CN101302158A - Method for synthesizing PVC plasticiser by reclaiming waste polyester - Google Patents
Method for synthesizing PVC plasticiser by reclaiming waste polyester Download PDFInfo
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- CN101302158A CN101302158A CNA2008101235441A CN200810123544A CN101302158A CN 101302158 A CN101302158 A CN 101302158A CN A2008101235441 A CNA2008101235441 A CN A2008101235441A CN 200810123544 A CN200810123544 A CN 200810123544A CN 101302158 A CN101302158 A CN 101302158A
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Abstract
The invention discloses a method for synthesizing PVC plasticizer DOTP by waste polyester resource utilization, which belongs to the plasticizer technical field. The method comprises the following steps that: 1. under the existence of catalyst, waste polyester scraps are heated with 2-ethyl hexanol to carry out the degradation reaction; 2. glycol produced by the reaction and the 2-ethyl hexanol are coboiled and condensed, and then the glycol is removed through water scrubbing and is reclaimed; 3. reactant coarse ester is orderly subject to aqueous alkali and water for washing, an aqueous layer and an organic layer are separated; the organic layer is added with adsorbent, then the unreacted 2-ethyl hexanol is steamed out, and the plasticizer product dioctyl terephthalate (DOTP) is obtained after the filtration. The raw material of the invention, namely waste polyester can be polyester fiber, waste terylene cloth, leftover materials, waste polyester bottles, and polyester films and so on; the removal method of the catalyst adopts a water scrubbing filtration mode, the catalyst is simultaneously removed during neutralization, water scrubbing and filtration processes, and no additional process operation needs to be added for the removal of the catalyst, so the method has short process flow and low production cost.
Description
Technical field
The method of the synthetic PVC plasticizer DOTP of a kind of reclaiming waste polyester utilization belongs to plasticizer technical field.Be specifically related to the method for synthetic softening agent terephthalic acid two (2-ethyl) the own ester (DOTP) of a kind of reclaiming waste polyester utilization.
Background technology
Polyester (polyethylene terephthalate, PET) is mainly used in produces polyster fibre and film, as mineral water bottle etc., after the nineties in 20th century, China becomes the center of polyester industrial development, not only original manufacturer enlarges its industrial scale, and some new enterprises build large-scale production line successively.The annual production of China's polyester has at present reached 1,000 ten thousand tons, and along with the going deep into of polyester material study on the modification, the consumption of polyester will inevitably increase rapidly.The scale operation of polyester material and use must be accompanied by the generation of a large amount of useless polyester, and how making these useless polyester become available resource is very significant research.
Terephthalic acid two (2-ethyl) own ester (DOTP) is a kind of Chemicals of of many uses, excellent property, mainly as the softening agent of PVC plastics, is specially adapted to 70 ℃ of level CABLE MATERIALS.Along with the requirement of electron trade to the CABLE MATERIALS resistance to elevated temperatures progressively improves, DOTP becomes the primary plasticizer of 70 ℃ of level CABLE MATERIALS.In addition, the toxicity problem of softening agent causes social extensive concern, to the also raising gradually of service requirements of softening agent.DOTP is listed in non-toxic plasticizer, can replace adjacent benzene class softening agent fully, uses as substituting phthalic acid two (2-ethyl) own ester (DOP), and its demand will increase day by day.
Suitability for industrialized production DOTP mainly adopts terephthalic acid and the preparation of 2-Ethylhexyl Alcohol esterification at present, the raw material terephthalic acid comes from petrochemicals, and oil price constantly rises violently, the world is caused tremendous influence, the price that with the oil is the Chemicals of raw material will certainly fluctuate thereupon, exerts heavy pressures on to chemical enterprise.The synthetic DOTP of the useless polyester of utilization not only raw material is easy to get, also effectively handle polyester waste material, realized turning waste into wealth, met modern environmental protection concept requirement, the present invention is the synthetic DOTP of raw material with the waste polyester, be current comparatively rationally and one of the approach that utilizes of the high reclaiming waste polyester of economic benefit.
Summary of the invention
The object of the present invention is to provide the method for the synthetic PVC plasticizer DOTP of a kind of reclaiming waste polyester utilization; solve a large amount of waste polyesters and cause the influence of the wasting of resources and oil crisis PVC softening agent industry; the method of utilizing the synthetic plasticizer DOTP of useless polyester is provided; not only the quality of product is good; and production process generation waste water is few, reaches the purpose of cleaner production.
Technical scheme of the present invention: the method for the synthetic PVC plasticizer DOTP of a kind of reclaiming waste polyester utilization:
(1) useless polyester and 2-Ethylhexyl Alcohol after washing, pulverizing are joined in the reactor, the mol ratio of useless polyester and 2-Ethylhexyl Alcohol is 1: 3-1: 20, stirring is warming up to 170 ℃-230 ℃, add catalyzer and carry out DeR, catalyzer is selected from one or more in titanic acid ester, metal acetate salt, metal carboxylate, solid acid, the metal chloride, catalyst consumption is the 0.1%-3.0% of the quality of useless polyester material, and the reaction times was controlled at 3-15 hour;
(2) ethylene glycol of reaction process generation together steams with 2-Ethylhexyl Alcohol, and the mixing steam condensing reflux is removed ethylene glycol and reclaimed ethylene glycol through water scrubber, and the 2-Ethylhexyl Alcohol Returning reactor that phlegma is removed behind the ethylene glycol continues to participate in reaction;
(3) after the DeR, with the alkali aqueous solution washing, reactant continues to wash with water under 50 ℃ of-100 ℃ of temperature reactant, separates water layer and organic layer under 50 ℃ of-100 ℃ of temperature; Add sorbent material in the organic layer, consumption is 5% of useless polyester quality, and unreacted 2-Ethylhexyl Alcohol and moisture content are removed in underpressure distillation, remove by filter sorbent material and solid impurity, catalyzer is separated through the washing filtering mode simultaneously, and filtrate is the product plasticizer DOTP;
Sorbent material is selected activated carbon, carclazyte, kaolin, alkalescence or neutral alumina for use.
The useless polyester material that is used for (1) is selected for use: beverage or food product pack polyester bottles, trevira silk, mylar scrap stock and the polymeric scrap that contains the polyester composition.
The catalyzer that is used for (1) reaction system is separated through the washing filtering mode.
The alkali that is used for (3) is selected one or more of potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood for use.
Reaction formula is:
The first step depolymerization reaction:
With a certain amount of through washing, pulverize pretreated useless polyester, 2-Ethylhexyl Alcohol, the catalyzer reaction unit of packing into, heated and stirred, controlled temperature is at 170 ℃-230 ℃, stirring and refluxing 3-15 hour, ethylene glycol that reaction generates and excessive 2-Ethylhexyl Alcohol form azeotropic and shift out reaction system rapidly, and reaction is constantly carried out to positive.Reaction finishes postcooling to 50 ℃-100 ℃, with the alkali aqueous solution neutralization, acid number is reduced to below the 0.05mgKOH/g, through washing, separate water layer and organic layer again, add sorbent material, intensification is removed excessive 2-Ethylhexyl Alcohol with vacuum, filters the product plasticizer DOTP that obtains faint yellow transparent liquid.
Beneficial effect of the present invention: reaction of the present invention is reversible reaction, carry out and the ethylene glycol that generates constantly need be shifted out from reaction system for helping reacting to forward, destroy the transesterification reaction balance, the present invention adopts the method that adds excessive 2-Ethylhexyl Alcohol, utilizes ethylene glycol and 2-Ethylhexyl Alcohol to form azeotrope rapidly, and phegma is through washing, and make ethylene glycol leave reaction system, reduce the reaction times, so technical process of the present invention is short, production cost is low.
One of raw material of the present invention, useless polyester can be trevira, waste and old terylene cloth and scrap stock, waste polyester bottle, polyester film etc., and the form of raw material is little to reaction process and quality product influence.
The removal method of technological process catalyzer of the present invention adopts the washing filtering mode, in and removed catalyzer simultaneously in the water washing process, needn't increase other technological operation at the problem of removing of catalyzer, shorten technical process, reduce production costs.
Description of drawings
Fig. 1 utilizes the infrared spectrogram of the synthetic DOTP product of useless polyester.
Embodiment
The present invention is further described with following embodiment.
In the there-necked flask that agitator, thermometer and water-and-oil separator are housed, add a certain amount of polyester bottle slice, 2-Ethylhexyl Alcohol, tetrabutyl titanate, wherein the mol ratio of polyester and 2-Ethylhexyl Alcohol is 1: 4, and the consumption of tetrabutyl titanate is 0.5% of a polyester quality.Controlled temperature stirred 5 hours at 180 ℃-220 ℃, was cooled to 70 ℃-90 ℃, and the aqueous sodium carbonate neutralization with 3% again through washing, separates water layer and organic layer; Add the sorbent material neutral alumina in the organic layer, consumption is 5% of a polyester bottle slice quality, and decompression adds the excessive 2-Ethylhexyl Alcohol of heat extraction, removes by filter neutral alumina, obtains light yellow transparent liquid product plasticizer DOTP.The infrared spectra of product D OTP is as shown in Figure 1: 1728.0cm
-1Be the stretching vibration of C=O in the ester group, 1268.9cm
-1And 1117.7cm
-1Be the characteristic peak of C-O stretching vibration in the ester group, 1579.2cm
-1, 1505.3cm
-1And 1463.1cm
-1Be phenyl ring skeletal vibration absorption peak, 2959.7cm
-1, 2930.3cm
-1, 2860.9cm
-1, be saturated alkane-CH on the side chain
3,-CH
2-stretching vibration absorb 874.7cm
-1Be the para-orientation characteristic absorbance of phenyl ring, present the feature of product ester.
Embodiment 2
The polyester bottle slice, 2-Ethylhexyl Alcohol, the zinc acetate that in the reaction unit of embodiment 1, add certain proportioning, solid acid catalyst, wherein the mol ratio of polyester and 2-Ethylhexyl Alcohol is 1: 6, and the total consumption of zinc acetate and solid acid catalyst is 1.0% of a polyester bottle slice quality.Heated and stirred, control reaction temperature stirred 6 hours at 180 ℃-220 ℃, were cooled to 70 ℃-90 ℃, and with 3% aqueous sodium hydroxide solution neutralization, water layer and organic layer are separated in the washing back; Add carclazyte in the organic layer, consumption is 5% of a polyester bottle slice quality, and decompression adds the excessive 2-Ethylhexyl Alcohol of heat extraction, removes by filter carclazyte, obtains light yellow transparent liquid product plasticizer DOTP.
The polyester dacron cloth waste, 2-Ethylhexyl Alcohol, the solid acid catalyst that in the reaction unit of embodiment 1, add certain proportioning, wherein the mol ratio of polyester dacron cloth waste and 2-Ethylhexyl Alcohol is 1: 20, and the consumption of solid acid catalyst is 0.5% of a polyester dacron cloth waste quality.Heated and stirred, control reaction temperature were reacted 5 hours at 180 ℃-220 ℃, were cooled to 70 ℃-90 ℃, and the aqueous sodium carbonate washing with 3% separates water layer and organic layer again after washing; Add activated carbon in the organic layer, consumption is 5% of a polyester dacron cloth waste quality, and decompression adds the excessive 2-Ethylhexyl Alcohol of heat extraction, removes by filter activated carbon, obtains light yellow transparent liquid product plasticizer DOTP.
Claims (4)
1, the method for the synthetic PVC plasticizer DOTP of a kind of reclaiming waste polyester utilization is characterized in that:
(1) useless polyester and 2-Ethylhexyl Alcohol after washing, pulverizing are joined in the reactor, the mol ratio of useless polyester and 2-Ethylhexyl Alcohol is 1: 3-1: 20, stirring is warming up to 170 ℃-230 ℃, add catalyzer and carry out DeR, catalyzer is selected from one or more in titanic acid ester, metal acetate salt, metal carboxylate, solid acid, the metal chloride, catalyst consumption is the 0.1%-3.0% of the quality of useless polyester material, and the reaction times was controlled at 3-15 hour;
(2) ethylene glycol of reaction process generation together steams with 2-Ethylhexyl Alcohol, and the mixing steam condensing reflux is removed ethylene glycol and reclaimed ethylene glycol through water scrubber, and the 2-Ethylhexyl Alcohol Returning reactor that phlegma is removed behind the ethylene glycol continues to participate in reaction;
(3) after the DeR, with the alkali aqueous solution washing, reactant continues to wash with water under 50 ℃ of-100 ℃ of temperature reactant, separates water layer and organic layer under 50 ℃ of-100 ℃ of temperature; Add sorbent material in the organic layer, consumption is 5% of useless polyester quality, and unreacted 2-Ethylhexyl Alcohol and moisture content are removed in underpressure distillation, remove by filter sorbent material and solid impurity, catalyzer is separated through the washing filtering mode simultaneously, and filtrate is the product plasticizer DOTP;
Sorbent material is selected activated carbon, carclazyte, kaolin, alkalescence or neutral alumina for use.
2, method according to claim 1 is characterized in that the useless polyester material that is used for (1) selects for use: beverage or food product pack polyester bottles, trevira silk, mylar scrap stock and the polymeric scrap that contains the polyester composition.
3, method according to claim 1 is characterized in that the catalyzer that is used for (1) reaction system is separated through the washing filtering mode.
4, method according to claim 1, the alkali that it is characterized in that being used for (3) are selected one or more of potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood for use.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101235441A CN101302158A (en) | 2008-06-06 | 2008-06-06 | Method for synthesizing PVC plasticiser by reclaiming waste polyester |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659599A (en) * | 2012-04-19 | 2012-09-12 | 中国林业科学研究院林产化学工业研究所 | Method for comprehensively improving utilization rate of raw supplementary material in polyester waste preparation DOPT (Dioctyl Terephthalate) process |
| CN104557550A (en) * | 2015-02-06 | 2015-04-29 | 山东同源环保新材料有限公司 | Production method for preparing dioctyl terephthalate by virtue of alcoholysis and esterification of polyester wastes |
| CN104961912A (en) * | 2015-06-18 | 2015-10-07 | 张家港市大能塑料制品有限公司 | Special plastic auxiliary |
| CN105255061A (en) * | 2015-11-16 | 2016-01-20 | 广东达华节水科技股份有限公司 | Environment-friendly soft PVC plasticizer |
| CN105936620A (en) * | 2016-05-23 | 2016-09-14 | 山东成武易信环保科技有限公司 | Ethylene glycol purifying apparatus in environmentally-friendly plasticizer DOTP preparation process, and purifying technology thereof |
| CN107216250A (en) * | 2017-06-14 | 2017-09-29 | 王林聪 | A kind of method that utilization polyethylene terephthalate waste material prepares Di-2-ethylhexyl terephthalate |
| CN109311798A (en) * | 2016-06-27 | 2019-02-05 | 沙特基础工业全球技术有限公司 | For the method by recycling raw material preparation dimethyl terephthalate ester |
| CN109879760A (en) * | 2019-03-26 | 2019-06-14 | 山东同源环保新材料有限公司 | A kind of method of terylene waste material alcoholysis esterification preparation dioctyl terephthalate |
| WO2020048444A1 (en) * | 2018-09-05 | 2020-03-12 | 长春美禾科技发展有限公司 | Method for refining non-petroleum-based ethylene glycol |
-
2008
- 2008-06-06 CN CNA2008101235441A patent/CN101302158A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659599A (en) * | 2012-04-19 | 2012-09-12 | 中国林业科学研究院林产化学工业研究所 | Method for comprehensively improving utilization rate of raw supplementary material in polyester waste preparation DOPT (Dioctyl Terephthalate) process |
| CN104557550A (en) * | 2015-02-06 | 2015-04-29 | 山东同源环保新材料有限公司 | Production method for preparing dioctyl terephthalate by virtue of alcoholysis and esterification of polyester wastes |
| CN104961912A (en) * | 2015-06-18 | 2015-10-07 | 张家港市大能塑料制品有限公司 | Special plastic auxiliary |
| CN105255061A (en) * | 2015-11-16 | 2016-01-20 | 广东达华节水科技股份有限公司 | Environment-friendly soft PVC plasticizer |
| CN105936620A (en) * | 2016-05-23 | 2016-09-14 | 山东成武易信环保科技有限公司 | Ethylene glycol purifying apparatus in environmentally-friendly plasticizer DOTP preparation process, and purifying technology thereof |
| CN109311798A (en) * | 2016-06-27 | 2019-02-05 | 沙特基础工业全球技术有限公司 | For the method by recycling raw material preparation dimethyl terephthalate ester |
| US20190308925A1 (en) * | 2016-06-27 | 2019-10-10 | Sabic Global Technologies B.V. | Process for the preparation of dialkyl terephthalates from recycle feedstocks |
| CN107216250A (en) * | 2017-06-14 | 2017-09-29 | 王林聪 | A kind of method that utilization polyethylene terephthalate waste material prepares Di-2-ethylhexyl terephthalate |
| CN107216250B (en) * | 2017-06-14 | 2020-11-24 | 王林聪 | Method for preparing diisooctyl terephthalate by using polyethylene glycol terephthalate waste |
| WO2020048444A1 (en) * | 2018-09-05 | 2020-03-12 | 长春美禾科技发展有限公司 | Method for refining non-petroleum-based ethylene glycol |
| CN109879760A (en) * | 2019-03-26 | 2019-06-14 | 山东同源环保新材料有限公司 | A kind of method of terylene waste material alcoholysis esterification preparation dioctyl terephthalate |
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