阅读说明：本技术 一种双（2-羟基乙基）对苯二甲酸酯块状单晶的制备方法 (Preparation method of bis (2-hydroxyethyl) terephthalate blocky single crystal ) 是由 辛加余 黄俊杰 吕兴梅 晏冬霞 张旗 周清 张锁江 于 2021-01-21 设计创作，主要内容包括：本发明公开了一种双(2-羟基乙基)对苯二甲酸酯(以下简称为“BHET”)块状单晶的制备方法,所述方法包括：取BHET粗品,加入结晶溶剂,加热溶解,得BHET溶液,再进行梯度降温结晶,然后经过滤、洗涤、干燥后获得BHET块状单晶。本发明涉及的BHET块状单晶的制备方法解决了聚对苯二甲酸乙二醇酯(PET)降解单体脱色困难、不彻底的问题,得到了高纯度的BHET块状单晶,对实现PET的闭环循环回收具有重要意义。该方法工艺简单,成本低,便于实现工业化生产。(The invention discloses a preparation method of a bis (2-hydroxyethyl) terephthalate (hereinafter referred to as BHET) bulk single crystal, which comprises the following steps: adding a crystallization solvent into the BHET crude product, heating and dissolving to obtain a BHET solution, performing gradient cooling crystallization, and then filtering, washing and drying to obtain the BHET bulk single crystal. The preparation method of the BHET bulk single crystal solves the problems of difficult and incomplete decolorization of polyethylene terephthalate (PET) degradation monomers, obtains the BHET bulk single crystal with high purity, and has important significance for realizing closed-loop recycling of PET. The method has simple process and low cost, and is convenient for realizing industrial production.)

1. A preparation method of a bis (2-hydroxyethyl) terephthalate bulk single crystal is characterized by comprising the following specific steps:

(1) adding a crystallization solvent into the crude bis (2-hydroxyethyl) terephthalate, and heating and dissolving to obtain a bis (2-hydroxyethyl) terephthalate solution;

(2) transferring the bis (2-hydroxyethyl) terephthalate solution to a crystallizer for crystallization, wherein the initial crystallization temperature is the temperature for heating and dissolving in the step (1);

(3) reducing the temperature to the crystallization temperature at a cooling rate of 1-10 ℃/h, and keeping the temperature for 6-24 h to observe obvious crystal precipitation;

(4) and then reducing the temperature to the final crystallization temperature at the cooling rate of 2-6 ℃/h, and obtaining the bis (2-hydroxyethyl) terephthalate blocky single crystal after filtering, washing and drying.

2. The crystallization method according to claim 1, wherein the crude bis (2-hydroxyethyl) terephthalate in step (1) is obtained from waste PET polyester by glycolysis.

3. The crystallization method according to claim 1, wherein the crystallization solvent in the step (1) is ethyl acetate or ethanol, and the mass ratio of the ethyl acetate or ethanol to the crude bis (2-hydroxyethyl) terephthalate is 2: 1-10: 1.

4. The crystallization method according to claim 1, wherein the heating temperature in the step (1) is 60 to 70 ℃.

5. The crystallization method according to claim 1, wherein the crystallization temperature in the step (3) is 35 to 50 ℃.

6. The crystallization method according to claim 1, wherein the crystallization final temperature in the step (4) is 5 to 25 ℃.

7. The crystallization method according to claim 1, wherein the impurity-containing crystallization solvent obtained by filtration in the step (4) is distilled at 75-80 ℃ to obtain a pure crystallization solvent which can be reused.

Technical Field

The invention relates to a preparation method of a bis (2-hydroxyethyl) terephthalate (hereinafter referred to as BHET) bulk single crystal, belonging to the field of solid waste resource utilization.

Background

BHET is a monomer product obtained by glycolysis of polyethylene terephthalate (hereinafter referred to as "PET") and has a chemical formula of C₁₂H₁₄O₆And the molecular weight is 254.24. In the chemical recovery process of PET, the PET can be alcoholyzed by ethylene glycol to obtain BHET monomer, and the monomer product is purified and polymerized again to obtain regenerated PET. Among the purification processes of BHET, recrystallization is one of the most commonly used methods. The conventional recrystallization purification method is to dissolve BHET in a crystallization solvent and then to perform cooling crystallization at a specific temperature (mostly room temperature). The BHET crystal obtained by the method has small size and large shape difference, is easy to adsorb and wrap residual coloring agent, catalyst, auxiliary agent, degradation solvent and the like in the degradation product, not only leads to unsatisfactory purification effect of the product, but also leads to difficult separation of the product and overhigh content of the solvent in the product. In addition, the national standard GB/T17931-2018 has strict regulations on the chromaticity of PET polyester for bottles, the L value of the PET polyester for food packaging is not less than 80, and the b value is not less than 2.0(HunterLab color system), so the decolorization of BHET monomer is particularly important.

Chinese patent CN110590551A discloses a method for producing bis (2-hydroxyethyl) terephthalate and a method for producing polyethylene terephthalate, wherein a method for purifying BHET by slow-cooling recrystallization with water is mentioned, i.e. BHET needle crystals with high quality are obtained by strictly controlling the cooling rate of water in the crystallization process, and the length of the BHET needle crystals can reach 100 μm. However, in this patent, in order to deeply remove coloring impurities in BHET, an additional step of adsorption treatment, decomposition treatment or reduction treatment is required in the purification process of BHET, and the fundamental reason is that deep decolorization of BHET is difficult to achieve by single crystal purification. Meanwhile, the crystallization solvent must be removed before the crystallized BHET enters the polymerization section, the boiling point of water is high, the removal difficulty is high, and particularly in the large-scale production process, a large amount of energy consumption is generated in the drying process.

Disclosure of Invention

The invention provides a preparation method of a BHET bulk single crystal aiming at the problems. BHET bulk single crystals with compact molecular arrangement and larger crystal size are prepared by screening crystallization solvents and adopting a gradient cooling crystallization method, and the side length of the BHET bulk single crystals can reach 1 cm. Compared with the needle-shaped crystal, the bulk crystal has larger volume and smaller specific surface area, the impurities doped into the crystal are greatly reduced, a small amount of impurities adsorbed on the surface of the crystal can be removed through simple water washing, and the effective separation of BHET and other impurities is realized.

The above object of the present invention is achieved by the following technical solutions:

a preparation method of BHET bulk single crystal comprises the following steps:

(1) taking a BHET crude product, adding a crystallization solvent, and heating for dissolving to obtain a BHET solution;

(2) transferring the BHET solution to a crystallizer for crystallization, wherein the initial crystallization temperature is the temperature for heating and dissolving in the step (1);

(3) reducing the temperature to the crystallization temperature at a cooling rate of 1-10 ℃/h, and keeping the temperature for 6-24 h to observe obvious crystal precipitation;

(4) and then reducing the temperature to the final crystallization temperature at the cooling rate of 2-6 ℃/h, and filtering, washing and drying to obtain the BHET bulk single crystal.

The BHET crude product in the step (1) is obtained by carrying out glycolysis on waste PET polyester.

Preferably, the crystallization solvent in the step (1) is ethyl acetate or ethanol, and the mass ratio of the ethyl acetate or ethanol to the BHET is 2: 1-10: 1.

Preferably, the heating temperature in the step (1) is 60-70 ℃.

Preferably, the crystallization temperature in the step (3) is 35-50 ℃.

Preferably, the crystallization final temperature in the step (4) is 5-25 ℃.

Preferably, the size of the bulk single crystal of BHET obtained in the above step (4) is not less than 500mm × 500mm × 100 mm.

Preferably, the impurity-containing crystallization solvent obtained by filtering in the step (4) is distilled at 75-80 ℃, and the obtained pure crystallization solvent can be recycled.

The preparation method of the BHET bulk single crystal has the beneficial effects that:

(1) the BHET bulk single crystal obtained by adopting a gradient cooling crystallization method has large size and side length up to 1 cm.

(2) The crystallization method can realize effective separation of BHET and other impurities, particularly separation of coloring impurities. Even if decolorization is not assisted by other purification methods, the L value of the BHET bulk single crystal can be controlled to be more than 95 and the absolute values of the a value and the b value can be controlled within 1.0 (HunterLab color system) by regulating and controlling crystallization conditions.

(3) The BHET bulk crystal with better form can be obtained only by matching specific crystallization solvent types and dosage with specific gradient cooling crystallization conditions, and the aim is difficult to realize by controlling a single condition factor.

(4) The boiling point of the solvent used for crystallization is lower, the energy consumption is lower when the crystallization solvent is removed, and the solvent can be recycled only by simple normal pressure distillation operation. This not only reduces the production cost, but also reduces the discharge of three wastes.

Drawings

The invention is further illustrated by the following figures and examples.

Fig. 1 is an XRD spectrum of the samples prepared in example 1 and comparative example 2.

Fig. 2 is a photograph of a bulk single crystal of BHET prepared in example 1.

Fig. 3 is a polarization microscope image of the bulk single crystal of BHET prepared in example 1.

Fig. 4 is a polarization microscope image of the BHET needle-shaped crystals prepared in comparative example 1.

Fig. 5 is a polarization microscope image of BHET crystals prepared in comparative example 2.

Fig. 6 is a polarization microscope image of BHET crystals prepared in comparative example 6.

Detailed Description

The present invention will be described below with reference to specific examples, but the application of the present invention is not limited to the scope of the examples, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the invention.

Example 1:

and (3) taking 20g of BHET crude product, adding 200g of ethyl acetate, heating to 65 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 35 ℃ at the cooling rate of 1 ℃/h, the temperature is kept for 24h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 25 ℃ at the speed of 2 ℃/h, and the BHET bulk single crystal is obtained after filtration, washing and drying. The obtained ethyl acetate solution containing impurities is distilled at 75 ℃ to obtain pure ethyl acetate for recycling.

Example 2:

taking 20g of BHET crude product, adding 160g of ethyl acetate, heating to 70 ℃, fully stirring and dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 50 ℃ at the cooling rate of 10 ℃/h, the temperature is kept for 6h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 25 ℃ at the cooling rate of 6 ℃/h, and the BHET bulk single crystal is obtained after filtration, washing and drying. The obtained ethyl acetate solution containing impurities is distilled at 80 ℃ to obtain pure ethyl acetate for recycling.

Example 3:

and (3) adding 40g of ethanol into 20g of BHET crude product, heating to 60 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 40 ℃ at the cooling rate of 5 ℃/h, the temperature is kept for 12h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 5 ℃ at the cooling rate of 6 ℃/h, and the BHET bulk single crystal is obtained after filtration, washing and drying. Distilling the obtained ethanol solution containing impurities at 75 ℃ to obtain pure ethanol for recycling.

Example 4:

and (3) taking 20g of BHET crude product, adding 80g of ethanol, heating to 60 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 35 ℃ at the cooling rate of 3 ℃/h, the temperature is kept for 24h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 5 ℃ at the cooling rate of 3 ℃/h, and the BHET bulk single crystal is obtained after filtration, washing and drying. Distilling the obtained ethanol solution containing impurities at 80 ℃ to obtain pure ethanol for recycling.

Comparative example 1:

the BHET crude product is purified by a water slow cooling recrystallization method disclosed in Chinese patent CN110590551A, and the specific operation process is as follows: and (3) taking 20g of BHET crude product, adding 200g of water, heating to 65 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. Transferring the solution into a crystallizer for crystallization, reducing the temperature to 40 ℃ at the rate of 3 ℃/h, then reducing the temperature to 20 ℃ at the rate of 20 ℃/h, and obtaining the BHET needle crystal after filtering and drying.

TABLE 1 results of color and purity tests of BHET obtained in examples 1-4 and comparative example 1

Among them, the "BHET purity" in Table 1 was obtained by high performance liquid chromatography analysis.

As shown in table 1, in comparative example 1 and comparative example 1, the chromaticity of bulk single crystal was significantly better than that of needle-shaped crystal, which indicates that the formation of bulk single crystal is more favorable for separation of BHET from other impurities, particularly coloring impurities, and the advantageous effects of the present invention are exhibited.

Comparative example 2:

ethyl acetate is used as a crystallization solvent, and a traditional cooling crystallization method is used for purifying a BHET crude product, wherein the specific operation process is as follows: and (3) taking 20g of BHET crude product, adding 200g of ethyl acetate, heating to 65 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is placed at room temperature (25 ℃) for cooling crystallization for 24 hours, and BHET crystal is obtained after filtration and drying. The crystal form of the BHET prepared under the condition is not uniform, the BHET is mainly granular, and the size of the BHET is small. Compared with the example 1, the method proves that the BHET bulk single crystal with better morphology can not be obtained by the traditional cooling crystallization method, and the application of the gradient cooling crystallization technology is one of the keys for preparing the BHET bulk single crystal. And the result of X-ray diffraction analysis is shown in figure 1, the crystal form of the BHET crystal synthesized under the condition is not pure, and the BHET single crystal obtained by the gradient cooling crystallization method has a more perfect crystal form.

Comparative example 3:

ethanol is used as a crystallization solvent, and a BHET crude product is purified by a traditional cooling crystallization method, wherein the specific operation process is as follows: and (3) taking 20g of BHET crude product, adding 80g of ethanol, heating to 60 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is placed at room temperature (25 ℃) for cooling crystallization for 24 hours, and BHET crystal is obtained after filtration and drying. The crystal form of the BHET prepared under the condition is not uniform, the BHET is mainly granular, and the size of the BHET is small. Compared with the example 4, the method proves that the traditional cooling crystallization method cannot obtain the BHET bulk single crystal with better morphology, and the application of the gradient cooling crystallization technology is one of the keys for preparing the BHET bulk single crystal.

Comparative example 4:

methanol is used as a crystallization solvent, and a BHET crude product is purified by a gradient cooling crystallization method, wherein the specific operation process is as follows: and (3) taking 20g of BHET crude product, adding 40g of methanol, heating to 60 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 40 ℃ at the cooling rate of 5 ℃/h, the temperature is kept for 12h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 5 ℃ at the cooling rate of 6 ℃/h, and BHET crystal is obtained after filtration, washing and drying. The BHET crystals produced under these conditions have a large size but a non-uniform morphology, and needle-like and bulk crystals are observed at the same time, but needle-like crystals are the main ones. Compared with example 3, it is demonstrated that not all organic solvents, or alcohols and esters with similar structures can prepare bulk single crystals of BHET, and the selection of crystallization solvent is one of the key points of the technology.

Comparative example 5:

and (3) adding 200g of ethanol into 20g of BHET crude product, heating to 65 ℃, fully stirring for dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 35 ℃ at the cooling rate of 1 ℃/h, the temperature is kept for 24h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 25 ℃ at the speed of 2 ℃/h, and BHET crystal is obtained after filtration, washing and drying. The crystal form of the BHET prepared under the condition is not uniform, the BHET is mainly granular, and the size of the BHET is small. In contrast to example 1, it was demonstrated that the conditions for gradient temperature-decreasing crystallization need to be changed depending on the kind of the crystallization solvent, and it is difficult to obtain an ideal bulk single crystal of BHET by controlling a single condition factor.

Comparative example 6:

taking 20g of BHET crude product, adding 160g of ethyl acetate, heating to 65 ℃, fully stirring and dissolving, and filtering to remove insoluble substances while the solution is hot to obtain the BHET solution. The solution is transferred to a crystallizer for crystallization, the temperature is reduced to 35 ℃ at the cooling rate of 1 ℃/h, the temperature is kept for 24h, and obvious crystal precipitation can be observed. Then the temperature is reduced to 25 ℃ at the speed of 2 ℃/h, and BHET crystal is obtained after filtration, washing and drying. The crystals of BHET prepared under these conditions still appeared in a block form, but the crystal size was significantly small, and stacking between crystals was severe, and colored impurities were trapped between crystals, and the color number was L-94.59, a-2.34, and b-2.28. Compared with examples 1 and 2, the condition of gradient cooling crystallization needs to be changed according to the change of the using amount of the crystallization solvent, and the ideal bulk single crystal of BHET is difficult to obtain by controlling a single condition factor.

The preparation of bulk single crystals by applying corresponding gradient crystallization conditions according to the type and the amount of a specific crystallization solvent is one of the keys of the technology.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.