CN101805263B - Cleaning production method of phthalic acid di-(2-ethyl) ethyl ester - Google Patents
Cleaning production method of phthalic acid di-(2-ethyl) ethyl ester Download PDFInfo
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- CN101805263B CN101805263B CN201010129431XA CN201010129431A CN101805263B CN 101805263 B CN101805263 B CN 101805263B CN 201010129431X A CN201010129431X A CN 201010129431XA CN 201010129431 A CN201010129431 A CN 201010129431A CN 101805263 B CN101805263 B CN 101805263B
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Abstract
The invention provides a cleaning production method of phthalic acid di-(2-ethyl) ethyl ester, which comprises the following steps of: putting purified phthalic acid and octanol into a reaction kettle; esterifying under the function of catalytic agent; neutralizing with alkaline water; performing dealcholization in vacuum; and filtering to obtain the finished product. The recycle of the esterified water in the production method comprises the step of collecting and pretreating the esterified water which is generated by esterification, wherein some treated esterified water is used for preparing the high-concentration alkaline water for neutralizing the follow-on esterification solution, and the residual treated esterified water is used for dealcholization in vacuum. with the recycle, the cleaning production method does not use the process water, thereby greatly reducing the production quality of waste water, and archiving the effect of cleaning production.
Description
Technical field
The invention belongs to the chemical field synthesis technique, refer in particular to a kind of phthalic acid two (2-ethyl) clean preparation method of ester, be specifically related to reduce wastewater flow rate, conserve water resource, help protecting the clean preparation method of environment.
Background technology
Terephthalic acid two (2-ethyl) ester is claimed dioctyl terephthalate again, is called for short DOTP, and its main application is the softening agent of PVC.Along with the further raising of the mankind to the toxicity property understanding and the Environmental awareness of chemical, the usage ratio of traditional adjacent benzene class softening agent reduces year by year significantly, and is replaced by environment-friendly plasticizers such as DOTP, ATBC, DINCH.DOTP is as a kind of excellent property, environment-friendly plasticizer that cost performance is moderate, approved rapidly by market and increases substantially.
The working method of DOTP mainly contains three kinds: a kind of is to pass through esterification with useless terephthalic acid (land material, bale broken material, pond material etc.) and octanol to produce; The 2nd, carry out transesterification reaction with useless terylene (piece, silk, sheet etc., staple is a polyethylene terephthalate) with octanol (2-EH) and produce; The 3rd, produce with octanol (2-EH) esterification with pure terephthalic acid (PTA).Industry at present go up main production methods be one, 3 two kind, its technological process is seen accompanying drawing.
CN1268675 " terephthalic acid and octanol prepare the technology of dioctyl terephthalate softening agent " patent announcement its technological principle be at first terephthalic acid is washed or pickling to remove monoprotic acid and sodium salt, become dried agent through drying then.Dried agent of terephthalic acid and octanol are dropped in the reaction kettle by a certain percentage, under catalyst action, carry out esterification, become the dioctyl terephthalate softening agent through technologies such as neutralization, washing, dealcoholysis, filtrations.
In general, the buck of the usefulness that more than neutralizes, NaOH concentration is 3-10%, and majority is about 5%, and the buck consumption is about 40% of an ester weight.The water yield of washing usefulness also is about 40% of an ester weight.
Can find out that from above technological process the link that produces waste water in the DOTP production process is more, wastewater flow rate is bigger.Because environment-friendly plasticizer growth in recent years is very fast, how solving the quantity that reduces environmental pollution when developping production is an extremely urgent important topic.
Summary of the invention
The present invention in order to overcome above-mentioned deficiency, to producing DOTP with pure terephthalic acid (PTA) with octanol (2-EH) reaction, improves traditional neutralization, washing process just, reduces the growing amount of waste water significantly.
Chemical equation: PTA+2-EH * 2 → DOTP+H
2O * 2
Molecular weight position 166 260 390 36
DOTP finished product per ton, the amount of the water that generates in theory: 36 ÷, 390 * 1000=92kg.In fact, owing to contain a spot of water in the raw material, also have a spot of organic impurity in the esterification water of generation sometimes, so the amount of the esterification water that product per ton generates is between 92-94kg.
The present invention implements like this: a kind of phthalic acid two (2-ethyl) is the clean preparation method of ester; Pure terephthalic acid and octanol are dropped in the reaction kettle; Under catalyst action, carry out esterification; Filter finished product through buck neutralization, vacuum dealcoholysis, mistake, it is characterized in that the esterification water circulation use in the working method, comprising:
(1) the esterification water that esterification is generated is collected and carried out pre-treatment, and pretreated method is: esterification water is heated to boiling, steams a part of water, the water that stays is esterification water after treatment, and is subsequent use to do;
(2) part esterification water is after treatment prepared the high density buck that is used for follow-up esterification liquid and usefulness;
(3) remaining esterification water after treatment is used for the vacuum dealcoholysis;
(4) circulate with this.
In this technology, control the acidity of esterification.Because this esterification is that alcohol is excessive; And rely on excessive alcohol to dewater, so the acidity of the thick ester of esterification is low more, esterification is thorough more; The yield of acid is high more; Can prolong the reaction times and increase energy consumption and product color is deepened but cross the low acidity of low pursuit, generally to grasp the acidity of reaction end be 0.1 ~ 0.2mgKOH/g to technology in the past, and the reaction end acidity of this technology controlling and process is≤0.08mgKOH/g.
During the esterification water pretreatment, evaporate the water of esterification water gross weight 3 ~ 5%, to reduce the content of organic impurity in the water, the water decontaminated water collecting tank that steams.
The buck that uses of neutralization is the NaOH solution of mass percent concentration as 20-30% in the technology, and is formulated by after treatment esterification water and solid NaOH, and finished product per ton is with the about 1-3kg of strong lye, preferably 1.2-1.5kg.The neutral temperature is 150-180 ℃, preferred 170 ℃ ± 3 ℃, under whipped state, add, and add continued and stirred 30 minutes.
This technology replaces traditional water vapor dealcoholysis by esterification water after treatment, and product per ton uses the esterification water yield after treatment to be 40-50kg, and the vacuum dealcoholysis time is 1.5-2 hour.
Can find out that from above process the water (product 92-94kg per ton) that esterification generates is absolutely necessary, but owing to adopt lower thick ester acidity and concentrated base neutralization; Reduced the neutralization of former process using, a large amount of waters of washing, and replaced steam or fresh water to carry out the vacuum dealcoholysis, do not introduced other waters with treated esterification water; Therefore; Do not use process water fully, reduced the waste water growing amount significantly, product per ton only produces waste water 92-94kg.The esterification water that product per ton generates is for enough being used to join alkali lye and vacuum dealcoholysis water through handling.The present invention is than reducing water with washing process in traditional, having reached the effect of cleaner production.
Description of drawings
Fig. 1 is the process flow sheet of background technology.
Embodiment
Embodiment 1; A kind of phthalic acid two (2-ethyl) is the clean preparation method of ester, and pure terephthalic acid and octanol are dropped in the reaction kettle, under catalyst action, carries out esterification; Filter finished product, the esterification water circulation use that produces in the production through buck neutralization, vacuum dealcoholysis, mistake:
(1) the esterification water that esterification is generated is collected and carried out pre-treatment, and pretreated method is: esterification water is heated to boiling, evaporates the water decontaminated water collecting tank of esterification water gross weight 3-5%, the water that stays is esterification water after treatment, and is subsequent use;
(2) part esterification water and solid sodium hydroxide after treatment prepared the high density buck that is used for follow-up esterification liquid and usefulness, it is 20-30% that buck concentration can be made into mass percent concentration as required;
(3) remaining esterification water after treatment is used for the vacuum dealcoholysis;
(4) circulate with this.
Esterification water reference implementation example 1 circular treatment in the technology is used.
Embodiment 3, with PTA4.4 ton, 10.3 tons of octanols, activated carbon 20kg, add 20m
3Whisking appliance in the reaction kettle, and add thermal material to 185 ℃, add titanate catalyst 5.3kg and carry out esterification; When esterification to still temperature to 215 ℃, add the same catalyzer 3.5kg again, esterification time 7 hours; Distillation removes the about 951kg of esterification water that dereaction generates, when about reaction kettle temperature rise to 225 ℃, and esterification end during reaction kettle material acid number≤0.08mgKOH/g; Close the heating fuel tap, vacuumize dealcoholysis, make temperature of reaction kettle reduce to 170 ℃ ± 3 ℃, add 25%NaOH alkali lye 13kg; Restir 30min continues to vacuumize and slowly import the treated esterification water of 500kg and carried out the coupling vacuum stripping dealcoholysis 1.5 hours, and reaction kettle still temperature keeps 160 ℃.Finishing, <behind the 500ppm, it is qualified to continue to be evacuated to material moisture, through filtering specification product for back detection material octanol content.
Esterification water reference implementation example 1 circular treatment in the technology is used.
Remarks: adding 20-30%NaOH alkali lye carries out the neutral temperature and can be controlled at 150-180 ℃.In the whole process for cleanly preparing; Do not use process water fully, product per ton only produces waste water 92-94kg, and the esterification water of these generations enough is used to join alkali lye and vacuum dealcoholysis water after treatment; Finished product phthalic acid two per ton (2-ethyl) ester with strong lye 1-3kg (the best is 1.2-1.5kg); Use the esterification water yield to carry out the vacuum dealcoholysis, like a little circulations, than having significantly reduced water with washing process in traditional, having reached the effect of cleaner production as 40-50kg.
Claims (8)
1. a phthalic acid two (2-ethyl) clean preparation method of ester; Pure terephthalic acid and octanol are dropped in the reaction kettle, under catalyst action, carry out esterification, filter finished product through buck neutralization, vacuum dealcoholysis, mistake; It is characterized in that the esterification water circulation use in the working method, comprising:
(1) the esterification water that esterification is generated is collected and carried out pre-treatment, and pretreated method is: esterification water is heated to boiling, steams a part of water, the water that stays is esterification water after treatment, and is subsequent use to do;
(2) part esterification water is after treatment prepared the buck that is used for follow-up esterification liquid and usefulness;
(3) remaining esterification water after treatment is used for the vacuum dealcoholysis;
(4) circulate with this;
In the technology, the esterification catalyst system therefor is a titanate catalyst, and the terminal point acidity of esterification is≤0.08mgKOH/g that the buck that neutralization is used is the NaOH solution of mass percent concentration as 20-30%, and is formulated by after treatment esterification water and solid NaOH.
2. a kind of phthalic acid two according to claim 1 (2-ethyl) is the clean preparation method of ester, when it is characterized in that the esterification water pretreatment, evaporates the water of esterification water gross weight 3-5%.
3. a kind of phthalic acid two according to claim 1 (2-ethyl) is the clean preparation method of ester, it is characterized in that finished product phthalic acid two per ton (2-ethyl) ester use buck 1-3kg.
4. a kind of phthalic acid two according to claim 3 (2-ethyl) is the clean preparation method of ester, it is characterized in that finished product phthalic acid two per ton (2-ethyl) ester use buck 1.2-1.5kg.
5. a kind of phthalic acid two according to claim 1 (2-ethyl) is the clean preparation method of ester, it is characterized in that buck neutral temperature is 150-180 ℃, under whipped state, adds, and adds continued and stirs 30 minutes.
6. a kind of phthalic acid two according to claim 5 (2-ethyl) is the clean preparation method of ester, it is characterized in that buck neutral temperature is 170 ℃ ± 3 ℃.
7. a kind of phthalic acid two according to claim 1 (2-ethyl) is the clean preparation method of ester, it is characterized in that products benzene dioctyl phthalate two per ton (2-ethyl) ester use the esterification water yield after treatment to carry out the vacuum dealcoholysis as 40-50kg.
8. a kind of phthalic acid two according to claim 7 (2-ethyl) is the clean preparation method of ester, it is characterized in that the vacuum dealcoholysis time is 1.5-2 hour.
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| CN101967098A (en) * | 2010-09-26 | 2011-02-09 | 昆山合峰化工有限公司 | Preparation method of bis(2-propylheptyl) phthalate |
| CN101973884A (en) * | 2010-09-26 | 2011-02-16 | 昆山合峰化工有限公司 | Method for preparing triisononyl trimellitate (TINTM) |
| CN102531903A (en) * | 2011-06-08 | 2012-07-04 | 巢湖香枫塑胶助剂有限公司 | Preparation method and application of phthalic acid diester (2-propyl group heptanol) |
| CN105237401B (en) * | 2015-10-16 | 2017-12-01 | 江苏森禾化工科技有限公司 | A kind of manufacture craft of plasticizer |
| CN110451625A (en) * | 2019-07-17 | 2019-11-15 | 江苏新东风化工科技有限公司 | A kind of neutralization reaction technique of n-butyl acrylate production |
| CN113354536B (en) * | 2020-03-05 | 2024-08-06 | 王群朋 | Process for preparing terephthalic acid esters |
| WO2021174487A1 (en) * | 2020-03-05 | 2021-09-10 | 王群朋 | Method for preparing terephthalate |
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| US4284793A (en) * | 1977-11-30 | 1981-08-18 | Chisso Corporation | Method for producing plasticizers |
| CN1563159A (en) * | 2004-03-18 | 2005-01-12 | 杨家勇 | Technique for preparing plasticizer of dioctyl terephthalate from terephthalic acid and capryl alcohol |
| CN101402473A (en) * | 2008-11-06 | 2009-04-08 | 河南庆安化工高科技股份有限公司 | Method for reutilization of wastewater in elasticizer production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284793A (en) * | 1977-11-30 | 1981-08-18 | Chisso Corporation | Method for producing plasticizers |
| CN1563159A (en) * | 2004-03-18 | 2005-01-12 | 杨家勇 | Technique for preparing plasticizer of dioctyl terephthalate from terephthalic acid and capryl alcohol |
| CN101402473A (en) * | 2008-11-06 | 2009-04-08 | 河南庆安化工高科技股份有限公司 | Method for reutilization of wastewater in elasticizer production |
Non-Patent Citations (1)
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| 蔡文祥等.DBP、DOP清洁生产工艺及实施效果.《环境污染与防治》.1998,第20卷(第6期),28-31. * |
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Inventor after: Zhou Jianan Inventor after: Zhou Yongfang Inventor after: Zhou Hong Inventor after: Cao Lijun Inventor after: Chen Ping Inventor before: Zhou Yongfang Inventor before: Chen Ping Inventor before: Cao Lijun |
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Address after: Qiting street of Yixing city Jiangsu province 214213 Kaixuan Road No. 1 Patentee after: Jiangsu Raymond New Material Co., Ltd. Address before: 214213 No. 8 West Yongan Road, Yixing Economic Development Zone, Jiangsu, Wuxi Patentee before: Jiangsu Lemon Chemical Industry Technology Co., Ltd. |