Resourceful treatment equipment and method for polyolefin catalyst mother liquor

文档序号：1826066 发布日期：2021-11-12 浏览：29次中文

阅读说明：本技术 聚烯烃催化剂母液的资源化处理设备及处理方法 (Resourceful treatment equipment and method for polyolefin catalyst mother liquor ) 是由杜宏斌任靖张祥安包满祝平张毅肖军孙晓薇李孝平冯超于 2020-04-27 设计创作，主要内容包括：本发明涉及催化剂母液处理领域,公开了一种聚烯烃催化剂母液的资源化处理设备及处理方法。本发明的聚烯烃催化剂母液的资源化处理设备包括蒸馏塔、第一精馏塔、第二精馏塔以及第三精馏塔,其特征在于,该设备还包括萃取釜。采用本发明的聚烯烃催化剂母液的资源化处理设备处理聚烯烃催化剂母液,不但能够提高四氯化钛的回收率,而且解决了现有技术中高沸物水解带来的诸多不足,有利于工业化。(The invention relates to the field of catalyst mother liquor treatment, and discloses recycling treatment equipment and a recycling treatment method for polyolefin catalyst mother liquor. The recycling treatment equipment for the polyolefin catalyst mother liquor comprises a distillation tower, a first rectifying tower, a second rectifying tower and a third rectifying tower, and is characterized by further comprising an extraction kettle. The polyolefin catalyst mother liquor recycling treatment equipment provided by the invention is used for treating the polyolefin catalyst mother liquor, so that the recovery rate of titanium tetrachloride can be improved, a plurality of defects caused by hydrolysis of high-boiling-point substances in the prior art are overcome, and the industrialization is facilitated.)

1. A resource treatment device of polyolefin catalyst mother liquor comprises a distillation tower, a first rectifying tower, a second rectifying tower and a third rectifying tower, and is characterized by also comprising an extraction kettle,

the top of the distillation tower is provided with a tower top component outlet and is connected with the inlet of the first rectifying tower, and the bottom of the distillation tower is provided with a tower bottom component outlet and is connected with the inlet of the extraction kettle;

the top of the first rectifying tower is provided with a tower top component outlet and is connected with the inlet of the second rectifying tower, and the bottom of the first rectifying tower is provided with a tower bottom component outlet and is connected with the inlet of the third rectifying tower;

the top of the second rectifying tower is provided with a tower top component outlet, and the bottom of the second rectifying tower is provided with a tower bottom component outlet and is connected with the inlet of the extraction kettle;

the top of the third rectifying tower is provided with a tower top component outlet, and the bottom of the third rectifying tower is provided with a tower bottom component outlet and is connected with the inlet of the extraction kettle;

the extraction kettle is provided with an inlet, an extraction material outlet and a raffinate material outlet, wherein the extraction material outlet is connected with the inlet of the distillation tower.

2. The apparatus of claim 1, wherein the top of the first rectification column is provided with an overhead component outlet and is connected to the extraction vessel inlet.

3. The apparatus according to claim 1, wherein the number of the first rectifying column, the second rectifying column, and the third rectifying column is 1 or more;

preferably, the number of the first rectifying tower, the second rectifying tower and the third rectifying tower is 1.

4. The apparatus of claim 1, wherein the overhead component outlet of the second rectification column is connected to an organic solvent storage tank and the overhead component outlet of the third rectification column is connected to a titanium tetrachloride storage tank.

5. A resource treatment method of polyolefin catalyst mother liquor is characterized by comprising the following steps,

1) feeding the polyolefin catalyst mother liquor into a distillation tower for distillation, discharging tower top components through a tower top component outlet arranged at the top, and discharging tower bottom components through a tower bottom component outlet arranged at the bottom;

2) the tower top component obtained in the step 1) enters a first rectifying tower, and is rectified, the tower top component is discharged through a tower top component outlet arranged at the top, and the tower bottom component is discharged through a tower bottom component outlet arranged at the bottom;

3) the tower top component obtained in the step 2) enters a second rectifying tower, and is rectified to discharge the organic solvent through a tower top component outlet arranged at the top and the tower bottom component through a tower bottom component outlet arranged at the bottom;

4) the tower bottom component obtained in the step 3) enters a third rectifying tower, and is rectified, the tower top component is taken as refined titanium tetrachloride and is discharged through a tower top component outlet arranged at the top, and the tower bottom component is discharged through a tower bottom component outlet arranged at the bottom;

5) and (3) feeding the tower bottom component obtained in the step 1), the tower bottom component obtained in the step 3), the tower bottom component obtained in the step 4) and an extracting agent into an extraction kettle, and extracting and separating to obtain an extract material and an extract raffinate.

6. The method according to claim 5, wherein the method further comprises feeding the extract obtained in step 5) to a distillation column for distillation.

7. The method as claimed in claim 5, wherein the top component of the first rectifying tower is partially fed into the second rectifying tower for rectification, and partially fed into the extraction kettle to be used as a partial extractant.

8. The process according to any one of claims 5 to 7, wherein the polyolefin catalyst mother liquor contains titanium tetrachloride, an organic solvent and a titanium chloroalkoxide and/or titanium ester complex;

preferably, the polyolefin catalyst mother liquor contains 70 to 90 wt% of titanium tetrachloride, 10 to 25 wt% of organic solvent and 1 to 10 wt% of titanium alkoxide and/or titanium ester complex.

9. The method of claim 8, wherein the organic solvent is an alkane having 6 to 12 carbon atoms;

preferably, the organic solvent I is at least one of hexane, heptane, octane, nonane and decane.

10. The process according to any one of claims 5 to 7, wherein in step 1), the distillation is carried out by atmospheric or vacuum distillation for separating the organic solvent and titanium tetrachloride from the mother liquor;

preferably, the distillation is carried out such that the mass ratio of the overhead component to the bottom component is from 3 to 10: 1.

11. the method according to any one of claims 5 to 7, wherein in step 2), the operating conditions of the first rectification column comprise: the pressure is 0-50 kPa, the temperature at the top of the tower is 67-100 ℃, and the temperature at the bottom of the tower is 80-150 ℃;

preferably, in step 3), the operating conditions of the second distillation column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 67-70 ℃, and the temperature at the bottom of the tower is 70-110 ℃;

preferably, in step 4), the operating conditions of the third distillation column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 136-138 ℃, and the temperature at the bottom of the tower is 137-150 ℃.

12. The method according to any one of claims 5 to 7, wherein in step 5), the extracted extractant is alkane with 6 to 12 carbon atoms;

preferably, the extractant is at least one of hexane, heptane, octane, nonane and decane.

Preferably, the extractant is the same as the organic solvent contained in the polyolefin catalyst mother liquor.

13. The process of any one of claims 5 to 7, wherein in step 5) the extraction conditions comprise: the temperature is-20-50 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 0.5-3: 1;

preferably, the extraction conditions include: the temperature is-20-0 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 1-2: 1.

14. The process according to any one of claims 5 to 7, wherein in step 5), after extraction, an extract is obtained comprising the extractant, titanium tetrachloride and the organic solvent, and a raffinate comprises the titanium alkoxide.

Technical Field

The invention relates to the field of catalyst mother liquor treatment, in particular to recycling treatment equipment and a treatment method for polyolefin catalyst mother liquor.

Background

Polyolefin catalysts are generally formed by reacting a magnesium chloride alcoholate support, titanium tetrachloride and an electron donor. In the preparation process of the catalyst, excessive titanium tetrachloride is used for treating solid magnesium chloride alcoholate in an organic solvent (such as alkane), solid-liquid separation is needed after the synthesis of the catalyst is finished, and the separated liquid part is called mother liquor. The main components of the mother liquor are titanium tetrachloride, organic solvent, a small amount of chloroalkoxytitanium and titanium ester complex, wherein the high boiling point substances mainly comprise chloroalkoxytitanium, titanium ester complex and other substances with boiling points higher than that of the titanium tetrachloride. The mother liquor may also contain solid catalyst particles.

For a long time, the common method for recovering titanium tetrachloride from mother liquor is to use atmospheric or vacuum distillation. Since the mother liquor contains solid catalyst particles, alkoxy titanium and titanium ester complex, complex reaction with titanium tetrachloride may occur during distillation to form "high boiling substance" having a boiling point higher than that of titanium tetrachloride. The high-boiling-point substances have high viscosity and poor fluidity and are easy to adhere to the wall of the distillation kettle, so that the treatment capacity of the distillation kettle is reduced. In order to facilitate discharging, a certain amount of titanium tetrachloride is left to ensure the fluidity of high-boiling residues in the distillation kettle, so that the recovery rate of the titanium tetrachloride is reduced, and the subsequent hydrolysis treatment capacity and the treatment difficulty are increased. In addition, in the rectification process of titanium tetrachloride and solvent, a part of solid particles and complex enter a rectification system, and a reboiler is seriously coked through high temperature, so that the treatment capacity of a recovery device is influenced, and the quality of the recovered titanium tetrachloride and hexane is unstable. The high boiling point substance is generally transferred to a hydrolysis kettle for hydrolysis, a large amount of high COD hydrochloric acid liquid slag is generated after the treatment, a large amount of HCl gas is discharged at the same time, and high-concentration hydrochloric acid is formed after the absorption of water. The treatment cost of waste residues and waste liquid is high, the treatment way is not easy to monitor, and great potential safety hazards exist. From the viewpoint of environmental protection and resource utilization, the problem of waste residue and waste liquid treatment has become a bottleneck restricting the production of the catalyst.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a recycling treatment device and a recycling treatment method for polyolefin catalyst mother liquor. The resource treatment equipment for the polyolefin catalyst mother liquor is adopted to treat the polyolefin catalyst mother liquor, so that the recovery rate of titanium tetrachloride can be improved, a plurality of defects caused by hydrolysis of high-boiling-point substances in the prior art are overcome, industrialization is facilitated, the method can change all the polyolefin catalyst mother liquor into valuable, and the resource treatment target of waste liquor is realized.

The present inventors have unexpectedly found that titanium tetrachloride and chloroalkoxytitanium in a high boiling residue can be efficiently separated by an extraction method using an extractant, thereby increasing the yield of titanium tetrachloride, and have completed the present invention.

Therefore, the first aspect of the invention provides a resource treatment device of polyolefin catalyst mother liquor, which comprises a distillation tower, a first rectifying tower, a second rectifying tower and a third rectifying tower, wherein the device also comprises an extraction kettle,

Preferably, the top of the first rectifying tower is provided with an overhead component outlet and is connected with the inlet of the extraction kettle.

Preferably, the number of the first rectifying tower, the second rectifying tower and the third rectifying tower is more than 1; more preferably, the number of the first rectifying tower, the second rectifying tower and the third rectifying tower is 1.

Preferably, the tower top component outlet of the second rectifying tower is connected with an organic solvent storage tank, and the tower top component outlet of the third rectifying tower is connected with a titanium tetrachloride storage tank.

According to a second aspect of the present invention, there is provided a method for recycling a polyolefin catalyst mother liquor, wherein the method comprises the steps of,

Preferably, the method also comprises the step of feeding the extract obtained in the step 5) into a distillation tower for distillation.

Preferably, part of the top component of the first rectifying tower enters the second rectifying tower for rectification, and part of the top component enters the extraction kettle to be used as part of the extractant.

Preferably, the polyolefin catalyst mother liquor contains titanium tetrachloride, an organic solvent, and a titanium chloroalkoxide and/or titanium ester complex.

Preferably, the polyolefin catalyst mother liquor contains 70 to 90 wt% of titanium tetrachloride, 10 to 25 wt% of organic solvent and 1 to 10 wt% of titanium alkoxide and/or titanium ester complex.

Preferably, the organic solvent is alkane with 6-12 carbon atoms; more preferably, the organic solvent is at least one of hexane, heptane, octane, nonane and decane.

Preferably, in step 1), the distillation employs atmospheric or vacuum distillation for separating the organic solvent and titanium tetrachloride from the mother liquor.

Preferably, the distillation is carried out such that the mass ratio of the overhead component to the bottom component is from 3 to 10: 1.

preferably, in step 2), the operating conditions of the first rectification column include: the pressure is 0-50 kPa, the temperature at the top of the tower is 67-100 ℃, and the temperature at the bottom of the tower is 80-150 ℃.

Preferably, in step 3), the operating conditions of the second distillation column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 67-70 ℃, and the temperature at the bottom of the tower is 70-110 ℃.

Preferably, in step 4), the operating conditions of the third distillation column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 136-138 ℃, and the temperature at the bottom of the tower is 137-150 ℃.

Preferably, in the step 5), the extracted extractant is alkane with 6-12 carbon atoms; more preferably, the extractant is at least one of hexane, heptane, octane, nonane and decane.

Preferably, the extractant is the same as the organic solvent contained in the polyolefin catalyst mother liquor.

Preferably, the extraction conditions include: the temperature is-10-50 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 0.5-3: 1; more preferably, the extraction conditions include: the temperature is-10-0 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 1-2: 1.

Preferably, in the step 5), after extraction, the obtained extract material contains an extracting agent, titanium tetrachloride and an organic solvent, and the raffinate material contains alkoxy titanium.

According to the equipment and the treatment method, the recovery rate of the titanium tetrachloride can be improved, and a plurality of defects caused by hydrolysis of high-boiling-point substances in the prior art are overcome, so that the equipment and the treatment method are beneficial to industrialization. In addition, the method can change all polyolefin catalyst mother liquor into valuables and realize the aim of recycling the waste liquor.

Drawings

FIG. 1 is a schematic view of an apparatus for recycling an olefin catalyst mother liquor according to the present invention.

FIG. 2 is a schematic diagram of a prior art processing apparatus for processing a polyolefin catalyst mother liquor.

Description of the reference numerals

R1: distillation column C1: first rectifying tower

C2: second rectification column C3: third rectifying tower

R2: hydrolysis kettle R3: extraction kettle

A: mother liquor B: qualified material

C: qualified material D: extracting agent

E: liquid phase F: solid phase

G: hydrolysate

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a resource treatment device of polyolefin catalyst mother liquor, which comprises a distillation tower, a first rectifying tower, a second rectifying tower and a third rectifying tower, wherein the device also comprises an extraction kettle,

According to the equipment of the invention, preferably, the top of the first rectifying tower is provided with an overhead component outlet and is connected with an extraction kettle inlet. The top component of the first rectification column can be fed into the extraction kettle as an extractant by connecting the top component outlet of the first rectification column with the inlet of the extraction kettle.

According to the equipment of the invention, preferably, the number of the first rectifying tower, the second rectifying tower and the third rectifying tower is more than 1; more preferably, the number of the first rectifying tower, the second rectifying tower and the third rectifying tower is 1.

According to the apparatus of the present invention, preferably, the overhead component outlet of the second distillation column is connected to an organic solvent storage tank.

According to the apparatus of the present invention, preferably, the overhead component outlet of the third distillation column is connected to a titanium tetrachloride storage tank.

The distillation column, the first rectification column, the second rectification column, the third rectification column, and the extraction still are not particularly limited, and may be a distillation column, a rectification column, and an extraction still commonly used in the art.

According to a second aspect of the present invention, there is provided a method for recycling a polyolefin catalyst mother liquor, wherein the method comprises the steps of,

According to the method of the invention, the method preferably further comprises feeding the extract obtained in the step 5) into a distillation tower for distillation. The extraction material obtained in the step 5) enters a distillation tower for distillation, so that the method has the advantage of completely recycling the liquid phase material in the system.

According to the method of the invention, preferably, the top component of the first rectifying tower partially enters the second rectifying tower for rectification, and partially enters the extraction kettle to be used as a part of the extractant.

According to the process of the present invention, preferably, the polyolefin catalyst mother liquor contains titanium tetrachloride, an organic solvent and a titanium chloroalkoxide and/or a titanium ester complex. Specifically, in the polyolefin catalyst mother liquor, the content of titanium tetrachloride is 70-90 wt%, the content of organic solvent is 10-25 wt%, and the content of alkoxy titanium and/or ester titanium complex is 1-10 wt%; preferably, the mother liquor contains 70-85 wt% of titanium tetrachloride, 10-20 wt% of organic solvent I and 3-10 wt% of alkoxy titanium and/or ester titanium complex.

In the present invention, the titanium tetrachloride content in the mother liquor is: total content of titanium-containing compounds based on titanium tetrachloride. The content of titanium chloroalkoxide means: content of titanium chloroalkoxide in terms of alkoxy group. The content of the titanium ester complex is: the content of the titanium ester complex in terms of the ester compound.

According to the method of the present invention, the organic solvent is any of various organic solvents commonly used in the art in the preparation of polyolefin catalysts, and preferably, the organic solvent is an alkane having 6 to 12 carbon atoms; more preferably, the organic solvent is at least one of hexane, heptane, octane, nonane and decane.

According to the process of the present invention, in step 1), the distillation employs atmospheric or vacuum distillation for separating the organic solvent and titanium tetrachloride from the mother liquor. Preferably, the distillation is carried out such that the mass ratio of the overhead component to the bottom component is from 3 to 10: 1; more preferably, the distillation is such that the weight ratio of separation of the light and heavy components is from 4.5 to 8.5: 1.

the temperature of the atmospheric distillation may be, for example, 140-165 ℃. The temperature of the reduced pressure distillation may be, for example, 70 to 110 ℃ and the degree of vacuum of the distillation may be, for example, 50 to 300 Pa.

According to the method of the present invention, preferably, in step 2), the operating conditions of the first rectification column include: the pressure is 0-50 kPa, the temperature at the top of the tower is 67-100 ℃, and the temperature at the bottom of the tower is 80-150 ℃; more preferably, the operating conditions of the first rectification column include: the pressure is 5-20kPa, the temperature at the top of the column is 69-98 ℃, and the temperature at the bottom of the column is 105-143 ℃. The tower top components obtained in the step 2) are mainly alkane and a small amount of titanium tetrachloride, and the tower bottom components are mainly titanium tetrachloride and alkoxy titanium.

According to the method of the present invention, preferably, in step 3), the operating conditions of the second rectification column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 67-70 ℃, and the temperature at the bottom of the tower is 70-110 ℃; more preferably, the operating conditions of the second rectification column include: the pressure is 5-15kPa, the temperature at the top of the tower is 67-68 ℃, and the temperature at the bottom of the tower is 80-107 ℃. The components at the top of the tower obtained in the step 3) are alkane, and the components at the bottom of the tower are mainly titanium tetrachloride and a small amount of alkane.

According to the method of the present invention, preferably, in step 4), the operating conditions of the third rectification column include: the pressure is 0-20 kPa, the temperature at the top of the tower is 136-138 ℃, and the temperature at the bottom of the tower is 137-150 ℃; more preferably, the operating conditions of the third rectification column include: the pressure is 8-18kPa, the temperature at the top of the tower is 137-138 ℃ and the temperature at the bottom of the tower is 140-147 ℃. The tower top component obtained in the step 4) is refined titanium tetrachloride, and the tower bottom component mainly comprises a small amount of titanium tetrachloride and alkoxy titanium.

According to the method of the present invention, preferably, in the step 5), the extracted extractant is alkane with 6-12 carbon atoms; more preferably, the extractant is at least one of hexane, heptane, octane, nonane and decane. Further, it is preferable that the extractant is the same as the organic solvent contained in the polyolefin catalyst mother liquor.

According to the process of the present invention, preferably, the extraction conditions comprise: the temperature is-20-50 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 0.5-3: 1; more preferably, the extraction conditions include: the temperature is-20-0 ℃, and the volume ratio of the dosage of the extracting agent to the extracting raw material is 1-2: 1. In the step 5), after extraction, the obtained extraction material contains an extracting agent, titanium tetrachloride and an organic solvent, and the raffinate mainly contains alkoxy titanium.

The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

In the present invention, percentages and percentages are by weight unless explicitly stated otherwise.

In the invention, an Ageilent 6890N-type gas chromatograph is adopted for measuring the content of the ethoxy group, and the experimental conditions are as follows: column temperature 150 ℃, detector temperature 200 ℃, injection port temperature 180 ℃, column flow: 30 mL/min.

In the invention, a 722 type ultraviolet-visible spectrophotometer is adopted for measuring the content of titanium tetrachloride, and the experimental conditions are as follows: under acidic conditions, the titanium particles complex with hydrogen peroxide to form a tan complex, rendering the aqueous phase yellow. The titanium tetrachloride content is as follows: titanium tetrachloride, chloroethoxytitanium as titanium tetrachloride and titanium ester complex as titanium tetrachloride.

In the invention, the hexane content is measured by an Ageinent 6890N type gas chromatograph under the following experimental conditions: column temperature 50 ℃, detector temperature 180 ℃, injection port temperature 180 ℃, column flow 10 mL/min.

Example 1

The polyolefin catalyst mother liquor recycling treatment apparatus shown in fig. 1 was used to perform the polyolefin catalyst mother liquor recycling treatment.

As shown in fig. 1, the apparatus includes: the distillation tower R1, the first rectifying tower C1, the second rectifying tower C2, the third rectifying tower C3 and the extraction kettle R3, wherein the top of the distillation tower R1 is provided with a tower top component outlet which is connected with an inlet of the first rectifying tower C1, and the bottom of the distillation tower R1 is provided with a tower bottom component outlet which is connected with an inlet of the extraction kettle R3; the top of the first rectifying tower C1 is provided with a tower top component outlet which is connected with the inlet of the second rectifying tower C2, and the bottom of the first rectifying tower C1 is provided with a tower bottom component outlet which is connected with the inlet of the third rectifying tower; the top of the second rectifying tower C2 is provided with a tower top component outlet, the bottom of the second rectifying tower C2 is provided with a tower bottom component outlet, and the second rectifying tower C2 is connected with the inlet of the extraction kettle R3; the top of the third rectifying tower C3 is provided with a tower top component outlet, the bottom of the third rectifying tower C3 is provided with a tower bottom component outlet, and the third rectifying tower C3 is connected with the inlet of the extraction kettle R3; the extraction kettle R3 is provided with an extraction material outlet and a raffinate material outlet, wherein the extraction material outlet is connected with the inlet of the distillation tower R1.

The feeding amount of polyolefin catalyst mother liquor A is 3635kg, wherein the content of titanium tetrachloride is 81%, the content of hexane is 16%, the content of chloroalkoxytitanium is 3%, the mother liquor A enters a distillation kettle R1, and a tower top component and a tower bottom component are obtained after distillation. The overhead component obtained after the distillation weighed 3235kg and consisted essentially of 18.0% hexane, 79.9% titanium tetrachloride and 2.1% chloroalkoxytitanium. The weight of the components at the bottom of the tower obtained after distillation is 400kg, and the components are mainly 90 percent of titanium tetrachloride and 10 percent of chloroalkoxytitanium. Wherein, the tower top component obtained after distillation is discharged from the top of the distillation still and enters a first rectifying tower C1, and is rectified and separated in the first rectifying tower C1, and the operation conditions are as follows: the operating pressure was 10kPa, the overhead temperature 98 ℃ and the bottom temperature 143 ℃. After the fractional distillation separation in the first rectification column C1, the overhead component weighed 606kg, mainly 96% of hexane and 4% of titanium tetrachloride, and the bottom component 2629kg, mainly 97.4% of titanium tetrachloride and 2.6% of chloroalkoxytitanium. The tower top component discharged from the top of the first rectifying tower C1 enters a second rectifying tower C2, and is rectified and separated in the second rectifying tower C2, the operating pressure is 5kPa, the tower top temperature is 68 ℃, and the tower bottom temperature is 100 ℃. After the rectification separation in the second rectification column C2, the overhead component weighed 570kg, the main component was 99% of hexane and was used as the accept material B, and the bottom component weighed 36kg, the main components were 51.5% of titanium tetrachloride and 48.5% of hexane. The bottom component discharged from the bottom of the first rectifying tower C1 enters a third rectifying tower C3, and is rectified and separated in the third rectifying tower C3, the operating pressure is 8kPa, the tower top temperature is 138 ℃, and the tower bottom temperature is 147 ℃. After the rectification separation in the third rectification column C3, the weight of the top component was 2191kg, the main component was 98% titanium tetrachloride as the qualified material C, and the weight of the bottom component was 438kg, the main components were 84% titanium tetrachloride and 16% chloroalkoxytitanium. 894kg of the tower bottom components obtained after distillation, the tower bottom components discharged from the bottom of the second rectifying tower C2 and the tower bottom components discharged from the bottom of the third rectifying tower C3 enter an extraction kettle R3, 330kg of hexane (an extracting agent D) is added for extraction and separation, the extraction temperature is 0 ℃, 1194kg of liquid-phase E components and 100kg of solid-phase F components are obtained, the liquid-phase E components mainly comprise 29% of hexane, 70.2% of titanium tetrachloride and 0.8% of chloroalkoxytitanium, the solid-phase F components mainly comprise chloroalkoxytitanium, the liquid-phase E components are recycled to the distillation kettle R1, and the solid-phase F components are discharged to be used as byproducts.

As can be seen from example 1, the method of the present invention can recycle all the hexane and titanium tetrachloride in the mother liquor, and the obtained chloroalkoxytitanium can be used as a byproduct, and no hazardous waste is generated.

Example 2

The polyolefin catalyst mother liquor was subjected to the same recycling treatment as in example 1.

The amount of the polyolefin catalyst mother liquor A fed was 5452kg, wherein the titanium tetrachloride content was 78.5%, the hexane content was 16%, and the chloroalkoxytitanium content was 5.5%, and these mother liquors A were fed into a distillation still R1 and distilled to obtain a top component and a bottom component. The overhead component obtained after the distillation weighed 4490kg and consisted essentially of 19.4% hexane, 79.5% titanium tetrachloride and 1.1% chloroalkoxytitanium. The weight of the bottom component obtained after distillation was 962kg, and the components were mainly 74% titanium tetrachloride and 26% chloroalkoxytitanium. Wherein, the tower top component obtained after distillation is discharged from the top of the distillation still and enters a first rectifying tower C1, and is rectified and separated in the first rectifying tower C1, and the operation conditions are as follows: the operating pressure was 20kPa, the temperature at the top of the column was 69 ℃ and the temperature at the bottom of the column was 105 ℃. After the rectification separation in the first rectification column C1, the top component weighed 890kg, mainly 98% hexane and 2% titanium tetrachloride, and the bottom component 3600kg, mainly 98.6% titanium tetrachloride and 1.4% chloroalkoxytitanium. The tower top component discharged from the top of the first rectifying tower C1 enters a second rectifying tower C2, and is rectified and separated in the second rectifying tower C2, the operating pressure is 15kPa, the tower top temperature is 67 ℃, and the tower bottom temperature is 97 ℃. After the rectification separation in the second rectification column C2, the overhead component weighed 874kg and the main component was 99.8% of hexane, which can be used as qualified material B, and the bottom component weighed 16kg and the main component was 99.9% of titanium tetrachloride. The bottom component discharged from the bottom of the first rectifying tower C1 enters a third rectifying tower C3, and is rectified and separated in the third rectifying tower C3, the operating pressure is 18kPa, the tower top temperature is 137 ℃, and the tower bottom temperature is 140 ℃. After the rectification separation in the third rectification column C3, the weight of the tower top component is 3486kg, the main component is 99.8 percent of titanium tetrachloride which can be used as qualified material C, and the weight of the tower bottom component is 114kg, and the main components are 62 percent of titanium tetrachloride and 38 percent of chloro alkoxy titanium. 1092kg of the tower bottom components obtained after distillation, the tower bottom components discharged from the bottom of the second rectifying tower C2 and the tower bottom components discharged from the bottom of the third rectifying tower C3 enter an extraction kettle R3, 2000kg of hexane (an extracting agent D) is added for extraction and separation, the extraction temperature is-18 ℃, 2802kg of liquid-phase E components and 290kg of solid-phase F components are obtained, the liquid-phase E components mainly comprise 71% of hexane, 28.6% of titanium tetrachloride and 0.4% of chlorinated alkoxy titanium, the solid-phase F components mainly comprise chlorinated alkoxy titanium, the liquid-phase E components are recycled to the distillation kettle R1, and the solid-phase F components are discharged to be used as byproducts.

In the embodiment 2, the hexane and the titanium tetrachloride in the mother liquor are all recycled, and the obtained chloroalkoxytitanium can be used as a byproduct, so that no hazardous waste is generated.

Example 3

The polyolefin catalyst mother liquor was subjected to the same recycling treatment as in example 1.

The feeding amount of the polyolefin catalyst mother liquor A was 7270kg, wherein the titanium tetrachloride content was 79.6%, the hexane content was 12% and the chloroalkoxytitanium content was 8.4%, and these mother liquors A were fed into a distillation still R1 and distilled to obtain a top component and a bottom component. The overhead composition obtained after distillation weighed 6270kg and consisted essentially of 13.9% hexane, 84.3% titanium tetrachloride and 1.8% chloroalkoxytitanium. The weight of the components at the bottom of the tower obtained after distillation is 1000kg, and the components are mainly 50 percent of titanium tetrachloride and 50 percent of chloroalkoxytitanium. Wherein, the tower top component obtained after distillation is discharged from the top of the distillation still and enters a first rectifying tower C1, and is rectified and separated in the first rectifying tower C1, and the operation conditions are as follows: the operating pressure was 5kPa, the temperature at the top of the column was 80 ℃ and the temperature at the bottom of the column was 115 ℃. After the rectification separation in the first rectification column C1, the overhead components weighed 886kg, mainly 98.5% hexane and 1.5% titanium tetrachloride, and the bottoms components weighed 5384kg, mainly 98% titanium tetrachloride and 2% chloroalkoxytitanium. The tower top component discharged from the top of the first rectifying tower C1 enters a second rectifying tower C2, and is rectified and separated in the second rectifying tower C2, the operating pressure is 10kPa, the tower top temperature is 67 ℃, and the tower bottom temperature is 80 ℃. After the rectification separation in the second rectification column C2, the overhead component weighed 873kg, the main component was 99.9% of hexane, which can be used as qualified material B, and the bottom component weighed 13kg, the main component was 99.9% of titanium tetrachloride. The bottom component discharged from the bottom of the first rectifying tower C1 enters a third rectifying tower C3, and after the third rectifying tower C3 is subjected to rectification separation, the operating pressure is 12kPa, the tower top temperature is 137 ℃ and the tower bottom temperature is 145 ℃. After rectification separation is carried out in a third rectifying tower C3, the weight of the tower top component is 5200kg, the main component is 99.9 percent titanium tetrachloride which can be used as qualified material C, and the weight of the tower bottom component is 184kg, and the main components are 40 percent titanium tetrachloride and 60 percent chloro alkoxy titanium. The tower bottom component obtained after distillation, the tower bottom component discharged from the bottom of the second rectifying tower C2 and the tower bottom component discharged from the bottom of the third rectifying tower C3 are added into an extraction kettle R3 for extraction and separation by adding 1500kg of hexane (an extracting agent D), wherein the extraction temperature is-15 ℃, so that 2097kg of liquid phase E component and 600kg of solid phase F component are obtained, the liquid phase E component mainly comprises 71.5% of hexane, 28% of titanium tetrachloride and 0.5% of chloroalkoxytitanium, the solid phase F component mainly comprises chloroalkoxytitanium, the liquid phase E component is recycled to the distillation kettle R1, and the solid phase F component is discharged to be used as a byproduct.

In the embodiment 3, the hexane and the titanium tetrachloride in the mother liquor are all recycled, and the obtained chloro alkoxy titanium can be used as a byproduct, so that no hazardous waste is generated.

Comparative example 1

The polyolefin catalyst mother liquor treatment was carried out by using the polyolefin catalyst mother liquor treatment apparatus used in the prior art shown in FIG. 2.

As shown in fig. 2, the apparatus for treating a polyolefin catalyst mother liquor used in the prior art comprises: the distillation tower R1, the first rectifying tower C1, the second rectifying tower C2, the third rectifying tower C3 and the hydrolysis kettle R2, wherein the top of the distillation tower R1 is provided with a tower top component outlet which is connected with an inlet of the first rectifying tower C1, and the bottom of the distillation tower R1 is provided with a tower bottom component outlet which is connected with an inlet of the hydrolysis kettle R2; the top of the first rectifying tower C1 is provided with a tower top component outlet which is connected with the inlet of the second rectifying tower C2, and the bottom of the first rectifying tower C1 is provided with a tower bottom component outlet which is connected with the inlet of the third rectifying tower; the top of the second rectifying tower C2 is provided with a tower top component outlet, the bottom of the second rectifying tower C2 is provided with a tower bottom component outlet, and the second rectifying tower C2 is connected with the inlet of the distillation tower R1; the top of the third rectifying tower C3 is provided with a tower top component outlet, the bottom of the third rectifying tower C3 is provided with a tower bottom component outlet, and the third rectifying tower C3 is connected with the inlet of the distillation tower R1; the hydrolysis kettle R3 is provided with a product outlet.

As can be seen from comparative example 1, the prior art method can completely recycle hexane in the mother liquor, recover 74 percent of titanium tetrachloride, consume a large amount of water and generate a large amount of dangerous waste products.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

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