阅读说明：本技术 一种由工业级乙二醇间歇制备聚酯级乙二醇的方法 (Method for intermittently preparing polyester-grade ethylene glycol from industrial-grade ethylene glycol ) 是由 冯文秀 随帅 冯加亮 朱涛 王英杰 靳景 于 2021-08-06 设计创作，主要内容包括：本发明公开了一种由工业级乙二醇间歇制备聚酯级乙二醇的方法,包括以下步骤：(1)以工业级乙二醇为原料,将一定量的原料一次性输入乙二醇暂存罐,通过氧化循环泵将乙二醇暂存罐中的原料连续循环泵送入塔式反应器的塔顶入口,在塔式反应器的塔底入口连续输入氧化剂；(2)将氧化后的乙二醇泵送至吸附塔的顶部入口,进行吸附操作；(3)将吸附后的乙二醇泵送至间歇精馏塔底部的间歇精馏塔塔釜,开启间歇精馏塔加热并稳定建立冷凝和回流,当样品220nm处透光率≥70%后开始收集产品,得到聚酯级乙二醇产品；该方案具有产品紫外透光率高、无其他化学物质的添加,工艺路线简单,产品收率高的有益效果。(The invention discloses a method for intermittently preparing polyester-grade ethylene glycol from industrial-grade ethylene glycol, which comprises the following steps: (1) taking industrial-grade ethylene glycol as a raw material, inputting a certain amount of raw material into an ethylene glycol temporary storage tank at one time, sending a raw material continuous circulating pump in the ethylene glycol temporary storage tank into a tower top inlet of a tower reactor through an oxidation circulating pump, and continuously inputting an oxidant into a tower bottom inlet of the tower reactor; (2) pumping the oxidized glycol to an inlet at the top of the adsorption tower for adsorption operation; (3) pumping the adsorbed glycol to a tower kettle of an intermittent rectification tower at the bottom of the intermittent rectification tower, starting the intermittent rectification tower for heating, stably establishing condensation and reflux, and collecting a product when the light transmittance at the 220nm position of the sample is more than or equal to 70% to obtain a polyester-grade glycol product; the scheme has the beneficial effects of high ultraviolet transmittance of the product, no addition of other chemical substances, simple process route and high product yield.)

1. A process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol, comprising the steps of:

(1) taking industrial grade ethylene glycol as a raw material, inputting a certain amount of raw material into an ethylene glycol temporary storage tank at one time, sending a raw material continuous circulating pump in the ethylene glycol temporary storage tank into a tower top inlet of a tower reactor through an oxidation circulating pump, continuously inputting an oxidant into a tower bottom inlet of the tower reactor, detecting ultraviolet light transmittance of the ethylene glycol in the ethylene glycol temporary storage tank at 220nm after continuous operation for 5-12 hours, stopping introducing the oxidant when the ultraviolet light transmittance at 220nm is more than or equal to 23%, and stopping the operation of the oxidation circulating pump to obtain oxidized ethylene glycol;

(2) pumping the oxidized ethylene glycol obtained in the step (1) to an adsorption liquid temporary storage tank through an oxidation circulating pump, continuously and circularly conveying the oxidized ethylene glycol to a top inlet of an adsorption tower through the adsorption liquid temporary storage tank through the adsorption liquid circulating pump, carrying out adsorption operation for 2-8 hours, detecting supernatant of the adsorption liquid temporary storage tank, and stopping the adsorption operation when ultraviolet light transmittance at 220nm is detected to be more than or equal to 42% to obtain the adsorbed ethylene glycol;

(3) pumping the adsorbed glycol obtained in the step (2) to an intermittent rectifying tower kettle at the bottom of the intermittent rectifying tower through an adsorption liquid circulating pump, starting the intermittent rectifying tower to heat and stably establish condensation and reflux, detecting a tower top sample every 15 minutes, starting to collect a product when the light transmittance at 220nm of the sample is more than or equal to 70%, stopping collecting when the ultraviolet light transmittance at 220nm of a product extracted from the tower top is less than 70%, and condensing the collected product through a rectifying tower condenser to obtain a polyester-grade glycol product.

2. The process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol according to claim 1, characterized in that: the oxidant is ozone.

3. The process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol according to claim 1, characterized in that: two layers of adsorption devices are arranged in the adsorption tower, and adsorbents are filled in the adsorption devices and are the combination of molecular sieves and activated alumina.

4. The process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol according to claim 3, characterized in that: the lower layer adsorption device of the adsorption tower is filled with a molecular sieve, and the upper layer adsorption device is filled with activated alumina.

5. The process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol according to claim 1, characterized in that: the number of theoretical plates of the batch distillation tower is 31-61, the reflux ratio is 2: 1-10: 1, and the operation pressure is 1-50 kPa.

6. The process for the batch production of polyester grade ethylene glycol from technical grade ethylene glycol according to claim 1, characterized in that: the number of theoretical plates of the tower reactor is 24-52.

Technical Field

The invention relates to the field of chemical product production, in particular to a method for intermittently preparing polyester-grade ethylene glycol from industrial-grade ethylene glycol.

Background

Ethylene glycol is an important organic chemical raw material and is widely used for producing polyethylene terephthalate (PET), automobile antifreeze fluid, nonionic surfactant, plasticizer and the like. At present, the polymer grade glycol used for producing polyester not only occupies more than 90 percent of the total output, but also the quality specification of the product reaches the superior product specified in the national standard of industrial glycol. In recent years, with the rapid increase of the demand of domestic and foreign markets for polyester products, the production scale and production technology of ethylene glycol are rapidly developed, and the technical requirements are obviously improved. Currently, the standards for polyester grade ethylene glycol, established by the American Society for Testing and Materials (ASTM), specify the purity standards for polyester grade ethylene glycol, especially in UV spectrophotometers requiring a transmittance at 220nm of greater than 70%. The requirement is to avoid uncontrollable product quality caused by noise interference caused by absorbance in the working sections of synthetic reaction and the like of polyester grade glycol.

The production method of the polyester grade high ultraviolet transmittance ethylene glycol mainly adopts a process route of oxidizing ethylene into ethylene oxide and then hydrolyzing to obtain the industrial grade ethylene glycol. However, since a trace amount of impurities such as aldehydes and esters are generated in the production process of industrial grade ethylene glycol, the influence on the purity is small, but the influence on the ultraviolet transmittance is large. Patent cn201510583086.x mentions a method for improving the ultraviolet transmittance of ethylene glycol, but the method has the disadvantages that the treatment process is too complicated, and other components such as inorganic acid, water, low carbon alcohol and the like are required to be added, so that the difficulty of post-treatment is increased. Therefore, a method for preparing polyester-grade ethylene glycol with high ultraviolet transmittance, no addition of other chemical substances, simple process route and high product yield is urgently needed to be designed.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the method for preparing the polyester-grade glycol, which has the advantages of high ultraviolet transmittance, no addition of other chemical substances, simple process route and high product yield.

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

a process for the batch preparation of polyester grade ethylene glycol from technical grade ethylene glycol comprising the steps of:

(1) taking industrial grade ethylene glycol as a raw material, inputting a certain amount of raw material into an ethylene glycol temporary storage tank at one time, sending a raw material continuous circulating pump in the ethylene glycol temporary storage tank into a tower top inlet of a tower reactor through an oxidation circulating pump, continuously inputting an oxidant into a tower bottom inlet of the tower reactor, detecting ultraviolet light transmittance of the ethylene glycol in the ethylene glycol temporary storage tank at 220nm after continuous operation for 5-12 hours, stopping introducing the oxidant when the ultraviolet light transmittance at 220nm is more than or equal to 23%, and stopping the operation of the oxidation circulating pump to obtain oxidized ethylene glycol;

(2) pumping the oxidized ethylene glycol obtained in the step (1) to an adsorption liquid temporary storage tank through an oxidation circulating pump, continuously and circularly conveying the oxidized ethylene glycol to a top inlet of an adsorption tower through the adsorption liquid temporary storage tank through the adsorption liquid circulating pump, carrying out adsorption operation for 2-8 hours, detecting supernatant of the adsorption liquid temporary storage tank, and stopping the adsorption operation when ultraviolet light transmittance at 220nm is detected to be more than or equal to 42% to obtain the adsorbed ethylene glycol;

(3) pumping the adsorbed glycol obtained in the step (2) to an intermittent rectifying tower kettle at the bottom of the intermittent rectifying tower through an adsorption liquid circulating pump, starting the intermittent rectifying tower to heat and stably establish condensation and reflux, detecting a tower top sample every 15 minutes, starting to collect a product when the light transmittance at 220nm of the sample is more than or equal to 70%, stopping collecting when the ultraviolet light transmittance at 220nm of a product extracted from the tower top is less than 70%, and condensing the collected product through a rectifying tower condenser to obtain a polyester-grade glycol product.

In order to improve the oxidation reaction effect of the tower reactor in the step (1), the technical scheme of the invention also comprises that the oxidant is ozone.

Furthermore, in order to improve the impurity removal effect of the ethylene glycol, the technical scheme of the invention also comprises that two layers of adsorption devices are arranged in the adsorption tower, the adsorption devices are filled with adsorbents, and the adsorbents are the combination of molecular sieves and activated alumina.

Furthermore, as a preferable scheme, the technical scheme of the invention also comprises that a lower layer adsorption device of the adsorption tower is filled with a molecular sieve, an upper layer adsorption device is filled with activated alumina, and an upper layer adsorption device are arranged to effectively adsorb aldehyde and lipid impurities in the ethylene glycol.

The technical scheme of the invention also comprises that the number of theoretical plates of the batch distillation tower is 31-61, the reflux ratio is 2: 1-10: 1, and the operation pressure is 1-50 kPa.

The technical scheme of the invention also comprises that the theoretical plate number of the tower reactor is 24-52.

The invention has the beneficial effects that: compared with the prior art, the invention aims to provide the method for preparing the polyester-grade glycol, which has the advantages of high ultraviolet transmittance, no addition of other chemical substances, simple process route and high product yield, and in order to realize the technical effects:

firstly, the preparation of high-quality polyester-grade ethylene glycol is realized by intermittently operating equipment such as a tower reactor, an adsorption tower, a rectifying tower and the like and sequentially performing oxidation-adsorption-rectification coupling operation on industrial-grade ethylene glycol, the overall process is simple, chemical substances such as inorganic acid and the like are not required to be added, and the purity and the yield of the product are higher;

secondly, the technical scheme of the application is verified on site for many times, after the intermittent rectifying tower is heated and stabilized, the quality purity of the collected polyester-grade ethylene glycol product is more than or equal to 99.9 percent, the ultraviolet light transmittance at 220nm is more than or equal to 75 percent, the ultraviolet light transmittance at 250nm is more than or equal to 92 percent, the ultraviolet light transmittance at 275nm is more than or equal to 92 percent, the ultraviolet light transmittance at 350nm is more than or equal to 99 percent, and the application value is high.

Drawings

In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.

FIG. 1 is a process flow diagram of the batch production of polyester grade ethylene glycol from technical grade ethylene glycol in the example.

Wherein, 1 is the ethylene glycol temporary storage tank, 2 is the tower reactor, 3 is the oxidation circulating pump, 4 is the absorption liquid temporary storage tank, 5 is the adsorption tower, 6 is the absorption liquid circulating pump, 7 is the batch distillation tower cauldron, 8 is the batch distillation tower, 9 is the distillation column condenser.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the description of the present invention, it is to be understood that the terms "center", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used for descriptive purposes only to simplify the description of the present invention, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and therefore, are not to be construed as limiting the present invention.

Example 1

A process for the batch preparation of polyester grade ethylene glycol from technical grade ethylene glycol comprising the steps of:

(1) taking industrial grade ethylene glycol as a raw material, inputting 500kg of the raw material into an ethylene glycol temporary storage tank 1 at one time, sending a continuous circulating pump of the raw material in the ethylene glycol temporary storage tank 1 into an inlet at the top of a tower reactor 2 through an oxidation circulating pump 3, continuously inputting ozone as an oxidant into an inlet at the bottom of the tower reactor 2, wherein the number of theoretical plates of the tower reactor 2 is 40, discharging tail gas through an outlet at the top of the tower, continuously operating for 5 hours, detecting the ultraviolet light transmittance at 220nm of the ethylene glycol in the ethylene glycol temporary storage tank 1, stopping ozone introduction when the ultraviolet light transmittance at 220nm is larger than or equal to 23%, and simultaneously stopping the operation of the oxidation circulating pump 3 to obtain oxidized ethylene glycol;

(2) pumping the oxidized ethylene glycol obtained in the step (1) to an adsorption liquid temporary storage tank 4 through an oxidation circulating pump 3, continuously and circularly conveying the oxidized ethylene glycol to a top inlet of an adsorption tower 5 through an adsorption liquid circulating pump 6 by the adsorption liquid temporary storage tank 4, carrying out adsorption operation for 5 hours, detecting supernatant of the adsorption liquid temporary storage tank 4, and stopping the adsorption operation when ultraviolet transmittance at a position of 220nm is detected to be more than or equal to 42% to obtain the adsorbed ethylene glycol; an upper layer and a lower layer of adsorption devices are arranged in the adsorption tower 5, the lower layer of adsorption devices are filled with molecular sieves, and the upper layer of adsorption devices are filled with activated alumina.

(3) Pumping the adsorbed ethylene glycol obtained in the step (2) to an intermittent rectification tower kettle 7 at the bottom of an intermittent rectification tower 8 through an adsorption liquid circulating pump 6, starting the intermittent rectification tower 8 to heat and stably establish condensation and reflux, wherein the theoretical plate number of the intermittent rectification tower 8 is 41, the reflux ratio is 6:1, the operating pressure is absolute pressure of 1 kPa-50 kPa, once every 15 minutes, a tower top sample is detected, before the ultraviolet light transmittance at the position of 220nm is less than or equal to 70%, the ethylene glycol is treated as front distillate, kettle residue is discharged from the bottom of the intermittent rectification tower kettle 7, when the ultraviolet light transmittance at the position of 220nm of the sample is greater than or equal to 70%, the collection is stopped when the ultraviolet light transmittance at the position of 220nm of the product extracted from the tower top is less than 70%, and the collected product is condensed by a rectification tower condenser 9 to obtain a polyester grade ethylene glycol product.

The rectification process lasts for 8 hours, the average value of the light transmittance of the collected product at 220nm is 78%, the detected highest value is 88%, the ultraviolet transmittance of the finally obtained product is 220nm, the ultraviolet transmittance is approximately 77%, 250nm is approximately 96%, 275nm is approximately 99%, 350nm is more than or equal to 99% of polyester grade glycol, and the product yield is approximately 65%.

Example 2:

the operation was carried out as in example 1, wherein the adsorption operation time of the adsorption column 5 was adjusted to 8 hours, the reflux ratio of the batch distillation column 8 was adjusted to 10:1, and the other conditions were the same as in example 1.

Finally, the obtained polyester grade glycol with the ultraviolet transmittance of 220nm of about 81 percent, the ultraviolet transmittance of 250nm of about 95 percent, the ultraviolet transmittance of 275nm of more than or equal to 99 percent and the ultraviolet transmittance of 350nm of more than or equal to 99 percent is obtained, and the product yield is about 66 percent.

Example 3:

the procedure was as in example 1, wherein the theoretical plate number of the batch column 8 was adjusted to 61, and the other conditions were the same as in example 1.

Finally, the polyester grade glycol with the ultraviolet transmittance of 220nm of about 77 percent, the ultraviolet transmittance of 250nm of about 96 percent, the ultraviolet transmittance of 275nm of about 99.3 percent and the ultraviolet transmittance of 350nm of more than or equal to 99 percent is obtained, and the product yield is about 62 percent.

Example 4:

the procedure is as in example 1, with the theoretical plate number of the column reactor 2 being adjusted to 50 and the other conditions being the same as in example 1.

The final product of polyester grade glycol with ultraviolet transmittance of 220nm of about 81 percent, 250nm of about 97 percent, 275nm of about 98.8 percent and 350nm of more than or equal to 99 percent is obtained, and the product yield is about 64 percent.

Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.