WO2012119520A1 - Procédé d'élaboration d'un plastifiant à partir de résidus d'atb - Google Patents

Procédé d'élaboration d'un plastifiant à partir de résidus d'atb Download PDF

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Publication number
WO2012119520A1
WO2012119520A1 PCT/CN2012/071753 CN2012071753W WO2012119520A1 WO 2012119520 A1 WO2012119520 A1 WO 2012119520A1 CN 2012071753 W CN2012071753 W CN 2012071753W WO 2012119520 A1 WO2012119520 A1 WO 2012119520A1
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WO
WIPO (PCT)
Prior art keywords
benzoate
plasticizer
isooctyl
alcohol
methyl
Prior art date
Application number
PCT/CN2012/071753
Other languages
English (en)
Chinese (zh)
Inventor
黄珍华
李凌
Original Assignee
福建天大化工有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福建天大化工有限公司 filed Critical 福建天大化工有限公司
Publication of WO2012119520A1 publication Critical patent/WO2012119520A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • 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

Definitions

  • the present invention relates to the field of chemical industry, and in particular to a method for comprehensive utilization of CTA residue resources in a PTA production process.
  • Purified terephthalic acid is one of the main raw materials for polyester chips and polyester fibers. Its domestic production capacity has exceeded 12 million tons per year, and there is still huge room for growth.
  • the main by-product produced in the PTA production process is the CTA residue of the paraxylene chemical section, which accounts for about three-thousandths to five thousandths of the PTA production.
  • the main component in the residue is mixed phthalic acid, methylbenzene.
  • Conventional harmless treatment methods such as formic acid, benzoic acid, etc. are incineration and sewage treatment. Both of these methods have disadvantages such as inconvenient operation, energy consumption, large investment, and the risk of secondary pollution.
  • An object of the present invention is to provide a method for comprehensive utilization of CTA residue resources to solve the above problems in the prior art.
  • the CTA residue generally contains p-dibenzoic acid, o-dibenzoic acid, m-dibenzoic acid, and methylbenzoic acid, and is a mixed benzoic acid.
  • the method for comprehensive utilization of the present invention the first CTA residue ester To form a mixed phthalic acid diester, methyl benzoate, benzoate, and then separate, the heavy component is mixed phthalic acid diester, the light component is methyl benzoate and benzoic acid a mixture of esters, the heavy component is used directly as a plasticizer, and the light component is then transesterified to form a mixture of diethylene glycol benzoate and diethylene glycol benzoate. This mixture is used as a plasticizer. .
  • the first step is to prepare a mixed organic isooctyl ester by reacting CTA residue with excess isooctanol;
  • the third step separates isooctyl methylbenzoate and diisooctyl phthalate by distillation; [10] The fourth step is to refine the crude ester of diisooctyl phthalate;
  • Step 5 Transesterification of (methyl) isooctyl benzoate to di(ethylene) benzoate;
  • the first step is: charging the CTA residue, the catalyst and the excess isooctanol into the reaction vessel to a temperature of 220-240 ° C, maintaining the reaction, and refluxing for 8-12 hours.
  • the acid value was measured until the acid value was 0.5 mg KOH/g, and the reaction was terminated, and the obtained crude ester was subjected to the second step.
  • the second step recovers three processes of atmospheric pressure dealcoholization, vacuum de-alcoholization, and steam stripping and dealcoholization
  • normal pressure dealcoholization means crude ester in a normal pressure state.
  • the alcohol in the distillation is distilled off, and the de-alcoholization under vacuum means that the alcohol is distilled off under vacuum, and the stripping of the alcohol in the steam is to remove the trace amount of the alcohol in the crude ester after the de-alcoholization by vacuum.
  • the third step of the dealcoholized crude ester is subjected to vacuum distillation, first separating the lower boiling methyl isophthalate to the next transesterification step. Next, the mixed phthalic acid and isooctyl ester are distilled out, and the next step of the refining process is carried out; finally, a small amount of bottom slag is excluded from the autoclave, and the solid waste is harmlessly treated.
  • the fourth step includes five processes of neutralization, water washing, stripping, vacuum drying, and pressure filtration.
  • the fifth step is carried out by adding an excess amount of diethylene glycol to the crude product of isobutyl (methyl)benzoate and performing transesterification under normal pressure.
  • the refining of the sixth step of diethylene glycol (meth)benzoate comprises:
  • H00C-R-C00H stands for phthalic acid (ie terephthalic acid, phthalic acid, isophthalic acid)
  • H00C-R-CH3 represents methylbenzoic acid
  • R-C00H represents benzoic acid and methylbenzoic acid
  • H0-R, _0H represents diethylene glycol
  • the CTA residue is first esterified into diisooctyl phthalate, isooctyl methyl benzoate, isooctyl benzoate, and then separated, and the heavy component is mixed benzene.
  • the CTA residue is used for the production of plasticizer products, achieving comprehensive utilization of resources, and having high economic benefits and society. benefit.
  • the isooctyl alcohol in the crude ester is recovered and used in the production of the next batch.
  • the recovery is divided into three processes of atmospheric pressure dealcoholization, vacuum de-alcoholization, and steam stripping and dealcoholation.
  • Atmospheric de-alcoholization the alcohol in the crude ester is distilled off under normal pressure.
  • the de-alcoholization under vacuum means that the alcohol is distilled under vacuum, and the stripping of the alcohol is carried out by the partial pressure principle.
  • the trace amount of alcohol in the crude ester is removed to the maximum extent to meet the final product quality requirements.
  • the purified product is the di(ethylene) benzoic acid diethylene glycol ester of the product of the present invention.
  • [54] Basically the same as the first embodiment, except that in the first step: 4 kg of CTA residue, catalyst and isooctyl alcohol 9.45 kg were charged into the reaction vessel and heated to 240 ° C, the reaction was kept, and reflux was carried out. After about an hour, the acid value was measured until the acid value was 0.5 mg koh/g, and the reaction was terminated, and the obtained crude ester was passed to the next step.
  • the present invention first esterifies the CTA residue into a mixed phthalic acid diester, a methyl benzoate, a benzoate, and then separates it, and the heavy component is a mixed phthalic acid.
  • a mixture of glycol esters, the latter mixture is also an excellent plasticizer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé d'utilisation exhaustive de résidus d'ATB en tant que ressource. Dans la présente invention, le résidu d'ATB est estérifié en esters de phtalate mixtes, méthylbenzoate et benzoate, qui sont ensuite séparés pour obtenir un composant lourd à partir des esters de phtalate mixtes et un composant léger à partir du mélange de méthylbenzoate et de benzoate. Le composant lourd est un plastifiant qui peut être directement utilisé, tandis que le composant léger est transestérifié pour élaborer un mélange de (méthyl)benzoate de diéthylène glycol, qui est également un plastifiant efficace. De cette façon, le résidu d'ATB est entièrement employé dans la production de produits plastifiants ce qui permet d'exploiter de façon exhaustive les ressources et d'obtenir des bénéfices économiques et sociaux importants.
PCT/CN2012/071753 2011-03-08 2012-02-29 Procédé d'élaboration d'un plastifiant à partir de résidus d'atb WO2012119520A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201110056079 CN102206156B (zh) 2011-03-08 2011-03-08 Cta残渣资源化综合利用的方法
CN201110056079.6 2011-03-08

Publications (1)

Publication Number Publication Date
WO2012119520A1 true WO2012119520A1 (fr) 2012-09-13

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Application Number Title Priority Date Filing Date
PCT/CN2012/071753 WO2012119520A1 (fr) 2011-03-08 2012-02-29 Procédé d'élaboration d'un plastifiant à partir de résidus d'atb

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CN (1) CN102206156B (fr)
WO (1) WO2012119520A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206156B (zh) * 2011-03-08 2013-04-03 福建天大化工有限公司 Cta残渣资源化综合利用的方法
CN104650332B (zh) * 2014-12-09 2017-01-11 福建天大化工有限公司 一种树脂中间体--苯二甲酸二乙二醇聚酯的制备方法
RU2612302C1 (ru) * 2015-10-14 2017-03-06 Общество с ограниченной ответственностью "ХИМТЕХ-ИНЖИНИРИНГ" Способ получения диоктилтерефталата
RU2666739C1 (ru) * 2017-06-15 2018-09-12 Общество с Ограниченной Ответственностью "НПЦ Башкомпаунд" Способ получения пластификатора диоктилтерефталата из кубового остатка ректификации 2-этилгексанола и технической терефталевой кислоты
CN109776313B (zh) * 2019-01-28 2023-01-13 上海炼升化工股份有限公司 一种源自pta残渣的混合酯及其合成方法
RU2708641C1 (ru) * 2019-07-22 2019-12-10 Сергей Николаевич Лакеев Способ получения терефталатного и бензоатного пластификаторов из побочных продуктов
CN111205182B (zh) * 2020-02-13 2020-10-27 厦门大学 用pta残渣制备混合型增塑剂及环保型增塑剂的方法
CN112851503A (zh) * 2021-01-20 2021-05-28 江苏福昌环保科技集团有限公司 一种pta氧化残渣综合利用工艺
CN112876357A (zh) * 2021-01-20 2021-06-01 江苏福昌环保科技集团有限公司 一种pta氧化残渣生产增塑剂的生产工艺

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US4284793A (en) * 1977-11-30 1981-08-18 Chisso Corporation Method for producing plasticizers
CN101811970A (zh) * 2010-05-05 2010-08-25 江苏强林生物能源有限公司 对苯二甲酸二辛酯复合增塑剂的生产方法
CN102206156A (zh) * 2011-03-08 2011-10-05 福建天大化工有限公司 Cta残渣资源化综合利用的方法

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CN1073549C (zh) * 1998-03-10 2001-10-24 辽阳市石油化工研究所 对苯二甲酸混合酯的制备方法
CN100400498C (zh) * 2003-10-31 2008-07-09 中国石油化工股份有限公司 一种对苯二甲酸水洗残渣回收利用的方法
CN101139293B (zh) * 2007-08-17 2010-08-25 郭立耀 对苯二甲酸二辛酯的生产方法

Patent Citations (3)

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US4284793A (en) * 1977-11-30 1981-08-18 Chisso Corporation Method for producing plasticizers
CN101811970A (zh) * 2010-05-05 2010-08-25 江苏强林生物能源有限公司 对苯二甲酸二辛酯复合增塑剂的生产方法
CN102206156A (zh) * 2011-03-08 2011-10-05 福建天大化工有限公司 Cta残渣资源化综合利用的方法

Non-Patent Citations (1)

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CN102206156A (zh) 2011-10-05

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