CN111138279A - Mixed ester derived from PTA residue and preparation method thereof - Google Patents
Mixed ester derived from PTA residue and preparation method thereof Download PDFInfo
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- CN111138279A CN111138279A CN202010002536.2A CN202010002536A CN111138279A CN 111138279 A CN111138279 A CN 111138279A CN 202010002536 A CN202010002536 A CN 202010002536A CN 111138279 A CN111138279 A CN 111138279A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a mixed ester derived from PTA residues and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing PTA residues with diethylene glycol, and reacting to obtain a first mixture; (2) adding a catalyst and excessive isooctanol into the first mixture, and reacting to obtain a crude mixed ester product; (3) and (3) sequentially carrying out vacuum dehydration and bubbling dealcoholization on the crude mixed ester to obtain the mixed ester. The preparation method has simple process, the prepared mixed ester has high content, can be used as a plasticizer, and has the plasticizing effect equivalent to that of pure diisooctyl terephthalate.
Description
Technical Field
The invention relates to the technical field of chemical waste recycling, and particularly relates to a mixed ester derived from PTA residues and a preparation method thereof.
Background
The current PTA production process mainly comprises two stages of catalytic oxidation and hydrofining. The organic waste material produced during the catalyst and solvent recovery in the oxidation stage is referred to as TA oxidation residue. The waste materials generated in the refining stage are named as PTA refining slag, PTA residues cleaned out by a wastewater pool of the device every year, and ground falling materials and broken materials generated in the process of a small amount of packaging, loading and transporting are collectively named as PTA residues.
China is a large country where PTA is produced, producing at least 4000 million tons of PTA per year, producing about 5 kilograms of PTA residue per ton of PTA produced, and producing at least 20 million tons of PTA residue per year. The composition of the PTA residue is complicated due to the different processes used, but the main components include benzoic acid, p-toluic acid, p-carboxybenzaldehyde, phthalic acid, isophthalic acid, terephthalic acid, and the like. 90% of the components have recycling value. The chemical method for recycling PTA residues at present mainly comprises the steps of preparing a plasticizer by an esterification method, synthesizing a methyl ester compound by esterification of methanol, preparing unsaturated resin by esterification of the methyl ester compound and ethylene glycol, preparing activated carbon by utilizing the PTA residues and the like.
In the method, the environment-friendly plasticizer prepared by the esterification method has wide application prospect. Accordingly, there is a continuing need in the art to develop a process for the preparation of mixed esters derived from PTA residues that can be used as plasticizers.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art by providing a process for the preparation of mixed esters derived from PTA residues, useful as plasticizers.
The present application also aims to provide a mixed ester prepared by the above preparation method.
In order to achieve the object of the present invention, the present application provides the following technical solutions.
In a first aspect, the present application provides a process for the preparation of mixed esters derived from PTA residues, characterized in that it comprises the following steps:
(1) mixing PTA residues with diethylene glycol, and reacting to obtain a first mixture;
(2) adding a catalyst and excessive isooctanol into the first mixture, and reacting to obtain a crude mixed ester product;
(3) and (3) sequentially carrying out vacuum dehydration and bubbling dealcoholization on the crude mixed ester to obtain the mixed ester.
In one embodiment, the process for making the mixed ester derived from PTA residue consists of:
(1) mixing PTA residues with diethylene glycol, and reacting to obtain a first mixture;
(2) adding a catalyst and excessive isooctanol into the first mixture, and reacting to obtain a crude mixed ester product;
(3) and (3) sequentially carrying out vacuum dehydration and bubbling dealcoholization on the crude mixed ester to obtain the mixed ester.
In the preparation method, the following processes are mainly included:
the first step is as follows: at 160-170 ℃, the diethylene glycol reacts with the monobasic acid (such as benzoic acid) in the PTA residue, the dibasic acid hardly participates in the reaction, and under the condition that the content of the benzoic acid in the PTA residue is known, the molar ratio of the alkyd is controlled to be 1-1.05: 1, the desired diethylene glycol dibenzoate can be obtained;
the second step is that: adding excessive isooctanol, heating to 200-240 ℃, and reacting dibasic acid such as terephthalic acid, phthalic acid, isophthalic acid and the like in PTA residues to generate diisooctyl terephthalate; so that the ester content in the product is up to more than 97 percent.
In one embodiment of the first aspect, the content of benzoic acid in the PTA residue is 40-60% by mass.
In one embodiment of the first aspect, the molar ratio of diethylene glycol to benzoic acid is 1 to 1.05: 1.
In one embodiment of the first aspect, in the step (1), the reaction temperature is 160-170 ℃, and the reaction time is 4-6 h.
In one embodiment of the first aspect, the catalyst comprises an alkyl titanate.
In one embodiment of the first aspect, the alkyl titanate is tetrabutyl titanate.
In one embodiment of the first aspect, in the step (2), the reaction temperature is 200 to 240 ℃, and the reaction time is 6 to 10 hours.
In one embodiment of the first aspect, the vacuum degree used for vacuum dehydration is less than or equal to-0.02 MPa, and the acid value of the crude mixed ester after vacuum dehydration is less than or equal to 1.0 mgKOH/g.
In one embodiment of the first aspect, the steam used for the bubbling dealcoholization is water vapor, the steam pressure is not less than 0.2MPa, and the steam temperature is 180-190 ℃.
In a second aspect, the present application also provides a mixed ester prepared by the above preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) by adopting the preparation method, the ester content in the product is up to more than 97%;
(2) the mixed ester prepared by the method can be directly used as a plasticizer, and the plasticizing effect is equivalent to that of pure DOP diisooctyl terephthalate.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. The numerical ranges within this application provide, among other things, the amount of each comonomer in the acrylate copolymer, the amount of each component in the photoresist composition, the temperature at which the acrylate is synthesized, and the various characteristics and properties of these components.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, insofar as such terms are necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In one embodiment, the PTA residue used herein is derived from a PTA residue from Shanghai petrochemical, but one skilled in the art will also appreciate that the processes of the present disclosure are applicable to PTA residues from other sources or of different compositions.
In a specific embodiment, the preparation method of the present application comprises the following steps:
(1) adding PTA oxidation residue and diethylene glycol into a reaction kettle, and reacting at the temperature of 160-170 ℃ for 4-6 hours;
(2) adding excessive isooctyl alcohol and a catalyst TBT, and reacting for 6-10 hours at the temperature of 200-240 ℃;
(3) vacuum dewatering to make acid value less than or equal to 1.0mgKOH/g and vacuum temperature less than or equal to-0.02 MPa;
(4) after the acid value is qualified, carrying out steam bubbling to remove excessive alcohol, wherein the steam pressure is more than or equal to 0.2MPa, and the temperature is controlled at 180 ℃ and 190 ℃.
Examples
The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the benzoic acid content in the PTA residue was 50% by mass.
Example 1
A process for the preparation of mixed esters derived from PTA residues comprising the steps of:
1. 5000Kg of PTA oxidation residue (Shanghai petrochemical) and 1500Kg of diethylene glycol are added into a reaction kettle, the reaction is carried out for 6 hours at 160 ℃, and then the top temperature is reduced;
2. adding 3000kg of isooctyl alcohol and 15kg of tetrabutyl titanate serving as a catalyst after water does not flow out, and heating to 200 ℃ for reaction for 10 hours;
3. after the reaction is finished, vacuum dehydration is carried out at-0.03 MPa until the acid value is less than or equal to 1.0 mgKOH/g;
4. after the acid number reached, excess alcohol was removed by steam sparging to give the mixed ester derived from the PTA residue.
The mixed ester prepared in the example has the following properties by detection: the acid value is 1.0mgKOH/g, and the determination is carried out according to GB/T1668-2008; the ester content was 97%.
Example 2
A process for the preparation of mixed esters derived from PTA residues comprising the steps of:
1. 6000Kg of PTA oxidation residue (Shanghai petrochemical) and 1600Kg of diethylene glycol are put into a reaction kettle, the reaction is carried out for 4 hours at 160 ℃, and then the top temperature is reduced;
2. adding 3000kg of isooctyl alcohol and 10kg of tetrabutyl titanate serving as a catalyst after water does not flow out, and heating to 240 ℃ for reaction for 6 hours;
3. after the reaction is finished, vacuum dehydration is carried out at-0.03 MPa until the acid value is less than or equal to 1.0 mgKOH/g;
4. after the acid number reached, excess alcohol was removed by steam sparging to give the mixed ester derived from the PTA residue.
The mixed ester prepared in the example has the following properties by detection: the acid value is 1.0mgKOH/g, and the determination is carried out according to GB/T1668-2008; the ester content was 98%.
Example 3
A process for the preparation of mixed esters derived from PTA residues comprising the steps of:
1. 6000Kg of PTA oxidation residues (Shanghai petrochemical) and 1600Kg of diethylene glycol are put into a reaction kettle, the reaction is carried out for 5 hours at 165 ℃, and then the top temperature is reduced;
2. adding 3000kg of isooctyl alcohol and 10kg of tetrabutyl titanate serving as a catalyst after water does not flow out, and heating to 220 ℃ for reacting for 8 hours;
3. after the reaction is finished, vacuum dehydration is carried out under-0.05 MPa until the acid value is less than or equal to 1.0 mgKOH/g;
4. after the acid number reached, excess alcohol was removed by steam sparging to give the mixed ester derived from the PTA residue.
The mixed ester prepared in the example has the following properties by detection: the acid value is 0.9mgKOH/g, determined according to GB/T1668-2008; the ester content was 98%, determined according to GB/T1665-2008.
Example 4
A process for the preparation of mixed esters derived from PTA residues comprising the steps of:
1. 6000Kg of PTA oxidation residue (Shanghai petrochemical) and 1600Kg of diethylene glycol are put into a reaction kettle, and react for 4 hours at the temperature of 160-;
2. adding 3000kg of isooctyl alcohol and 10kg of tetrabutyl titanate serving as a catalyst after water does not flow out, and heating to 200 ℃ and 240 ℃ for reaction for 10 hours;
3. after the reaction is finished, vacuum dehydration is carried out at-0.03 MPa until the acid value is less than or equal to 1.0 mgKOH/g;
4. after the acid number reached, excess alcohol was removed by steam sparging to give the mixed ester derived from the PTA residue.
The mixed ester prepared in the example has the following properties by detection: the acid value is 1.0mgKOH/g, and the determination is carried out according to GB/T1668-2008; the ester content was 99%.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. A process for the preparation of mixed esters derived from PTA residues, comprising the steps of:
(1) mixing PTA residues with diethylene glycol, and reacting to obtain a first mixture;
(2) adding a catalyst and excessive isooctanol into the first mixture, and reacting to obtain a crude mixed ester product;
(3) and (3) sequentially carrying out vacuum dehydration and bubbling dealcoholization on the crude mixed ester to obtain the mixed ester.
2. The process for producing a mixed ester derived from a PTA residue as recited in claim 1, wherein the content of benzoic acid in the PTA residue is 40-60% by mass.
3. The process of claim 2, wherein the molar ratio of diethylene glycol to benzoic acid is 1-1.05: 1.
4. The process of claim 1, wherein in step (1), the temperature of the reaction is 160-170 ℃ and the reaction time is 4-6 h.
5. The process of claim 1, wherein the catalyst comprises an alkyl titanate.
6. The process of claim 5, wherein the alkyl titanate is tetrabutyl titanate.
7. The process of claim 1, wherein in the step (2), the temperature of the reaction is 200-240 ℃ and the reaction time is 6-10 h.
8. The process of claim 1, wherein the vacuum degree of the vacuum dehydration is less than or equal to-0.02 MPa, and the crude mixed ester has an acid value of less than or equal to 1.0mgKOH/g after the vacuum dehydration.
9. The process for producing a mixed ester derived from PTA residues as in claim 1, wherein the steam used for the bubble dealcoholization is steam, the steam pressure is 0.2MPa or more, and the steam temperature is 180 to 190 ℃.
10. A mixed ester derived from PTA residues, wherein the mixed ester is prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010002536.2A CN111138279A (en) | 2020-01-02 | 2020-01-02 | Mixed ester derived from PTA residue and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010002536.2A CN111138279A (en) | 2020-01-02 | 2020-01-02 | Mixed ester derived from PTA residue and preparation method thereof |
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| CN111138279A true CN111138279A (en) | 2020-05-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876357A (en) * | 2021-01-20 | 2021-06-01 | 江苏福昌环保科技集团有限公司 | Production process for producing plasticizer from PTA oxidation residues |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534652A (en) * | 1994-10-18 | 1996-07-09 | Exxon Chemical Patents Inc. (Ecpi) | Preparation of plasticizer esters from phthalic anhydride residue |
| CN101880232A (en) * | 2010-06-04 | 2010-11-10 | 镇江联成化学工业有限公司 | Method for synthesizing environment-friendly plasticizer by using benzoic acid, diethylene glycol and isooctyl alcohol |
| CN109776313A (en) * | 2019-01-28 | 2019-05-21 | 上海炼升化工股份有限公司 | A kind of mixed ester and its synthetic method from PTA residue |
-
2020
- 2020-01-02 CN CN202010002536.2A patent/CN111138279A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534652A (en) * | 1994-10-18 | 1996-07-09 | Exxon Chemical Patents Inc. (Ecpi) | Preparation of plasticizer esters from phthalic anhydride residue |
| CN101880232A (en) * | 2010-06-04 | 2010-11-10 | 镇江联成化学工业有限公司 | Method for synthesizing environment-friendly plasticizer by using benzoic acid, diethylene glycol and isooctyl alcohol |
| CN109776313A (en) * | 2019-01-28 | 2019-05-21 | 上海炼升化工股份有限公司 | A kind of mixed ester and its synthetic method from PTA residue |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876357A (en) * | 2021-01-20 | 2021-06-01 | 江苏福昌环保科技集团有限公司 | Production process for producing plasticizer from PTA oxidation residues |
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