 1 to 15 carbon atoms; Wherein R and R ₁ are linear or branched alkyl groups having 1 to 15 carbon atoms, R ₁ may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 6 substituents; or A combination of the above. In some embodiments, the diaromatic hydrocarbon may be Wherein R is a linear or branched alkyl group having 1 to 15 carbon atoms; Wherein R and R ₁ are linear or branched alkyl groups having 1 to 15 carbon atoms, R and R ₁ may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 10 substituents; R and R ₁ are straight or branched alkyl groups having 1 to 15 carbon atoms, R and R ₁ may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 8 substituents; Wherein R and R ₁ are linear or branched alkyl groups having 1 to 15 carbon atoms, R and R ₁ may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 10 substituents. X ₁ and X ₂ refer to hydrogen or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; R and R ₁ are straight or branched alkyl groups having 1 to 15 carbon atoms, R and R 1 may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 10 substituents; Wherein R and R ₁ are linear or branched alkyl groups having 1 to 15 carbon atoms, R and R ₁ may be located at any position on the aromatic ring, and the total number of R and R ₁ is less than 10 substituents; Or a combination of the above. In some embodiments, the triaromatic hydrocarbon may be Wherein R is a linear or branched alkyl group having 1 to 15 carbon atoms; Where Ph ₁ can be , Ph ₂ can be Ph ₁ and Ph ₂ can be located at any position on the aromatic ring. R, R ₁ and R ₂ are linear or branched alkyl groups with 1-15 carbon atoms. R, R ₁ and R ₂ can be located in the aromatic ring. Any position on the ring, and the total number of R, R ₁ and R ₂ is less than 14 substituents; Wherein R, R ₁ and R ₂ are straight or branched alkyl groups having 1-15 carbon atoms, R, R ₁ and R ₂ may be located at any position on the aromatic ring, and R, R ₁ and R ₂ The total number is less than 10 substituents; Wherein R, R ₁ and R ₂ are straight or branched alkyl groups having 1-15 carbon atoms, R, R ₁ and R ₂ may be located at any position on the aromatic ring, and R, R ₁ and R ₂ The total number is less than 14 substituents. X ₁ , X ₂ , X ₃ and X ₄ refer to hydrogen or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; Wherein R, R ₁ and R ₂ are straight or branched alkyl groups having 1-15 carbon atoms, R, R ₁ and R ₂ may be located at any position on the aromatic ring, and R, R ₁ and R ₂ The total number is less than 14 substituents; Wherein R, R ₁ and R ₂ are straight or branched alkyl groups having 1-15 carbon atoms, R, R ₁ and R ₂ may be located at any position on the aromatic ring, and R, R ₁ and R ₂ The total number is less than 14 substituents; or a combination thereof.

The solvent 12 suitable for the present disclosure may be a halogenated hydrocarbon, such as dichloroethane, cyclohexane, or other halogenated hydrocarbons that can dissolve aromatic hydrocarbons.

The brominating agent 11 suitable for the present disclosure may be bromine water (Br ₂ ). It should be noted that although bromine water (Br ₂ ) is easier to obtain, it is highly dangerous in handling, transportation and use. Therefore, the brominating agent 11 is preferably a combination of hydrobromic acid (HBr) and an aqueous hydrogen peroxide solution; a combination of sodium bromide (NaBr), sulfuric acid (H ₂ SO ₄ ) and an aqueous hydrogen peroxide solution, or other capable of generating bromine water (Br ₂ ).

The order in which the brominating agent 11 is added can be adjusted according to the design. For example, after cooling the mixture, hydrobromic acid 11a is first added to the photobromination reaction zone A, and then the temperature is about -10 ° C-30 ° C (preferably Under the environment of about 0 ° C. to 10 ° C., an aqueous hydrogen peroxide solution 11b is titrated into the above mixture. In other embodiments, an aqueous hydrogen peroxide solution 11b may be added first, and then a hydrobromic acid 11a may be added. In some embodiments, the molar equivalent ratio of the aromatic hydrocarbon 10, the hydrobromic acid 11a to the solvent 12 is 1: 2-3: 1-20. In some embodiments, the molar equivalent ratio of the aqueous hydrogen peroxide solution 11b to the aromatic hydrocarbon 10 is 2-5: 1.

Then, a light source is used to irradiate to perform a photocatalytic reaction, thereby forming an aromatic hydrocarbon bromide 16.

In some embodiments, the wavelength of the light source is about 400-700 nm, preferably about 420 nm, and the power of the light source is about 20-200 watts (Watt), preferably about 40-100 watts, more preferably about 80 watts. In some embodiments, the reaction time of the photobromination reaction is about 0.5-24 hours, preferably about 4-12 hours.

It should be noted that since the addition of an aqueous hydrogen peroxide solution 11b to the photobromination reaction zone A is an exothermic reaction, overheating may produce unnecessary products. Therefore, during the titration process, the temperature of the photobromination reaction zone A is preferably controlled at Below about 15 ° C, if the above temperature is exceeded, the addition of the hydrogen peroxide aqueous solution 11b is stopped, and the reaction can be continued when the temperature is lowered.

Please continue to refer to FIG. 1. The substitution reaction zone C is used to perform a substitution reaction on the aromatic hydrocarbon bromide 16 from the photobromination reaction zone A. Specifically, water 13 and a basic alkali metal compound 14a or an alkali metal carboxylate 14b are added to the substitution reaction zone C, and heated to about 80-160 ° C. (preferably at about 1-10 atm). It is heated to about 100 ~ 120 ° C under about 1 atm, more preferably under reflux state under about 2-5 atm and reacted for about 0.5-24 hours to perform substitution reaction with aromatic hydrocarbon bromide 16, A reaction mixture 18 is further formed. The reaction mixture 18 includes a crude product of an aromatic alcohol 26a or an aromatic ester 26b, an alkali metal bromide 27, a solvent 12, an acidic compound 28, and water 29.

In some embodiments, the basic alkali metal compound 14a may be sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), or a combination thereof. In some embodiments, the alkali metal carboxylate 14b may be sodium formate, sodium acetate, or a combination thereof. In some embodiments, the molar equivalent ratio of the basic alkali metal compound 14a or the alkali metal carboxylate 14b to the aromatic hydrocarbon bromide 16 is 2-5: 1, preferably 2.5: 1.

In some embodiments, a surfactant may be selectively added in the substitution reaction zone C to improve the compatibility between organics and water. In these embodiments, the surfactant may be acetone, 1,4-dioxane (1,4-Dioxane) or a combination thereof, The weight ratio of the surfactant to the water 13 may be 0.5-4: 1.

It is worth noting that in this embodiment, the substitution reaction zone C directly receives the crude product from the photobromination reaction zone A without undergoing recrystallization or distillation purification unit, that is, forming an aromatic alcohol or aromatic from an aromatic hydrocarbon. The crude ester product was not subjected to any recrystallization or distillation purification steps. Therefore, the aromatic alcohol or aromatic ester is prepared by a one-pot process, so the preparation steps can be simplified.

Please continue to refer to FIG. 1. The extraction unit D (for example, a commercially available extraction equipment) separates a product stream (here, the product stream including the reaction mixture 18) formed in place of the reaction zone C into an aqueous phase stream and an organic phase. Phase flow, where the organic phase flow includes an aromatic derivative, such as an aromatic alcohol or an aromatic ester. In other words, the extraction unit D is used to perform an extraction step on the reaction mixture 18 from the substitution reaction zone C. Specifically, an extraction solvent 20 is added to the extraction unit D to separate the reaction mixture 18 into an organic phase 22 and an aqueous phase 24. The organic phase 22 includes a crude product of the extraction solvent 20 and the aromatic alcohol 26a or the aromatic ester 26b, and the aqueous phase includes an alkali metal bromide 27, a solvent 12, an acidic compound 28, and water 29. In some embodiments, the extraction solvent 20 may be Methyl isobutyl ketone (MIBK), ethyl acetate, or other suitable solvents. In some embodiments, the weight ratio of the reaction mixture 18 to the extraction solvent 20 is 1: 1.

As shown in FIG. 1, the purification unit E is used for purifying the organic phase 22 from the extraction unit D to separate the product of the aromatic alcohol 26a or the aromatic ester 26b from the extraction solvent 20 and recover the extraction solvent 20 Into the extraction unit D. In some embodiments, the purification unit E includes a crystallization unit and / or a distillation unit, such as a commercially available crystallization equipment or distillation equipment. Therefore, the purification step may include a crystallization step, a distillation step, or a combination thereof. For example, using reduced pressure distillation The extraction solvent 20 is distilled off and recovered to the extraction unit D. In the embodiment using the preparation system 100, the yield of the aromatic alcohol 26a or the aromatic ester 26b can be more than 62%, and in some experimental examples, the yield can be 62% -92%. The purity can reach more than 85%. In some experimental examples, the purity is more than 90%.

The obtained aromatic derivative product is, for example, an aromatic alcohol 26a or an aromatic ester 26b, depending on whether the reactant added in the substitution reaction is a basic alkali metal compound 14a or an alkali metal carboxylate 14b. As exemplified by the following formula (2a), when the reactant added in the substitution reaction is a basic alkali metal compound (for example, sodium hydroxide), the formed product is an aromatic alcohol. Furthermore, as exemplified by the following formula (2b), in the case where the reactant added in the substitution reaction is an alkali metal carboxylate (for example, sodium acetate), the formed product is an aromatic ester. In certain embodiments, where the reactant added to the substitution reaction is sodium formate, the product formed is an aromatic alcohol. For example, as shown in the formula (1) mentioned above, in the case where the reactant added in the substitution reaction is sodium formate, p-xylene finally forms p-xylylene glycol. It should be noted that the compounds used in formula (1), formula (2a) and formula (2b) are only examples, and the disclosure is not limited thereto.

Continuing to refer to FIG. 1, the distillation unit F, such as a commercially available distillation equipment, is used to perform a distillation step on the water phase 24 from the extraction unit D. Specifically, in the distillation unit F, the solvent 12, the acidic compound 28, and the water 29 of the aqueous phase 24 are sequentially distilled out by the difference in boiling points, and the remaining part is an alkali metal bromide 27. Next, the alkali metal bromide 27, the solvent 12, the acidic compound 28 and the water 29 separated from the distillation unit F are separately subjected to a recovery step, as described in detail below: The regeneration unit G is used to separate the alkali metal bromide 27 from the distillation unit F Treatment is performed to regenerate hydrobromic acid 11a. Specifically, concentrated sulfuric acid 30 is added to the regeneration unit G and allowed to react with the alkali metal bromide 27 to form hydrobromic acid 11a and alkali metal salts 32. Furthermore, the regeneration unit G is in fluid communication with the photobromination reaction zone A, so that the hydrobromic acid 11a obtained by the regeneration unit G is recovered into the photobromination reaction zone A. In some embodiments, the molar equivalent ratio of alkali metal bromide 27 to concentrated sulfuric acid 30 is 1: 2-4. In some embodiments, the alkali metal bromide 27 from the distillation unit F is subjected to an additional purification step (for example, a recrystallization step) before being transferred to the regeneration unit G for reaction. It is worth noting that, since the reaction of treating the alkali metal bromide 27 to regenerate the hydrobromic acid 11a can be performed only by simple operations such as heating and concentration under reduced pressure, in comparison, the conventional technology The chlorinating agent used (for example: chlorine gas) requires electrolysis of the chloride produced by the reaction to regenerate and recover the chlorinating agent. In the chlor-alkali industrial process, the purity of sodium chloride is very high, so Recovery of sodium chloride is relatively expensive. Therefore, the system provided by this disclosure can complete the recovery of hydrobromic acid without using the aforementioned electrolysis technology, thereby saving the production cost and improving the production efficiency.

The neutralization unit H is, for example, a commercially available acid-base neutralization tank, and is used to neutralize the acidic compound 28 and water 29 from the distillation unit F. Specifically, a basic compound 34 is added to the neutralization unit H, and a neutralization reaction with the acidic compound 28 and water 29 is performed to form a basic alkali metal compound 14a or an alkali metal carboxylate 14b. Furthermore, the neutralization unit H is in fluid communication with the substitution reaction zone C, so that the alkaline alkali metal compound 14a or the alkali metal carboxylate 14b obtained by neutralizing the unit H is recovered into the substitution reaction zone C.

It can be understood that, in the embodiment of the present disclosure, after processing the by-products generated in the photobromination reaction zone and the substitution reaction zone, they can become the reactants again and be recovered and reused in the reactor. Therefore, the reaction can be reduced. Energy consumption, reduce preparation costs and improve production efficiency.

FIG. 2 is a schematic diagram of an aromatic derivative preparation system 200 according to the second embodiment of the present disclosure. In this embodiment, the photobromination reaction and the substitution reaction are respectively performed in different reactors, thereby improving the reaction efficiency.

Referring to FIG. 2, the aromatic derivative preparation system 200 is substantially similar to the aromatic derivative preparation system 100 in the above embodiment, but the difference between the two is that the photobromination reaction zone A and the substitution reaction zone C are respectively different. They are located in separate reactors R1 and R2. The reactor can be adjusted by design, for example using a continuous reactor.

In detail, after performing a photocatalytic reaction in the photobromination reaction zone A of the reactor R1 to form an aromatic hydrocarbon bromide 16, the aromatic hydrocarbon bromide 16 is taken out from the reactor R1 and moved to another reactor R2 Further, substitution is performed in the substitution reaction zone C of the reactor R2 to form a reaction mixture 18 including a crude product of the aromatic alcohol 26a or the aromatic ester 26b.

Furthermore, in another embodiment, the preparation system 200 may further include a separation unit B for separating the aromatic hydrocarbon bromide 16 formed in the reactor R1, and then moving the aromatic hydrocarbon bromide 16 to the reactor R2. Medium to improve production efficiency.

In the embodiment using the preparation system 200, the yield of the aromatic alcohol 26a or the aromatic ester 26b purified by the purification unit E can reach more than 75%, and in some experimental examples, it can reach 75% -96%, and the aromatic alcohol 26a or The purity of aromatic ester 26b can reach 90%, and in some experimental examples, it can reach 90-95%.

It should be noted that in the preparation system 200, although the photobromination reaction Zone A and substitution reaction zone C are located in different reactors, but substitution reaction zone C can directly receive the crude product from photobromination reaction zone A without undergoing recrystallization or distillation purification unit, that is, from aromatic hydrocarbons In the process of forming the crude product of the aromatic alcohol or aromatic ester, the intermediate is not subjected to any recrystallization or distillation purification steps, so the process steps can be simplified.

In addition, in the preparation system 100 shown in FIG. 1, the photobromination reaction and the substitution reaction are performed in the same reactor, so it is to batchly add the reaction raw materials to the reactor to perform the reaction in batches; and In the preparation system 200 shown in FIG. 2, the photobromination reaction and the substitution reaction are performed in different reactors, so the reaction raw materials can be continuously added to the reactors to perform the reaction continuously. Therefore, compared with the preparation system 100, using the preparation system 200 to prepare aromatic derivatives can obtain higher yield and process efficiency.

FIG. 3 is a schematic diagram of an aromatic derivative preparation system 300 according to a third embodiment of the present disclosure. In this embodiment, in addition to the advantages of the above embodiment, since the photobromination reaction can be continuously reacted in an external circulation system, the process efficiency can be further improved.

Referring to FIG. 3, the aromatic derivative preparation system 300 includes a reaction tank I, a lighting device J, a separation unit K, a replacement reactor L, a distillation unit M, a neutralization unit N, an extraction unit O, a regeneration unit Q, and a purification unit. P.

As shown in FIG. 3, the reaction tank I, such as a commercially available continuous reactor, is used to contain a reaction liquid, which includes an aromatic hydrocarbon and a brominating agent. In this embodiment, the reaction liquid includes an aromatic hydrocarbon 10, a brominating agent 11 and a solvent 12, which are stirred uniformly to obtain a mixture. After the mixture is cooled, the hydrogen peroxide aqueous solution is titrated into the mixture to obtain a reaction mixture 55 including a liquid unreacted aromatic hydrocarbon 10 and a solid aromatic bromide 58.

In this embodiment, the aromatic hydrocarbon 10, the brominating agent 11, the solvent 12 and the reaction conditions used may be the same as those of the first embodiment, and will not be repeated here.

Please continue to refer to FIG. 3. In the third embodiment, the reaction tank I is in fluid communication with the separation unit K and the illumination device J, and the separation unit K is disposed in front of the illumination device J according to the direction of fluid flow, and then comes from the reaction tank I. The reaction mixture 55 is sequentially passed through the separation unit K and the illumination device J, and then returned to the reaction tank I for a cycle process (solid line portion).

In this embodiment, first, the separation unit K may be a centrifugal device with a filter plate for performing a separation step. Specifically, the reaction mixture 55 obtained in the reaction tank I is moved to a separation unit K, and the reaction mixture 55 is separated into a liquid unreacted aromatic hydrocarbon 10 and a solid aromatic hydrocarbon bromide 58 and a solid aromatic hydrocarbon bromine The compound 58 is retained in the separation unit K, and then moved to the replacement reactor L (described later). In other embodiments, the separation unit K may be located in the reaction tank I, so that the reaction mixture 55 is directly separated by the separation unit K in the reaction tank I.

The lighting device J includes a cooling system and a light source for performing a photobromination reaction. In detail, the illuminating device J is in fluid communication with the separation unit K, and the liquid unreacted aromatic hydrocarbon 10 from the separation unit K is further subjected to a photobromination reaction to form a brominated product stream. The stream includes liquid unreacted aromatics and solid aromatic bromides.

More specifically, the liquid unreacted aromatic hydrocarbon 10 in the separation unit K is moved to the lighting device J, so that the liquid unreacted aromatic hydrocarbon 10 is at about -10 ° C to 30 ° C (preferably about 0 ° C to- 10 ° C), through a light source to irradiate for photocatalytic reaction to form a brominated product stream, here brominated mixture 56, which includes liquid unreacted aromatic hydrocarbons 10 and solid Aromatic hydrocarbon bromide 58. In some embodiments, the wavelength of the light source is about 400-700 nm, It is preferably about 420 nm, and the power of the light source is about 20-200 Watts, preferably about 40-100 Watts, and more preferably about 80 Watts. In some embodiments, the reaction time of the photobromination reaction is about 0.5-24 hours, preferably about 4-12 hours.

Furthermore, the illumination device J and the reaction tank I are in communication with each other, so that the brominated mixture 56 is recovered into the reaction tank I, and a cycle process is performed to re-enter the liquid unreacted aromatic hydrocarbon 10 and the solid aromatic hydrocarbon bromide 58 again. The separation is performed in the separation unit K.

In addition, in other embodiments, another separation unit may be additionally provided between the illumination device J and the reaction tank I, and the another separation unit is in fluid communication with the replacement reactor L. Thereby, the brominated mixture 56 from the lighting device J is separated to recover the liquid unreacted aromatic hydrocarbon 10 into the reaction tank I, and the solid aromatic bromide 58 is retained in the other separation unit. In order to subsequently move to the replacement reactor L.

Please continue to refer to FIG. 3. In another embodiment, the reactor I is in fluid communication with the lighting device J and the separation unit K, and the separation unit K is arranged behind the photomask device J according to the fluid flow direction, and then comes from the reaction tank I The reaction mixture 55 is sequentially passed through the illumination device J and the separation unit K, and then returned to the reaction tank I for a cycle process (indicated by a dotted line).

In this embodiment, first, the lighting device J has a cooling system and a light source, and the aromatic hydrocarbons 10 and the brominating agent 11 in the reaction mixture 55 from the reaction tank I are subjected to a photobromination reaction to form a brominated product stream ( stream), the brominated product stream includes a liquid unreacted aromatic hydrocarbon and a solid aromatic hydrocarbon bromide. Specifically, the reaction mixture 55 in the reaction tank I is moved to the lighting device J, and the reaction mixture 55 is conducted through a light source under a temperature environment of about -10 ° C to 30 ° C (preferably about 0 ° C to 10 ° C). Irradiation to effect a photocatalytic reaction to form a brominated product stream, This is a brominated mixture 56 which includes unreacted aromatic hydrocarbons 10 in liquid form and aromatic hydrocarbon bromides 58 in solid form. In this embodiment, the conditions of the photobromination reaction may be the same as those of the foregoing embodiment, and details are not described herein again.

In addition, the separation unit K may be a centrifugal device with a filter plate for performing the separation step. Specifically, the brominated mixture 56 obtained by the illumination device J is moved to a separation unit K, and the brominated mixture 56 is separated into a liquid unreacted aromatic hydrocarbon 10 and a solid aromatic hydrocarbon bromide 58. The separation unit K is in fluid communication with the reaction tank I, so that the liquid unreacted aromatic hydrocarbons 10 are recovered into the reaction tank I, and the solid aromatic bromide 58 is retained in the separation unit K to facilitate subsequent transfer to replacement Reactor L (explained later).

Since the reaction tank I, the lighting device J and the separation unit K form an external circulation system, the liquid unreacted aromatic hydrocarbon 10 can repeatedly enter the lighting device 56 for photobromization reaction until a solid aromatic hydrocarbon bromide 58 is formed. So far, all aromatic hydrocarbon reactants can be fully reacted. Furthermore, since most of the solid aromatic bromide 58 is retained in the separation unit K, and does not follow the above-mentioned external circulation system to the lighting device J, it can reduce the influence on the progress of the photobromination reaction and cause a decrease in efficiency. In addition, an aromatic hydrocarbon 10 and a brominating agent 11 can be continuously added to the reaction tank I, so that the photobromination reaction forms a continuous reaction in the external circulation system, so that the product can be mass-produced and the process efficiency can be improved.

In addition, in the embodiment in which a separation unit is provided before the aforementioned photomask device, since all mixtures pass through the separation unit K before entering the lighting device J, all solid matters (for example, solid aromatic hydrocarbons) can be more ensured. Bromide 58) will be trapped in the separation unit, and will not enter the lighting device J, which can further avoid affecting the progress of the photobromination reaction and reducing the efficiency.

Please continue to refer to Figure 3, instead of reactor L, for example a commercially available company The continuous reactor is used to perform the substitution reaction on the solid aromatic hydrocarbon bromide 58 from the separation unit K. Specifically, the solid aromatic hydrocarbon bromide 58 obtained from the separation unit K is transferred to the substitution reactor L, and water 53 and a basic alkali metal compound 14a or an alkali metal carboxylate 14b are added to the substitution reactor L, and Heated at about 1-10 atm (atm) to about 80-160 ° C (preferably at about 1 atm to about 100-120 ° C, more preferably at about 2-5 atm to about 110-140 ° C) The mixture is refluxed and reacted for about 0.5-24 hours to perform a substitution reaction, thereby forming a reaction mixture 60. The reaction mixture 60 includes a crude product of an aromatic alcohol 26a or an aromatic ester 26b, an alkali metal bromide 27, an acidic compound 28, and water 29.

The basic alkali metal compound 14a, the alkali metal carboxylate 14b, the aromatic hydrocarbon bromide 58 and the reaction conditions thereof may be the same as those in the first embodiment, and will not be repeated here.

Because the replacement reactor L directly receives the crude product from the separation unit K without undergoing recrystallization or distillation purification, that is, the process of forming the crude product of the aromatic alcohol or aromatic ester from the aromatic hydrocarbon 10 does not go through Any step of crystallization or distillation to purify the intermediate, thus simplifying the process steps.

Next, as shown in FIG. 3, the distillation unit M, such as a commercially available distillation equipment, is used to perform a distillation step on the reaction mixture 60 from the substitution reactor L. Specifically, in the distillation unit M, the acidic compound 28 and water 29 of the reaction mixture 60 are distilled off by the difference in boiling points, and the remaining part contains an alkali metal bromide 27 and an aromatic alcohol 26a or an aromatic ester 26b. The mixture of crude products 64.

The neutralization unit N, such as a commercially available acid-base neutralization tank, is used to neutralize the acidic compound 28 and water 29 from the distillation unit M. Specifically, a basic compound 34 is added to the neutralization unit N, and a neutralization reaction with the acidic compound 28 and water 29 is performed to form a basic alkali metal compound 14a or an alkali metal carboxylate. 物 14b。 14b. Furthermore, the neutralization unit N is in fluid communication with the substitution reactor L, so that the alkaline alkali metal compound 26a or the alkali metal carboxylate 26b obtained by the neutralization unit N is recovered into the substitution reactor L.

Please continue to refer to FIG. 3, the extraction unit O is used to perform the extraction step on the mixture 64 from the distillation unit M. Specifically, an extraction solvent 20 is added to the extraction unit O to separate the mixture 64 into an organic phase 68 and an aqueous phase. The organic phase 68 includes the crude product of the aromatic alcohol 26a or the aromatic ester 26b, and the aqueous phase is the alkali metal bromide 27. In some embodiments, the extraction solvent 20 includes Methyl isobutyl ketone (MIBK), ethyl acetate, or other suitable solvents. In some embodiments, the weight ratio of the mixture 64 to the extraction solvent 20 is 1: 1.

Next, as shown in FIG. 3, the regeneration unit Q is, for example, a redox reaction tank, and is used to react the alkali metal bromide 27 from the extraction unit O to generate hydrobromic acid 11a again. Specifically, concentrated sulfuric acid 30 is added to the regeneration unit Q, and is reacted with the alkali metal bromide 27 to form hydrobromic acid 11a and alkali metal salts 32. Furthermore, the regeneration unit Q is in fluid communication with the reaction tank I, so that the hydrobromic acid 11a obtained by the regeneration unit Q is recovered into the reaction tank I. In some embodiments, the molar equivalent ratio of alkali metal bromide 27 to concentrated sulfuric acid 30 is 1: 2-4.

Furthermore, as shown in FIG. 3, the purification unit P is used for purifying the organic phase 68 from the extraction unit O to separate the product of the aromatic alcohol 26a or the aromatic ester 26b from the extraction solvent 20 and extract the The solvent 20 is recovered into the extraction unit O. In some embodiments, the purification unit P includes a crystallization unit and / or a distillation unit. Therefore, the purification step includes a crystallization step, a distillation step, or a combination thereof. In the embodiment using the preparation system 300, the yield of the aromatic alcohol 26a or the aromatic ester 26b can reach more than 78%, and in some experimental examples, it can reach 78% -97%, and the purity of the aromatic alcohol 26a or the aromatic ester 26b can be Up to 92%, in some experimental cases up to 95%.

In this embodiment, since the photobromination reaction can be continuously performed, all aromatic hydrocarbon reactants can be fully reacted, and therefore, the production efficiency can be improved and an aromatic derivative having a higher yield can be obtained.

In summary, the present disclosure provides a preparation system and a preparation method for aromatic derivatives. Since by-products produced by the reaction can be recovered and reused, the energy consumption of the reaction can be reduced, the preparation cost can be saved, and the production efficiency can be improved. Furthermore, in some embodiments, the process of purifying intermediates such as recrystallization or distillation is not required in the process of forming aromatic derivatives from aromatic hydrocarbons, so the process can be simplified.

The following provides experimental examples of aromatic derivatives obtained by the preparation system and the preparation method of the present disclosure. Specifically, the preparation conditions of aromatic derivatives described in Experimental Examples 1-11, the reactant formulation, and the yield and purity obtained are summarized in Table 1 below. Among them, Experimental Examples 1-5 are using the preparation system 100 of the first embodiment to prepare aromatic derivatives; Experimental Examples 6-8 are using the preparation system 200 of the second embodiment to prepare aromatic derivatives. Experimental Examples 9-14 use the preparation system 300 of the third embodiment described above to prepare aromatic derivatives.

In the following experimental examples, the yield is defined as: the mole number of the aromatic derivative product / the mole number of the aromatic hydrocarbon reactant * 100%.

In the following experimental examples, a GC-FID detector was used (system product: Agilent 7890A Single FID SVOA GC System, purchased from Pace Analytical Services, LLC) to detect the purity of the product. The detection method is as follows: 0.5g of sample is dissolved In 10 g of tetrahydrofuran (THF), the sample was subjected to ultrasonic vibration for 0.5 hours. The sample was then filtered and the filtrate was analyzed by a GC-FID instrument.

GC conditions: J & W DB-1 (60m × 250um × 0.25um) capillary Column; column temperature was maintained at 80 ° C for 2 minutes, and then increased from 80 ° C to 260 ° C. Hold at 10 ° C / min, then at 260 ° C for 5 minutes. Injection temperature: 300 ° C. Injection volume: 0.2 μL; sample injection mode: split, split ratio is 100: 1; carrier gas flow rate: 1.50 mL / min; FID temperature: 300 ° C.

[Experimental Example 1]: Preparation of aromatic derivatives using the preparation system 100

Photobromination

At 1 atmosphere and room temperature, 1 mol equivalent of para-xylene (purchased from ACROS OEGANICS, Sigma-Aldrich), 2.05 mol equivalent of hydrobromic acid (HBr) (48wt%), and 2.15 Molar equivalents of dichloroethane were placed in a glass reactor and stirred with a mechanical stirrer.

After the above mixture was cooled to about 5-10 ° C in an ice water bath, 2.5 mol equivalent of hydrogen peroxide (35wt%) was slowly added using a peristaltic pump, and at the same time, a bulb with a wavelength of 400-700nm and a power of 80 watts Irradiation is performed to perform a photocatalytic reaction. During the process of adding hydrogen peroxide, the system temperature does not exceed 15 ° C. If it exceeds 15 ° C, stop adding hydrogen peroxide and wait until the temperature drops. When the addition of hydrogen peroxide is complete, the reaction can be terminated as the color of the mixed solution changes from dark yellow to light yellow, and the reaction time is about 6 hours. Then, the reaction system was warmed to room temperature.

Substitution reaction

2.1 mol equivalent of sodium formate (purchased from Li Changrong Chemical Industry Co., Ltd.) and 10 times the weight of water of sodium formate were directly added to the above glass reactor, and the reaction was heated to a reflux state of about 100 ° C at 1 atmosphere. To perform a substitution reaction. Through an oil-water separation device provided in the glass reactor, dichloroethane is removed and recovered, and water is left in the reaction system.

After carrying out the above substitution reaction for about 6 hours, the system temperature was lowered to At room temperature, move the reaction mixture to the extraction tank, and add the extraction solvent of methyl isobutyl ketone (MIBK) to the extraction tank for extraction. The weight ratio of the reaction mixture to methyl isobutyl ketone (MIBK) The ratio is 1: 1. Then, after taking the organic phase of the extract and recovering the solvent with a rotary concentrator, p-xylylene glycol can be obtained. The yield of the obtained p-xylylene glycol was 62%, and the purity was 85% measured by a GC-FID instrument.

Furthermore, the aqueous phase of the extract was distilled under reduced pressure, the formic acid and water were distilled off, the acid value of formic acid was detected, and sodium hydroxide (NaOH) was added for neutralization reaction to obtain sodium formate and recover it. .

The solid left by distillation under reduced pressure is sodium bromide. After recrystallization, purification and drying of sodium bromide, 1 mol equivalent of sodium bromide and 15 mol equivalent of water are mixed in a glass bottle, and The sodium bromide aqueous solution was heated to about 80 ° C., and then 1 mol equivalent of 97% concentrated sulfuric acid was slowly added dropwise to the sodium bromide aqueous solution, and the dropping time was controlled to about 30 minutes. After the addition of sulfuric acid is completed, the water and the hydrobromic acid (HBr) produced are concentrated together under reduced pressure at 1 atmosphere and 125 ° C (the azeotropic temperature of water and hydrobromic acid is 125 ° C at 1 atmosphere), Collecting the distillate gives a regenerated aqueous solution of hydrobromic acid.

[Experimental Example 2]: Preparation of aromatic derivatives using the preparation system 100

The reaction steps and reaction conditions of Experimental Example 2 are basically the same as those of Experimental Example 1. The difference is that in the substitution reaction of Experimental Example 2, the reactant formula was changed to 2.2 mole equivalents of sodium acetate and 10 times the weight of sodium acetate. . The obtained product was 1,4-benzenedimethanol diacetate, and the yield of 1,4-benzenedimethanol diacetate was 62% and the purity was 95%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 3]: Preparation of aromatic derivatives using the preparation system 100

The reaction steps and reaction conditions of Experimental Example 3 are basically the same as those of Experimental Example 1. The difference is that in the substitution reaction of Experimental Example 3, the formula of the reactant was changed to 3 mol equivalent of sodium hydroxide, water, and 1,4-diamine. 1,4-Dioxane (wherein the weight ratio of 1,4-dioxane to water is 1: 1, and the total weight of 1,4-dioxane and water is 10 times that of sodium hydroxide), The reaction time was increased to 12 hours. The resulting product, p-xylylene glycol, had a yield of 65% and a purity of _92_%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 4]: Preparation of aromatic derivatives using the preparation system 100

The reaction steps and reaction conditions of Experimental Example 4 are basically the same as those of Experimental Example 1. The difference is that in the photobromination reaction of Experimental Example 4, the formula of the reactant was changed to 5 mole equivalents of toluene (Toluene) and 1 mole equivalent. Hydrobromic acid (48 wt%), and the added hydrogen peroxide content was changed to 1.2 mole equivalents.

In addition, in the substitution reaction of Experimental Example 4, the reactant formula was changed to 2 mol equivalent of sodium hydroxide, water, and 1,4-dioxane (1,4-dioxane) The weight ratio of alkane to water was 1: 1, and the total weight of 1,4-dioxane and water was 10 times that of sodium hydroxide), and the reaction time was shortened to 6 hours. The obtained product was benzyl alcohol, and the yield of benzyl alcohol was 83% and the purity was 93%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 5]: Preparation of aromatic derivatives using the preparation system 100

The reaction steps and reaction conditions of Experimental Example 5 are basically the same as those of Experimental Example 1. The difference is that in the photobromination reaction of Experimental Example 5, the reactant formula was changed to 5 molar equivalents of toluene (Toluene) and 1 molar equivalent of hydrobromic acid (48 wt%), and the content of hydrogen peroxide added was changed to 1.2 molar equivalents.

In addition, in the replacement reaction of Experimental Example 5, the reactant formula was changed to 2.2 mol equivalent of sodium methacrylate, 1000 ppm of hydroquinone monomethyl ether (as an inhibitor), and 10 times the weight of sodium methacrylate. Water. The obtained product was benzyl methacrylate, and the yield of benzyl methacrylate was 76% and the purity was 90%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 6]: Preparation of aromatic derivatives using the preparation system 200

Photobromination

At 1 atmosphere and room temperature, 1 mol equivalent of p-xylene, 2.05 mol equivalent of hydrobromic acid (48 wt%), and 2.15 mol equivalent of dichloroethane were placed in a glass reactor and mechanically Stirrer.

After the above mixture was cooled to about 5-10 ° C in an ice water bath, 2.5 mol equivalent of hydrogen peroxide (35wt%) was slowly added using a peristaltic pump, and at the same time, a bulb with a wavelength of 400-700nm and a power of 80 watts Irradiation is performed to perform a photocatalytic reaction. During the process of adding hydrogen peroxide, the system temperature does not exceed 15 ° C. If it exceeds 15 ° C, stop adding hydrogen peroxide and wait until the temperature drops. When the addition of hydrogen peroxide is complete, the reaction can be terminated as the color of the mixed solution changes from dark yellow to light yellow, and the reaction time is about 6 hours. The reaction system was allowed to warm to room temperature, at which time the glass reactor was a mixed solution with a white solid.

Substitution reaction

Then, after separating the solid and liquid through the Buchner funnel, The white solid intermediate product (here, α, α'-dibromo-p-xylene) was weighed and put back into another reactor. Furthermore, 2.1 mol equivalent of sodium formate and 10 times the weight of sodium formate were added. It was directly added to the other reactor mentioned above, and the reaction was heated to a reflux state of about 100 ° C. under 1 atmosphere to perform a substitution reaction.

After the above-mentioned substitution reaction is performed for about 8 hours, the temperature of the system is reduced to room temperature, and the reaction mixture is moved to an extraction tank. An extraction solvent of methyl isobutyl ketone (MIBK) is added to the extraction tank for extraction, and the reaction is mixed The weight ratio of liquid to methyl isobutyl ketone (MIBK) is 1: 1. Then, after taking the organic phase of the extract and recovering the solvent with a rotary concentrator, p-xylylene glycol can be obtained. . The yield of the obtained p-xylylene glycol was 92%, and the purity was 90% measured by a G-C instrument.

Furthermore, the aqueous phase of the extract was distilled under reduced pressure, the formic acid and water were distilled off, the acid value of formic acid was detected, and sodium hydroxide (NaOH) was added to perform the reduction reaction to obtain sodium formate and recover it.

The solid left by distillation under reduced pressure is sodium bromide. After the sodium bromide is recrystallized, purified, and dried, 1 mole equivalent of sodium bromide and 15 mole equivalent of water are mixed in a glass bottle, and bromine is added. The sodium chloride aqueous solution was heated to about 80 ° C, and then 1 mol equivalent of 97% concentrated sulfuric acid was slowly added dropwise to the sodium bromide aqueous solution, and the dropping time was controlled to about 30 minutes. After the addition of sulfuric acid is completed, the water and the hydrobromic acid (HBr) produced are concentrated together under reduced pressure at 1 atmosphere and 125 ° C (the azeotropic temperature of water and hydrobromic acid is 125 ° C at 1 atmosphere), Collecting the distillate gives a regenerated aqueous solution of hydrobromic acid.

[Experimental Example 7]: Preparation of aromatic derivatives using the preparation system 200

The reaction steps and reaction conditions of Experimental Example 7 are basically the same as those of Example 6. Similarly, the difference is that in the substitution reaction of Experimental Example 7, the reactant formula was changed to 2.2 mol equivalent of sodium acetate and 10 times the weight of water of sodium acetate. The obtained product was 1,4-benzenedimethanol diacetate, and the yield of 1,4-benzenedimethanol diacetate was 96% and the purity was 95%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 8]: Preparation of aromatic derivatives using the preparation system 200

The reaction steps and reaction conditions of Experimental Example 8 are basically the same as those of Experimental Example 6. The difference is that in the substitution reaction of Experimental Example 8, the formula of the reactant was changed to 3 mol equivalent of sodium hydroxide, water, and 1,4-diamine. 1,4-Dioxane (wherein the weight ratio of 1,4-dioxane to water is 1: 1, and the total weight of 1,4-dioxane and water is 10 times that of sodium hydroxide), The reaction time was increased to 12 hours. The resulting product, p-xylylene glycol, has a yield of 75% and a purity of 93%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 9]: Preparation of aromatic derivatives using the preparation system 300

Photobromination

At 1 atmosphere and room temperature, place 1 mol equivalent of p-xylene, 2.05 mol equivalent of hydrobromic acid (48 wt%) and 2.15 mol equivalent of dichloroethane in a Teflon filter plate. The glass reactor was stirred with a mechanical stirrer.

After the above mixture was cooled to about 5-10 ° C in an ice water bath, 2.5 mol equivalent of hydrogen peroxide (35 wt%) was slowly added to the above glass reactor by using a peristaltic pump.

The reaction solution of the above glass reactor was beaten with another set of peristaltic pumps. In a photoreactor with a cooling system, a light bulb with a wavelength of 400-700nm and a power of 80 watts is irradiated while maintaining a temperature of 5-10 ° C to perform a photocatalytic reaction and form a mixed solution with a solid . The mixed solution was refluxed into the original glass reactor to form an external circulation system. During the entire process, the system temperature does not exceed 15 ° C. If it exceeds 15 ° C, the addition of hydrogen peroxide is stopped, and the temperature can be continued when the temperature drops.

Through the Teflon filter plate in the glass reactor, the solids are retained in the glass reactor, so that the solids will not run into the light reactor with the external circulation system, resulting in a decrease in the light reaction efficiency. When the addition of hydrogen peroxide is complete, the reaction can be terminated as the color of the mixed solution changes from dark yellow to light yellow, and the reaction time is about 6 hours.

Substitution reaction

Separate the solid and liquid directly through the Teflon filter plate in the glass reactor, obtain the intermediate product of white solid (here, α, α'-dibromo-p-xylene), weigh it, and put it back into another reactor Furthermore, 2.1 mol equivalent of sodium formate and 10 times the weight of water of sodium formate were directly added to the above another reactor, and the reaction was heated to a reflux state of about 100 ° C. at 1 atmosphere to perform a substitution reaction.

Furthermore, after the above-mentioned substitution reaction was performed for about 8 hours, the temperature of the system was reduced to room temperature, and the reaction mixture was distilled under reduced pressure. The formic acid and water were distilled off. (NaOH) is subjected to a reduction reaction to obtain sodium formate and recover it.

The solid left by the vacuum distillation is transferred to an extraction tank, and an extraction solvent of methyl isobutyl ketone (MIBK) is added to the extraction tank for extraction. The reaction mixture is mixed with the methyl isobutyl ketone (MIBK). The weight ratio is 1: 1. Next, extract After taking the organic phase of the liquid and recovering the solvent by a rotary concentrator, p-xylylene glycol can be obtained. The yield of the obtained p-xylylene glycol was 95%, and the purity was 92% measured by a G-C-FID instrument.

Furthermore, the aqueous phase of the extract is sodium bromide. After the sodium bromide is recrystallized, purified, and dried, 1 mol equivalent of sodium bromide and 15 mol equivalent of water are mixed in a glass bottle, and the bromine is The sodium chloride aqueous solution was heated to about 80 ° C, and then 1 mol equivalent of 97% concentrated sulfuric acid was slowly added dropwise to the sodium bromide aqueous solution, and the dropping time was controlled to about 30 minutes. After the addition of sulfuric acid is completed, the water and the hydrobromic acid (HBr) produced are concentrated together under reduced pressure at 1 atmosphere and 125 ° C (the azeotropic temperature of water and hydrobromic acid is 125 ° C at 1 atmosphere), Collecting the distillate gives a regenerated aqueous solution of hydrobromic acid.

[Experimental Example 10]: Preparation of aromatic derivatives using the preparation system 300

The reaction steps and reaction conditions of Experimental Example 10 are basically the same as those of Experimental Example 9. The difference is that in the substitution reaction of Experimental Example 10, the reactant formula was changed to 2.2 mole equivalents of sodium acetate and 10 times the weight of water of sodium acetate. . The obtained product was 1,4-benzenedimethanol diacetate, and the yield of 1,4-benzenedimethanol diacetate was 95% and the purity was 95%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 11]: Preparation of aromatic derivatives using the preparation system 300

The reaction steps and reaction conditions of Experimental Example 11 are basically the same as those of Experimental Example 9. The difference is that in the substitution reaction of Experimental Example 11, the reactant formula was changed to 3 mol equivalent of sodium hydroxide, water, and 1,4-diamine. 1,4-Dioxane (wherein the weight ratio of 1,4-dioxane to water is 1: 1, and the total weight of 1,4-dioxane to water is hydroxide 10 times sodium sulfide), and the reaction time was increased to 12 hours. The resulting product, p-xylylene glycol, had a yield of 78% and a purity of 93%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 12]: Preparation of aromatic derivatives using the preparation system 300

The reaction steps and reactant formulations of Experimental Example 12 are basically the same as those of Experimental Example 9. The difference is that in the substitution reaction of Experimental Example 12, the reaction conditions were changed to 3 atmospheres and a temperature of 130 ° C. for 3 hours. The obtained product was p-xylylene glycol, and the yield of p-xylylene glycol was 92% and the purity was 94%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 13]: Preparation of aromatic derivatives using the preparation system 300

The reaction steps of Experimental Example 13 are basically the same as those of Experimental Example 9. The difference is that in the substitution reaction of Experimental Example 13, the reactant formula was changed to 2.1 mol equivalent of sodium formate and 5 times the weight of sodium formate. The reaction conditions were changed to a reaction at 3 atmospheres and a temperature of 130 ° C for 1 hour. The obtained product was p-xylylene glycol, and the yield of p-xylylene glycol was 93% and the purity was 92%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

[Experimental Example 14]: Preparation of aromatic derivatives using the preparation system 300

The reaction steps and reactant formulations of Experimental Example 14 are basically the same as those of Experimental Example 9. The difference is that in the substitution reaction of Experimental Example 14, the reaction conditions were changed to 4 atm and 140 ° C. for 1 hour. The obtained product was p-xylylene glycol, and the yield of p-xylylene glycol was 97% and the purity was 94%. Please refer to Table 1 for detailed reagent formulation and reaction conditions.

It can be known from Table 1 that when the reactant formulation and reaction conditions are the same (for example: Experimental Example 1, Example 6 and Example 9), compared to Experimental Example 1 using the preparation system 100, the preparation system 200 is used. Example 6 has higher yield and purity, because in the preparation system 200, the photobromination reaction and the substitution reaction are performed in different reactors, respectively. In addition, compared with Example 6 using the preparation system 200, Example 9 using the preparation system 300 has higher yield and purity, because in the preparation system 300, the photobromination reaction can be performed continuously, All the p-xylene reactants can be fully reacted, and therefore, the yield and production efficiency can be improved.

The foregoing text summarizes the features of many embodiments so that those having ordinary skill in the art can better understand the various aspects of the present disclosure. Those with ordinary knowledge in the technical field should understand that they can easily design or modify other processes and structures based on this disclosure, and thereby achieve the same purpose and / or achieve the same as the embodiments described in this disclosure. The advantages. Those of ordinary skill in the art should also understand that these equivalent structures do not depart from the spirit and scope of the invention disclosed herein. Various changes, substitutions, and modifications can be made in the disclosure without departing from the spirit and scope of the disclosure.

100‧‧‧ Preparation System

10‧‧‧Aromatics

11‧‧‧ Brominating agent

11a‧‧‧hydrobromic acid

11b‧‧‧hydrogen peroxide solution

12‧‧‧ Solvent

13‧‧‧ water

14a‧‧‧Alkali alkali metal compounds

14b‧‧‧ alkali metal carboxylate

16‧‧‧Aromatic hydrocarbon bromide

18‧‧‧ reaction mixture

20‧‧‧extraction solvents

22‧‧‧ organic phase

24‧‧‧ water phase

26a‧‧‧Aromatic alcohol

26b‧‧‧Aromatic ester

27‧‧‧ Alkali metal bromide

28‧‧‧ acidic compounds

29‧‧‧ Water

30‧‧‧ concentrated sulfuric acid

32‧‧‧ alkali metal salts

34‧‧‧ basic compounds

R‧‧‧ Reactor

A‧‧‧Photobromination reaction zone

B‧‧‧ Separation Unit

C‧‧‧ replaces the reaction zone

D‧‧‧extraction unit

E‧‧‧purification unit

F‧‧‧Distillation unit

G‧‧‧Regeneration unit

H‧‧‧ Neutralization Unit

Claims (31)

An aromatic derivative preparation system includes: a photobromination reaction zone, where an aromatic hydrocarbon and a brominating agent are subjected to a photocatalytic reaction to form an aromatic hydrocarbon bromide; and a substitution reaction zone, which is derived from the photobromination reaction The aromatic hydrocarbon bromide is subjected to a substitution reaction with an alkali base compound or an alkali carboxylate compound to form an aromatic derivative; and a regeneration unit enables the substitution reaction zone An alkali metal bromide formed reacts with an acid to form monohydrobromic acid, and the regeneration unit is in fluid communication with the photobromination reaction zone to recover the hydrobromic acid to the photobromination reaction Area. The aromatic derivative preparation system according to item 1 of the scope of patent application, wherein the photobromination reaction zone and the substitution reaction zone are located in the same reactor. The aromatic derivative preparation system according to item 1 of the scope of patent application, wherein the photobromination reaction zone and the substitution reaction zone are located in different reactors. The aromatic derivative preparation system according to item 1 of the application, wherein the substitution reaction zone directly receives the crude product from the photobromination reaction zone without undergoing a recrystallization or a distillation purification unit. The aromatic derivative preparation system according to item 1 of the patent application scope further includes: an extraction unit that separates a product stream formed in the substitution reaction zone into an aqueous phase stream and an organic phase stream, wherein the organic phase stream Phase flow including the aromatic derivative A distillation unit to separate the aqueous phase stream from the extraction unit into the alkali metal bromide, an acidic compound, and a first solvent; wherein the distillation unit is in fluid communication with the photobromination reaction zone so that The first solvent is recovered into the photobromination reaction zone. The aromatic derivative preparation system described in item 5 of the scope of patent application, further comprising: a neutralization unit, which reacts the acidic compound from the distillation unit with a basic compound to form the basic alkali metal compound or the An alkali metal carboxylate, and the neutralization unit is in fluid communication with the substitution reaction zone, so that the alkali alkali metal compound or the alkali metal carboxylate is recovered into the substitution reaction zone. The aromatic derivative preparation system described in item 5 of the scope of patent application, further comprising: a purification unit in fluid communication with the extraction unit for purifying the organic phase stream from the extraction unit to obtain the purified Aromatic derivative. An aromatic derivative preparation system includes: a reaction tank for containing a reaction liquid, the reaction liquid including an aromatic hydrocarbon and a brominating agent; a light-emitting device, the aromatic hydrocarbon and the The brominating agent performs a photobromination reaction to form a brominated product stream including a liquid unreacted aromatic hydrocarbon and a solid aromatic hydrocarbon bromide; A separation unit that separates the solid aromatic hydrocarbon bromide from the liquid unreacted aromatic hydrocarbon, wherein the separation unit is in fluid communication with the reaction tank to circulate the liquid unreacted aromatic hydrocarbon to the reaction tank And a substitution reactor for subjecting the solid aromatic bromide from the separation unit to a substitution reaction with an alkali base compound or an alkali carboxylate compound to form An aromatic derivative. The aromatic derivative preparation system according to item 8 of the scope of patent application, wherein the illumination device includes a light source, and the wavelength of the light source is 400-700 nm. The aromatic derivative preparation system according to item 9 of the patent application, wherein the wavelength of the light source is about 420 nm. The aromatic derivative preparation system according to item 8 of the application, wherein the separation unit is located in the reaction tank. The aromatic derivative preparation system according to item 8 of the scope of patent application, wherein the yield of the aromatic derivative is greater than or equal to 78%. The aromatic derivative preparation system according to item 8 of the scope of the patent application, further comprising: a regeneration unit that reacts an alkali metal bromide formed in the substitution reactor with an acid to form monohydrobromic acid, and the The regeneration unit is in fluid communication with the reaction tank to recover the hydrobromic acid into the reaction tank. A method for preparing an aromatic derivative includes: (a) performing a photobromination reaction of an aromatic hydrocarbon and a brominating agent in a first solvent to form an aromatic hydrocarbon bromide; (b) performing a substitution reaction between the aromatic hydrocarbon bromide and an alkali base compound or an alkali carboxylate compound in a second solvent to form an aromatic derivative; And (c) reacting an alkali metal bromide formed by the substitution reaction with an acid to form monohydrobromic acid, and recovering the hydrobromic acid for use in step (a). The method for preparing an aromatic derivative according to item 14 of the scope of the patent application, wherein no recrystallization or distillation purification step is performed between steps (a) and (b). The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein step (a) and step (b) are performed in the same reactor. The method for preparing an aromatic derivative according to item 14 of the scope of the patent application, wherein step (a) and step (b) are performed in different reactors. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (a), the reaction temperature of the photobromination reaction is -10 ° C to 30 ° C, and the reaction time is 0.5 to 24 hours. The light source wavelength is 400-700nm. The method for preparing an aromatic derivative according to item 14 of the scope of the patent application, wherein in step (b), the reaction temperature of the substitution reaction is 80 ° C to 160 ° C, the reaction time is 0.5 to 24 hours, and the reaction pressure is 1 atmosphere to 10 atmospheres. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (a), the brominating agent comprises the hydrobromic acid and a hydrogen peroxide aqueous solution, the aromatic hydrocarbon, the hydrobromic acid and The molar equivalent ratio of the first solvent is 1: 2-3: 1-20, and the molar hydrocarbon of the aromatic hydrocarbon and the hydrogen peroxide solution is The quantity ratio is 1: 2-5. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (b), the molar equivalent ratio of the basic alkali metal compound or the alkali metal carboxylate to the aromatic hydrocarbon bromide is 2 -5: 1. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (c), the molar equivalent ratio of the alkali metal bromide to the acid is 1: 2-4. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (a), the first solvent includes halogenated hydrocarbons; wherein in step (b), the second solvent includes water. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (a), the brominating agent comprises: (1) bromine water (Br ₂ ); (2) hydrobromic acid (HBr) And a hydrogen peroxide aqueous solution; (3) a combination of sodium bromide (NaBr), sulfuric acid (H ₂ SO ₄ ) and an aqueous hydrogen peroxide solution; or a combination thereof. The method for preparing an aromatic derivative according to item 14 of the scope of patent application, wherein in step (b), the basic alkali metal compound includes sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), hydroxide Potassium (KOH) or a combination thereof. The method for preparing an aromatic derivative according to item 14 of the application, wherein in step (b), the alkali metal carboxylate includes sodium formate, sodium acetate, or a combination thereof. The method for preparing an aromatic derivative according to item 14 of the patent application scope, wherein after step (b), the method further comprises: (d) performing a product stream formed by the substitution reaction with an extraction solvent An extraction step to separate the product stream into an aqueous phase stream and an organic phase stream, wherein the organic phase stream includes the aromatic derivative; and (e) subjecting the aqueous phase stream to a distillation step such that the aqueous phase stream It is separated into the alkali metal bromide, an acidic compound and a first solvent. The method for preparing an aromatic derivative according to item 27 of the scope of patent application, wherein after step (e), it further comprises: (f) reacting the acidic compound with a basic compound to form the basic alkali metal compound or The alkali metal carboxylate, and the basic alkali metal compound or the alkali metal carboxylate is recovered for use in step (b); and (g) the first solvent is recovered for use in step (a). The method for preparing an aromatic derivative according to item 27 of the scope of patent application, wherein after step (d), the method further comprises: (h) subjecting the organic phase stream to a purification step, and extracting the extraction solvent from the purification step Recovered for step (d), wherein the purification step includes a crystallization step, a distillation step, or a combination thereof. The method for preparing an aromatic derivative according to item 14 of the scope of the patent application, wherein the aromatic hydrocarbon comprises a monoaromatic cyclic hydrocarbon, a biaromatic cyclic hydrocarbon or a triaromatic cyclic hydrocarbon. The method for preparing an aromatic derivative according to item 30 of the patent application, wherein the monoaromatic cyclic hydrocarbon includes or ; Wherein R and R ₁ are linear or branched alkyl groups having 1 to 15 carbon atoms.