CN106832397A - The method of online reuse PET Polymerization Wastes - Google Patents
The method of online reuse PET Polymerization Wastes Download PDFInfo
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- CN106832397A CN106832397A CN201510889711.3A CN201510889711A CN106832397A CN 106832397 A CN106832397 A CN 106832397A CN 201510889711 A CN201510889711 A CN 201510889711A CN 106832397 A CN106832397 A CN 106832397A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention relates to a kind of method of online reuse PET Polymerization Wastes, it is mainly comprised the following steps：(1) the Polymerization Waste produced in PET production processes is crushed, depolymerization kettle is then added together with the tower bottoms of esterification technique tower；(2) again to reaction kettle of the esterification vapour mixture is passed through in depolymerization kettle, until pressure is balanced with polymerization esterification system pressure in kettle；(3) depolymerization reaction is carried out under high-temperature and high-pressure conditions, the PET depolymerizing substances that inherent viscosity is 0.05-0.15dL/g low-molecular-weights are obtained；(4) depolymerizing substance delivers to esterification system, and polyester slice is obtained through techniques such as preshrunk, the poly-, pelletizings of final minification.The present invention realizes the online fully recovering of PET Polymerization Wastes, and the performance of gained reclaimed polyester is suitable with normal polyester performance, significantly reduces the production cost of PET.
Description
Technical field
The invention belongs to macromolecular compound production field, and in particular to a kind of method of the Polymerization Waste produced in online reuse PET production processes.
Background technology
PET (PET) has light weight, intensity is high, the transparency is good, heat-resist, good stability of the dimension and the features such as excellent chemical-resistance, and it is widely used in the fields such as beverage bottle, fiber, film, chip level and electrical apparatus insulation material, it has also become the maximum kind of product in synthetic fibers.But PET is mass produced and used, and is necessarily accompanied with the discharge and generation of a large amount of discarded objects.The end of the year 2013 China's polyester PET production capacity is up to 43,000,000 tons, the PET industry utilization of capacity is calculated with 60%, polymerization process waste discharge rate is calculated with 0.1%, often it is only polymeric rings section and just produces about 30,000 tons of waste discharge material, but this only accounts for the sub-fraction of waste polyester total amount, there are substantial amounts of polyester bottles every year, polyester film and clothing etc. are discarded in the form of waste polyester, therefore waste polyester amount is very huge.
Simultaneously, Natural Resources in China is again relatively deficient, and the half of average resource per capita deficiency world population average resource per capita, the situation of shortage of resources is extremely serious, therefore the exploitation of resources conservation and comprehensive utilization, especially regenerated resources seem particularly significant and urgent.By recycling waste PET, both can effectively curb environmental pollution, huge economic benefit can be created again, and will greatly alleviate the immense pressure that PET production costs and environmental pollution are brought.
At present, existing polyester waste material is as follows by the document situation for hydrolyzing with alcoholysis prepares PET depolymerizing substances both at home and abroad：
Chinese patent 201210055343.9 discloses a kind of production method of spent glycol depolymerization waste polyester fibers, with zinc acetate as catalyst, ethylene glycol is alcoholysis agent, through steps such as repeatedly washing, crystallization, purifications, obtains ethylene glycol terephthalate (BHET).Gained BHET must be purified by method for crystallising, and the method needs complicated processing step and device.
Chinese patent 200910081359.5 disclose it is a kind of using methyl alcohol and cosolvent, depolymerizing waste polyester obtains dimethyl terephthalate (DMT) (DMT) and ethylene glycol method at supercritical conditions, super critical condition depolymerization high energy consumption, while needing increase equipment recovery cosolvent.
Chinese patent 200910095295.4 discloses one kind with water as supercritical medium, the method that the useless PET of depolymerization obtains terephthalic acid (TPA) and ethylene glycol depolymerizing substance, depolymerization reaction is carried out under 375~450 DEG C of high temperature, 22.12Mpa~50Mpa high pressures, therefore, the requirement that the method is carried to consersion unit is very high.
United States Patent (USP) US 20070882941 discloses a kind of useless PET bottle recoverying and utilizing method, by the PET bottle after use through glycolysis alcoholysis, DMT is obtained by with methyl alcohol ester exchange reaction, terephthalic acid (TPA) depolymerizing substance is obtained by hydrolysis, the PET reclaimings are produced and various chemical processes such as are related to react, separate, crystallize, and PET removal process is relative complex.
World patent WO 2005CZ00076 disclose a kind of method of chemical recovery Waste Polyester, including pet waste are hydrolyzed, is separated, crystallized and obtain terephthalic acid (TPA), ethylene glycol.United States Patent (USP) US 20010967929 discloses one kind in anhydrous conditions, useless PET and one or more salt of weak acid and ethylene glycol is carried out into depolymerization reaction, the method for obtaining water miscible depolymerizing substance.The useless PET processes of above-mentioned recovery further relate to separation, crystallization process except depolymerization reaction, and recovery process is complex, it is necessary to increasing equipment carries out above-mentioned treatment.
In addition, the country also has been friends in the past, the depolymerizing substance of polyester is mixed with the report of PET with the melt of new polyester：
Chinese patent 200780017992.7 discloses a kind of method for manufacturing pellet from the mixture of old polyester and new polyester, by the fusing of old polyester, add the glycol for melting old polyester, the depolymerizing substance of old polyester is mixed with the melt of the new polyester from fusing reactor before whole polycondensation step, pet polymer is obtained through final minification is poly-, then PET sections are obtained through granulation underwater, full gear treatment.Melt viscosity high fluidity is poor in Last-polycondensatioreactor reactor, causes depolymerizing substance to be difficult to be well mixed in Last-polycondensatioreactor reactor, influences end product quality.
Chinese patent 99105533.0 discloses one kind and linear polyester process is continuously reclaimed from polyester waste material, by the melting of undried polyester waste material, polymer chain degraded that is hydrolyzed by the moisture content of attachment, will glycol corresponding with the basic component units of polymer added to carrying out sugar solution degraded in melt, and so processed melt is further condensed to the desired degree of polymerization.Polyester waste material is by melting extrusion, and thermal degradation and thermal-oxidative degradation degree are high, limits Pillar recovery product subsequent applications.
Document above report all rests on the aspect of theoretical and experimental study, do not refer to how the Polymerization Waste produced in online reuse PET production processes.This situation, for meeting with the demand of the production of polyester producer that " steady production, cost efficiency " is objective, still there is sizable distance.
The content of the invention
The invention aims to overcome prior art not enough, a kind of method of online reuse PET Polymerization Wastes is proposed, it is intended to the waste material fully recovering that will be produced in PET polymerization production process, reduce resource consumption and production cost, improve the on-road efficiency of polyplant.
Goal of the invention is achieved through the following technical solutions：
The method of online reuse PET Polymerization Wastes, it is characterised in that：The method step is,
1. the Polymerization Waste produced in PET production processes is ground into particle of the diameter less than 5mm；
2. the tower bottoms of PET particles and PET production Esterification Stages is pressed into (6~18):1 mass ratio carries out mix in depolymerization kettle；
3. depolymerization kettle nitrogen displacement and let out to normal pressure, the vapor-phase material in esterifying kettle is passed through depolymerization kettle；
4. depolymerization kettle opens heating, and material stands 20~30min in kettle, treats material liquid temperature higher than 200 DEG C of beginning low rate mixings；
5. after 10~20min of low rate mixing, speed of agitator is gradually adjusted to conventional rotating speed；
6. material carries out HTHP depolymerization reaction in depolymerization kettle, obtains inherent viscosity for 0.05-0.15dL/g low-molecular-weight PET depolymerizing substances；
7. the PET depolymerizing substances of gained are added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system, then, routinely the polymerization process of polyester completes polymerisation.
Further, the parameter of the step 2. tower bottoms is：Water content is 0.5~1.0wt%, and remaining main component is ethylene glycol, and temperature is 180~190 DEG C.
Further, the parameter of the 3. described vapor-phase material of step is：Ethylene glycol is (40 with water quality ratio:60)~(60:40), temperature be 250~265 DEG C, gauge pressure be 0.1~0.2MPa.
Further, step 6. middle depolymerization reaction temperature be 200~260 DEG C, pressure be 0.1~0.4MPa, the depolymerization reaction time be 1.0~3.0hr.
Further, step 7. in PET depolymerizing substances be by weight for 10%~50% ratio is added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system.
Further, 6. step adds catalyst in depolymehzation process, and the catalyst is metal acetate salt, inorganic acid or inorganic base；Preferably, the catalyst is zinc acetate, platinum acetate, magnesium acetate, manganese acetate, cobalt acetate；It is highly preferred that the catalyst is zinc acetate, a ten thousandth of its consumption less than pet waste quality.
Further, 6. step adds heat stabilizer and antioxidant in depolymehzation process；Preferably, the additive is phosphoric acid ester heat stabilizer and Hinered phenols antioxidant；It is highly preferred that the antioxidant is hindered phenol antioxygen 1010, a ten thousandth of its consumption less than pet waste quality.
Further, 7. the PET depolymerizing substances are added after the completion of esterification process in PET polymerization reaction systems or esterification to step.
Preferably, if the Reclaim of PET Scrap method is applied to PET continuous production devices, the depolymerizing substance system of step 6. gained is then added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system after being homogenized by homogeneous kettle；But, if the method is applied to PET intervalization process units, then step 6. gained depolymerizing substance can be added directly into ethylene glycol/terephthalic acid (TPA) polymerization reaction system, also can by homogeneous kettle be homogenized after be then added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system.
Compared with prior art, the progress of the present invention prominent substantive distinguishing features and conspicuousness is mainly reflected in：
1st, present invention optimizes the ethylene glycol consumption of waste discharge PET alcoholysis, alcohol content in depolymerizing substance is reduced, reduces the evaporation capacity that depolymerizing substance adds ethylene glycol in esterification system, reduce the energy consumption of device；
2nd, the present invention accelerates the depolymerization reaction speed of waste discharge PET by screening catalyst type, shortens the depolymerization time；Total ethylene glycol consumption in PET production processes is reduced, the generation of accessory substance (such as diethylene glycol (DEG)) is reduced；
3rd, present invention optimizes the depolymerization reaction technique of waste discharge PET, by adding thermal oxidation stabilizer, effectively prevent the thermal-oxidative degradation of depolymehzation process from reacting, improve the hot oxygen performance of depolymerizing substance；
4th, the inventive method is polymerized again when the process units of PET is applied to after PET waste discharges material is recycled, and realizes online reuse, reduces the waste discharge amount of PET process units, improves device benefit；
5th, the depolymerization process flow of waste discharge PET of the present invention is simple, by changing depolymerization process, can process the PET waste discharge material of variety classes, different viscosities.
Brief description of the drawings
Fig. 1 is existing PET process units figure；Wherein, 1 is esterification system, and 2 is pre- compression system, 3 is final minification system, and 4 is esterification tower, and 5 is depolymerization kettle, and 6 is depolymerization feed chamber, and 7 is pelleter.
Fig. 2 is the preferred scheme that technical scheme of the present invention is applied to PET process units；Mark implication in figure is：1-esterification system, 2-pre- compression system, 3-final minification system, 4-process tower, 5-depolymerization kettle, 6-homogeneous kettle, 5-1/5-4/5-5-regulating valve, 5-2/6-3-flowmeter, 5-3-meausring apparatus, 6-1-filter, 6-3-delivery pump, 7-pelleter.
Specific embodiment
The present invention relates to a kind of method of the online reuse of polyester waste material, the waste material that this method is discharged PET process units, such as useless slurry block, useless section, depolymerization kettle is added by crushing, depolymerization reaction is carried out under higher temperature, elevated pressures, the PET depolymerizing substances of low-molecular-weight are obtained, then above-mentioned depolymerizing substance is quantitatively adding in process units esterifying kettle, polyester slice is obtained through techniques such as preshrunk, the poly-, pelletizings of final minification.Specific method step is as follows：
(1) Polymerization Waste produced in PET production processes is ground into diameter less than 5mm particles.
(2) PET particles and device esterification technique tower bottoms (tower reactor 0.5~1.0wt% of liquid water content, remaining main component is ethylene glycol, 180~190 DEG C of temperature) are pressed into (6~18):1 mass ratio, carries out mix in depolymerization kettle.
(3) depolymerization kettle nitrogen displacement and let out to normal pressure, by esterifying kettle vapor-phase material, (ethylene glycol compares 40 with water quality in vapor-phase material:60~60:40th, 250~265 DEG C of temperature, 0.1~0.2MPa of gauge pressure) it is passed through depolymerization kettle.
(4) start the heating of depolymerization kettle, stand 20~30min and treat material liquid temperature>200 DEG C, low rate mixing.
(5) after 10~20min of low rate mixing, speed of agitator is gradually adjusted to conventional rotating speed.
(6) in depolymerization kettle material 200~260 DEG C of temperature, 0.1~0.4MPa of pressure, 1.0~3.0hr HTHP depolymerization reaction, obtain inherent viscosity be 0.05-0.15dL/g low-molecular-weight PET depolymerizing substances；The depolymehzation process time is short, and depolymerizing substance is without heterochromatic；Ethylene glycol content is few in depolymerization dispensing, and depolymerizing substance diethylene glycol content is low.
(7) ratio with above-mentioned PET depolymerizing substances with weight than 10%~50%, is added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system, is added after the completion of esterification process or esterification, and then, routinely the polymerization process of polyester completes polymerisation.The available PET performances that are polymerized again are suitable with traditional performance.Preferably, if the Reclaim of PET Scrap method is applied to PET continuous production devices, during the depolymerizing substance of gained need to be added to ethylene glycol/terephthalic acid (TPA) polymerization reaction system after homogeneous kettle homogenizing；Meanwhile, if being applied to PET intervalization process units, the depolymerizing substance of gained is a preferred mode in being added to ethylene glycol/terephthalic acid (TPA) polymerization reaction system after homogeneous kettle homogenizing.
In addition, in order to accelerate PET depolymerization reaction speed, catalyst is added in depolymehzation process.For the alcoholysis of PET high temperature and hydrolysis, available catalyst has metal acetate salt, inorganic acid or inorganic base.It is environment-friendly in view of depolymehzation process, first-selected metal acetate salt, such as zinc acetate, platinum acetate, magnesium acetate, manganese acetate, cobalt acetate, preferably zinc acetate.Optimization depolymerization process condition, zinc acetate consumption is less than 100ppm (PET mass).Polyester can be added in order to improve depolymerizing substance and depolymerization polymerizate appearance luster again, in PET depolymehzation process often with heat stabilizer and antioxidant, such as phosphoric acid ester heat stabilizer, Hinered phenols antioxidant.This depolymerization scheme selects hindered phenol antioxygen 1010, its consumption to be less than 100ppm (PET mass).
Below in conjunction with the accompanying drawings 1 and accompanying drawing 2 is vivider specifically illustrates technical scheme.It is as shown in Figure 1 a kind of existing PET process units figure, it has esterification, preshrunk, final minification polymeric segment.1 is esterification system, and 2 is pre- compression system, 3 is final minification system, and 4 is esterification tower, and 5 is depolymerization kettle, and 6 is depolymerization feed chamber, and 7 is pelleter.
The preferred scheme of PET productions is applied to for technical scheme such as Fig. 2, it is on the basis of existing PET production technologies (such as Fig. 1), by adding the device that waste discharge PET is recycled, PET waste discharge material is polymerized again, to reduce device waste discharge amount, lifting device benefit.Wherein, the adjusted valve 5-1 of the tower bottoms of process tower 4, flowmeter 5-2, into depolymerization kettle 5, additive is added on the tower bottoms pipeline of process tower 4；After waste discharge PET particles are weighed through meausring apparatus 5-3, it is quantitatively adding in storage tank 5；Nitrogen pipeline is connected by regulating valve 5-4 with depolymerization kettle 5；Esterification vapour mixture enters homogeneous kettle 6 by valve 5-5；Depolymerization kettle 5 is then communicated by filter 6-1 with homogeneous kettle 6；Depolymerizing substance after homogeneous enters esterifying kettle through delivery pump 6-2 and flowmeter 6-3.Wherein, nitrogen pipeline etc. is air in displacement depolymerization kettle 5 as the effect of pressure system first, next to that by material press-in homogeneous kettle 6.
Referring to the drawings 2, waste discharge PET of the present invention recycles the selection process flow for participating in producing is：The size-reduced particle as particle diameter less than 5mm of polyplant PET waste discharge material, then weighed through 5-3, into depolymerization kettle 5；Regulating valve 5-1 is opened, technique tower bottoms (180~190 DEG C of 0.5~1.0wt% of water content, temperature) is measured through flowmeter 5-2, add depolymerization kettle 5；Regulation 5-4 nitrogen valves, air in displacement depolymerization kettle 5, it is normal pressure to keep pressure in kettle；Opening valve 5-5 will be esterified vapour mixture (ethylene glycol and water vapour mass ratio 40:60~60:40th, 250~265 DEG C of temperature) depolymerization kettle 5 is introduced, until closing valve 5-5 when the pressure of depolymerization kettle 5 is with esterification system pressure balance；Start the heating medium for heating of depolymerization kettle 5, stand 20~30min and treat that the liquid temperature of depolymerization kettle 5 rises to more than 200 DEG C, start the agitator of depolymerization kettle 5, low rate mixing；After 10~20min of low rate mixing, speed of agitator is gradually promoted to conventional rotating speed；Material carries out the HTHP depolymerization reaction of 1.0~3.0hr in 200~260 DEG C of temperature, 0.1~0.4MPa of pressure in depolymerization kettle, obtains inherent viscosity for 0.05-0.15dL/g low-molecular-weight PET depolymerizing substances.
Wherein it should be noted that material depolymerizing substance relies on pressure difference and potential difference in depolymerization kettle 5, by filter 6-1, mix into homogeneous kettle 6 and be homogenized；Homogeneous kettle 6 has heating medium heating system, it is ensured that temperature of charge is higher than 240 DEG C；Material is measured by delivery pump 6-2 outputs, through flowmeter 6-3 in homogeneous kettle 6, and continuous and quantitative is added in esterification system 1.
Technical solution of the present invention is specifically illustrated below in conjunction with specific embodiment; but this is the preferred embodiment of the present invention; it should be understood that; for those skilled in the art; on the premise of the technology of the present invention principle is not departed from; some improvement and modification can also be made, these are improved and modification should also be considered as within protection scope of the present invention.
Firstly the need of explanation, useless PET the writing a Chinese character in simplified form for waste polyethylene terephthalate in following examples, PTA writes a Chinese character in simplified form for terephthalic acid (TPA), and EG writes a Chinese character in simplified form for ethylene glycol, Sb2EG3It is writing a Chinese character in simplified form for antimony glycol, ZnAC2It is writing a Chinese character in simplified form for zinc acetate, antioxidant 1010 is write a Chinese character in simplified form for four [β-(3,5- di-t-butyl -4- hydroxylphenyl esters) propionic acid] pentaerythritol esters.
Embodiment 1
Using 20L reactors, by useless PET particles 6.0kg, EG 1.0kg, deionized water 5.0g is together added to 20L reactors, and air in nitrogen displacement kettle is passed through high temperature esterification kettle vapour mixture, gauge pressure in kettle is maintained at 0.1MPa.Kettle heating is opened, 30min is stood, treats that liquid temperature is increased to more than 200 DEG C, low rate start stirring in kettle.After stirring at low speed 10min, speed of agitator is adjusted to rated speed.It is 0.10~0.40MPa in pressure, temperature carries out HTHP depolymerization reaction under conditions of 220 DEG C~260 DEG C, to stir 2.0hr.Pressure release discharges, and the PET depolymerizing substances that inherent viscosity is 0.070dL/g is obtained, without heterochromatic.
Using 20L polymerization reaction kettles, by 4.5kg PTA, 2.7kg EG, 1.8g Sb2EG3, add in 20L polymeric kettles, under conditions of 0.10~0.30MPa of pressure, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, normal pressure is reduced to, to the addition above-mentioned PET depolymerizing substances of 675g in kettle.280~290 DEG C are continuously heating to, vacuum is evacuated to below 100pa.Reactant viscosity in kettle is estimated according to power of agitator, so that it is determined that discharging time, obtains reuse PET sections.
Embodiment 2
Using 20L reactors, by useless PET particles 6.0kg, EG 1.0kg, deionized water 5.0g, ZnAC20.6g is together added to 20L reactors, and air in nitrogen displacement kettle is passed through high temperature esterification kettle vapour mixture, gauge pressure in kettle is maintained at 0.1MPa.Kettle heating is opened, 30min is stood, treats that liquid temperature is increased to more than 200 DEG C, low rate start stirring in kettle.After stirring at low speed 10min, speed of agitator is adjusted to rated speed.It is 0.10~0.30MPa in pressure, temperature carries out HTHP depolymerization reaction under conditions of 220 DEG C~250 DEG C, to stir 1.5hr.Pressure release discharges, and obtains the PET depolymerizing substances that inherent viscosity is 0.065dL/g, good colour.
Using 20L polymerization reaction kettles, by 4.5kg PTA, 2.7kg EG, 1.8g Sb2EG3, add in 20L polymeric kettles, under conditions of 0.10~0.30MPa of pressure, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, normal pressure is reduced to, to the addition above-mentioned PET depolymerizing substances of 675g in kettle.280~290 DEG C are continuously heating to, vacuum is evacuated to below 100pa.Reactant viscosity in kettle is estimated according to power of agitator, so that it is determined that discharging time, obtains reuse PET sections.
Embodiment 3
Using 20L reactors, by useless PET particles 6.0kg, EG 0.5kg, deionized water 2.5g, ZnAC20.6g, antioxidant 1010 1.2g are together added to 20L reactors, and air in nitrogen displacement kettle is passed through high temperature esterification kettle vapour mixture, gauge pressure in kettle is maintained at 0.1MPa.Kettle heating is opened, 30min is stood, treats that liquid temperature is increased to more than 200 DEG C, low rate start stirring in kettle.After stirring at low speed 10min, speed of agitator is adjusted to rated speed.It is 0.10~0.30MPa in pressure, temperature carries out HTHP depolymerization reaction under conditions of 220 DEG C~250 DEG C, to stir 1.0hr.Pressure release discharges, and obtains the PET depolymerizing substances that inherent viscosity is 0.075dL/g, and color and luster is excellent.
Using 20L polymerization reaction kettles, by 3.5kg PTA, 2.1kg EG, 1.4g Sb2EG3, add in 20L polymeric kettles, under conditions of 0.10~0.30MPa of pressure, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, normal pressure is reduced to, to the addition above-mentioned PET depolymerizing substances of 1.88kg in kettle.280~290 DEG C are continuously heating to, vacuum is evacuated to below 100pa.Reactant viscosity in kettle is estimated according to power of agitator, so that it is determined that discharging time, obtains reuse PET sections.
Embodiment 4
Using 20L reactors, by useless PET particles 6.0kg, EG 0.33kg, deionized water 1.6g, ZnAC20.6g is together added to 20L reactors, and air in nitrogen displacement kettle is passed through high temperature esterification kettle vapour mixture, gauge pressure in kettle is maintained at 0.1MPa.Kettle heating is opened, 30min is stood, treats that liquid temperature is increased to more than 200 DEG C, low rate start stirring in kettle.After stirring at low speed 10min, speed of agitator is adjusted to rated speed.It is 0.10~0.30MPa in pressure, temperature carries out HTHP depolymerization reaction under conditions of 220 DEG C~250 DEG C, to stir 1.5hr.Pressure release discharges, and obtains the PET depolymerizing substances that inherent viscosity is 0.090dL/g, good colour.
Using 20L polymerization reaction kettles, by 2.5kg PTA, 1.5kg EG, 1.0g Sb2EG3, add in 20L polymeric kettles, under conditions of 0.10~0.30MPa of pressure, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, normal pressure is reduced to, to the addition above-mentioned PET depolymerizing substances of 3.05kg in kettle.280~290 DEG C are continuously heating to, vacuum is evacuated to below 100pa.Reactant viscosity in kettle is estimated according to power of agitator, so that it is determined that discharging time, obtains reuse PET sections.
Embodiment 5
Using 20L reactors, by useless PET particles 6.0kg, EG 0.33kg, deionized water 1.6g, ZnAC20.6g, antioxidant 1010 1.2g are together added to 20L reactors, and air in nitrogen displacement kettle is passed through high temperature esterification kettle vapour mixture, gauge pressure in kettle is maintained at 0.1MPa.Kettle heating is opened, 30min is stood, treats that liquid temperature is increased to more than 200 DEG C, low rate start stirring in kettle.After stirring at low speed 10min, speed of agitator is adjusted to rated speed.It is 0.10~0.30MPa in pressure, temperature carries out HTHP depolymerization reaction under conditions of 220 DEG C~250 DEG C, to stir 1.5hr.Pressure release discharges, and obtains the PET depolymerizing substances that inherent viscosity is 0.090dL/g, and color and luster is excellent.
Using 20L polymerization reaction kettles, by 2.5kg PTA, 1.5kg EG, 1.0g Sb2EG3, add in 20L polymeric kettles, under conditions of 0.10~0.30MPa of pressure, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, normal pressure is reduced to, to the addition above-mentioned PET depolymerizing substances of 3.05kg in kettle.280~290 DEG C are continuously heating to, vacuum is evacuated to below 100pa.Reactant viscosity in kettle is estimated according to power of agitator, so that it is determined that discharging time, obtains reuse PET sections.
Comparative example 1
Using 20L polymerization reaction kettles, by 5.0kg PTA, 3.0kg EG, 2.0g catalyst Sb2EG3, add in polymeric kettle, under conditions of pressure 0.20MPa~0.30MPa, 230 DEG C~250 DEG C of temperature, stir about 2.0hr completes esterification.After water outlet reaches theoretical amount, decompression vacuum pumping raises temperature of reaction kettle, and at 280~290 DEG C, below vacuum 100pa carries out polycondensation reaction.Reactant viscosity in kettle is estimated according to power of agitator, discharging time is determined, PET sections are obtained.
Embodiment 6
The present embodiment uses the polyester production device of 80T/D, as shown in Fig. 2 EG and PTA is with 1.1:1 mole of ratio carries out slurry preparation, and slurry enters esterification system 1, and esterification system includes the first esterifying kettle and second esterification kettle, wherein the first esterification kettle meter pressure is in 0.1~0.2Mpa.
Device PET waste discharges lumps (inherent viscosity 0.30-0.67dL/g) is ground into 1mm powders with pulverizer.
Control valve 5-1 apertures and meausring apparatus 5-3 motor rotary speeds, make PET waste discharges material with process tower tower bottoms (185 DEG C of temperature, 0.5~1.0wt% of water content) mass ratio according to 12:1 is added in depolymerization kettle 5, while adding 50ppm ZnAC2, 100ppm antioxidant 1010s (relative to PET mass).With 0.05MPa is forced into after nitrogen displacement air, start the stirring motor of storage tank 5, stir 15min.
Control valve 5-4, air and to keep pressure in kettle be normal pressure in displacement depolymerization kettle 5；Opening valve 5-5 will be esterified vapour mixture (ethylene glycol and water vapour mass ratio 55:45th, 255~265 DEG C of temperature) depolymerization kettle 5 is introduced, closing valve 5-5 after pressure is with esterification system pressure balance in kettle.Open depolymerization kettle 5 to heat, stand 20~30min and treat that liquid temperature rises to more than 200 DEG C in kettle, starts agitator, stirring at low speed.After after stirring at low speed 15min, speed of agitator is gradually lifted, until conventional rotating speed.Material carries out the HTHP depolymerization reaction of 1.5hr in 200~250 DEG C of temperature, 0.1~0.4MPa of pressure in depolymerization kettle, obtains inherent viscosity 0.10dL/g or so low-molecular-weight PET depolymerizing substances.
Depolymerizing substance in depolymerization kettle relies on pressure difference and potential difference, by filter 6-1, mixes into homogeneous kettle 6 and is homogenized.Material is measured by delivery pump 6-3 outputs, through flowmeter 6-4 in homogeneous homogeneous kettle 6, and continuous and quantitative is added in esterification system 1.Depolymerization kettle outlet delivery pump 6-3 flows are adjusted to 8T/D, i.e. PET depolymerizing substances the second esterification kettle inlet pipeline that five kettle polymerization techniques are added with the ratio of slurry flow 10%.Esterification workshop section material supply preshrunk workshop section and final minification workshop section, according to common process control, polyester fondant obtains PET and cuts into slices through pelleter.
Comparative example 2
This comparative example uses the polyester production device of 80T/D, as shown in figure 1, EG and PTA is with 1.1:1 mole of ratio carries out slurry preparation, slurry supply esterification workshop section 1.PET waste discharge material are not used, normal production PET polyester slices.
The test performance of the PET polyester slices that various embodiments above and comparative example are produced is as shown in table 1：
The polyester slice performance of table 1
Embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 are the performance that the PET produced using technical scheme is cut into slices in table, comparative example 1 is the performance of the PET sections of conventional method production, be can be seen that by data in table, embodiment 1, embodiment 2, embodiment 3, embodiment 4, the performance of the PET polyester slices of the gained of implementation 5 and comparative example 1 are substantially more or less the same, but participate in polyester production process after the PET depolymerization due to the present invention using waste discharge, so compared with conventional method, cost of the present invention is lower, more environmentally friendly.Embodiment 6 is on the basis of the polyester production device of conventional 80T/D, waste discharge PET is equipped with to reclaim the device (such as Fig. 2) that is polymerized again to produce PET polyester slices, comparative example 2 is using the polyester production device production PET polyester slices of conventional 80T/D, as seen from Table 1, PET polyester slices performances of both gained are suitable, but embodiment 6 is the PET polyester slices for obtaining that are polymerized again by PET waste discharges material, compared with comparative example 1, device waste discharge amount is reduced, device benefit is improved.In addition, more also can be explained by above-mentioned, PET polyester waste materials can direct reuse, have no effect on the quality of polyester product.
Note：The performance test methods of the polyester slice of table 1 are with reference to GB/T14190-93.
Claims (15)
1. the method for online reuse PET Polymerization Wastes, it is characterised in that：The method step is,
1. the Polymerization Waste produced in PET production processes is ground into particle of the diameter less than 5mm；
2. PET particles are pressed with the tower bottoms of PET production Esterification Stages（6~18）:1 mass ratio carries out mix in depolymerization kettle；
3. depolymerization kettle nitrogen displacement and let out to normal pressure, the vapor-phase material in esterifying kettle is passed through depolymerization kettle；
4. depolymerization kettle opens heating, and material stands 20~30min in kettle, treats material liquid temperature higher than 200 DEG C of beginning low rate mixings；
5. after 10~20min of low rate mixing, speed of agitator is gradually adjusted to conventional rotating speed；
6. material carries out HTHP depolymerization reaction in depolymerization kettle, obtains inherent viscosity for 0.05-0.15dL/g low-molecular-weight PET depolymerizing substances；
7. the PET depolymerizing substances of gained are added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system, then, routinely the polymerization process of polyester completes polymerisation.
2. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：The parameter of the step 2. tower bottoms is：Water content is 0.5~1.0wt%, and remaining main component is ethylene glycol, and temperature is 180~190 DEG C.
3. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：The parameter of the 3. described vapor-phase material of step is：Ethylene glycol is with water quality ratio（40:60）~（60:40）, temperature be 250~265 DEG C, gauge pressure be 0.1~0.2 MPa.
4. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：Step 6. middle depolymerization reaction temperature be 200~260 DEG C, pressure be 0.1~0.4 MPa.
5. the method for online reuse PET Polymerization Wastes according to claim 4, it is characterised in that：The depolymerization reaction time is 1.0~3.0 hr.
6. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：Step 7. in PET depolymerizing substances be by weight for 10%~50% ratio is added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system.
7. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：6. step adds catalyst in depolymehzation process, and the catalyst is metal acetate salt, inorganic acid or inorganic base.
8. the method for online reuse PET Polymerization Wastes according to claim 7, it is characterised in that：The catalyst is zinc acetate, platinum acetate, magnesium acetate, manganese acetate, cobalt acetate.
9. the method for online reuse PET Polymerization Wastes according to claim 7, it is characterised in that：The catalyst is zinc acetate, a ten thousandth of its consumption less than pet waste quality.
10. the method for online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：6. step adds heat stabilizer and antioxidant in depolymehzation process.
The method of 11. online reuse PET Polymerization Wastes according to claim 10, it is characterised in that：The additive is phosphoric acid ester heat stabilizer and Hinered phenols antioxidant.
The method of 12. online reuse PET Polymerization Wastes according to claim 11, it is characterised in that：The antioxidant is hindered phenol antioxygen 1010, a ten thousandth of its consumption less than pet waste quality.
The method of 13. online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：7. the PET depolymerizing substances are added after the completion of esterification process in PET polymerization reaction systems or esterification to step.
The method of 14. online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：The polyester waste material reuse method is applied to PET continuous production devices, wherein, step 6. gained depolymerizing substance system by homogeneous kettle be homogenized after be then added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system.
The method of 15. online reuse PET Polymerization Wastes according to claim 1, it is characterised in that：The polyester waste material reuse method is applied to PET intervalization process units, wherein, step 6. gained depolymerizing substance be added directly into ethylene glycol/terephthalic acid (TPA) polymerization reaction system, or by homogeneous kettle be homogenized after be then added in ethylene glycol/terephthalic acid (TPA) polymerization reaction system.
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| CN109206596A (en) * | 2017-06-30 | 2019-01-15 | 远东新世纪股份有限公司 | Polyester preparation method for reducing content of diethylene glycol in polyester |
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| CN115160549A (en) * | 2022-08-26 | 2022-10-11 | 华润化学材料科技股份有限公司 | Production method for recycling and continuously operating polyester chips |
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