Patent Description:
Polyester (polyethylene terephthalate, PET) is the most produced synthetic fiber material, widely used in fiber, textile fabrics, clothing, polyester bottles, films, sheets, etc. Based on the needs of enhanced environmental awareness, resource conservation and sustainability, how to deal with the scraps produced in the manufacture of polyester products and the waste generated from the use of polyester products has become an urgent problem to be solved, and the recycling of waste polyester has become a development direction of green textile.

At present, the recycling methods of waste polyester mainly include physical recycling and chemical recycling. The physical recycling methods are relatively simple and economic, but the performance of the recycled products is poor. An important direction of the chemical recycling method is the alcoholysis of waste polyester with ethylene glycol (EG) into bishydroxy terephthalate (BHET) or oligomers, and then through transesterification in methanol to produce Dimethyl Terephthalate (DMT) and ethylene glycol. Pure DMT is obtained through purification and used as a raw material for polyester production, while methanol and ethylene glycol are used in the reaction system through purification and recycling to achieve the recycling of waste polyester.

The <CIT> provides a method for recycling waste polyester to produce DMT. The patent uses EG with a weight of <NUM>-<NUM> times of the weight of the waste polyester and alcoholizes the waste polyester in the presence of a catalyst and at a temperature of <NUM>-<NUM>. Then, the alcoholysis product is distilled and concentrated to distill out EG, and the weight ratio of EG to waste polyester in the concentrated alcoholysis product is controlled in <NUM>-<NUM>. The concentrated alcoholysis product is then transesterified with methanol to form DMT and purified by rectification to produce pure DMT. This technology uses solid polyester and EG alcoholysis reaction. The alcoholysis reaction is a solid-liquid heterogeneous reaction with long reaction time. At the same time, in the alcoholysis process of waste polyester, the amount of EG used for alcoholysis is large. In order to carry out the transesterification reaction well, it is necessary to distill out part of the EG in the alcoholysis product, which has a process of concentrating the alcoholysis product, leading to an increase in concentration devices and energy consumption.

Therefore, it is necessary to provide a method for continuously recycling waste polyester material to solve the problems of long reaction time and many impurities of products of the solid-liquid heterogeneous reaction and a lot more equipped concentration devices, so as to cause the problems of more energy consumption, high maintenance cost, etc..

<CIT> relates to a process and an apparatus for decomposing polyester waste.

<CIT> relates to a feedstock recycling process from polyester wastes and apparatus for using thereof.

<CIT> relates to a polyester material recycling and ultrasonic surface treating method.

<CIT> relates to regenerated PET melt or slice, preparation method thereof, ultralight and thermal-insulation regenerated polyester textile and preparation thereof.

<CIT> relates to a method for preparing polyester.

In order to achieve above objectives, a method for recycling of a waste polyester material by continuous alcoholysis as specified in any of claims <NUM>-<NUM> is provided and has the following steps of:.

Compared with the prior art, the present invention has at least the following beneficial effects:
The recycling method disclosed by the present invention adopts the technologies of continuous feeding and continuous alcoholysisin order to make the material undergo homogeneous alcoholysis in molten state. The time for alcoholysis is short, and two alcoholysis tanks connected to each other in series for continuous alcoholysis manufactures stable products. More, the amount of EG in alcoholysis process is optimized without any further distillation and concentration. Hence, the alcoholysis product directly enters a transesterification tank for transesterification reaction in order to save concentration devices.

The technical content, structural features, achieved objectives and effects of the technical solution of the present disclosure will be described in detail below.

The method for recycling the continuous alcoholysis of a waste polyester material comprises the steps of:.

After wide research, without proceeding dewatering and deoxidizing to the waste polyester material, the water content and the surface oxygen may greatly affect to the following alcoholysis reaction and the product. Otherwise, the waste polyester material being regularly dewatered and deoxidized makes a reduction of <NUM>% to 300ppm of the water contentin order to obtain a raw waste polyester material. Therefore, under the condition of a screw being melted, a possibility to a sub-reaction is greatly lowered down, so as to assure the purity and reaction efficiency.

The raw waste polyester material, an alcoholysis agent and an alcoholysis catalyst in a molten state are continuously and simultaneously fed into a first alcoholysis tank for a first alcoholysis. For instance, using the screw to heat the raw waste polyester material for being in a molten state. Hence, the screw may be melted and fed simultaneously through a rotary propulsion method. The rotary speed of the screw adjusts a delivery amount of the melted raw waste polyester material. The rotary speed of the screw is controlled by a liquid level in the first alcoholysis tank for achieving a relative stability of the liquid level in the first alcoholysis tank. An alcoholysis agent and an alcoholysis catalyst in a liquid state are continuously and simultaneously fed into the first alcoholysis tank through a fixed amount controlled by a metering pump in order to obtain a melt A after the first alcoholysis. The melt A is then fed into a second alcoholysis tank that is connected to the first alcoholysis tank in series for a second alcoholysis. Namely, the rotary speed of a pump controls a delivery amount of the melt A, and the rotary speed of the pump is decided by a liquid level in the second alcoholysis tank for achieving a relative stability of the liquid level in the second alcoholysis tank. The present invention takes the advantages of the alcoholysis reaction being carried out more thoroughly and the consistency of the alcoholysis degree being guaranteed, so as to obtain DMT, whichrecovery and purity are raised, after transesterification.

Further, the form of the raw waste polyester material has a certain influence on the effect of recycling alcoholysis. Before the raw waste polyester material fed into a alcoholysis tank, it is transformed from a solid state to a molten state. By conducting a filtration process, impurities are removed, thereby increasing the recovery rate and reaction rate of the alcoholysis. This results in energy savings and reduced equipment costs. More particularly, after the first alcoholysis, the molecular weight and viscosity of the melt A fed into the second alcoholysis tank are relatively low. Therefore, the filtration before feeding the melt A into the second alcoholysis tank is performed using a filter with a smaller pore size than the filter used before feeding the molten material into the first alcoholysis tank.

Preferably, a step, proceeding a filter process to the raw waste polyester material, is before the step of alcoholysis.

Further, the weight ratio of the waste polyester raw material and the alcoholysis agent has a certain influence on the depolymerization reaction. If the amount of alcoholysis agent is too high, it may cause excessive alcoholysis to be mixed into the alcoholysis product, and other sub-products will be formed in the alcoholysis. Too little alcoholysis agent dosage may cause incomplete alcoholysis, and the alcoholysis product contains more long-chain waste polyester, both of these situations will affect the product quality stability of the alcoholysis product, then affecting the subsequent transesterification reaction.

Preferably, the weight ratio of the raw waste polyester material to the alcoholysis agent is <NUM>:<NUM>~<NUM>, the raw waste polyester material and the alcoholysis agent are continuously and simultaneously fed into the first alcoholysis tank.

The amount of the alcoholysis catalyst in the alcoholysis reaction is an important factor to the alcoholysis product. Only a suitable range of the amount of the alcoholysis catalyst may assure the efficiency of the alcoholysis, but without wasting it.

Preferably, the amount of the alcoholysis catalyst added is <NUM>. 3wt%~<NUM>. 0wt% based on the weight of the waste polyester material.

A further study has found that, after the alcoholysis agent and the alcoholysis catalyst are fed into the first alcoholysis tank continuously and simultaneously in a liquid state, a mix of the alcoholysis agent and the alcoholysis catalyst in a quantitative relationship in a liquid state is with the best -COOH and -OH ratio, and then combined with the raw waste polyester materials in a quantitative range, wherein the raw waste polyester material has been removed from infusible impurities. Therefore, it can be ensured that the alcoholysis product with a desired degree is irreversibly obtained.

Preferably, the alcoholysis catalyst is dissolved in the alcoholysis agent in order to obtain alcoholysis catalyst liquid. The alcoholysis catalyst liquid and the raw waste alcoholysis material are continuously and simultaneously fed into the first alcoholysis tank. The amount of the alcoholysis catalyst is 10wt%~70wt% based on the weight of the alcoholysis agent.

The reaction temperature and reaction time in the alcoholysis tank may be two important factors in the quality stability of the product. The temperature of the alcoholysis tank is achieved by adding a heat source medium to the heating sheath outside the alcoholysis tank and the tube of the internal heating plate, and controlling the amount of the heat source medium. It is to be noted that, too low alcoholysis temperature will not be proper to the progress of the alcoholysis reaction, otherwise, too high temperature will cause side reactions.

Preferably, the temperature range of the alcoholysis in the first alcoholysis tank is <NUM>~<NUM>, and the time range of the alcoholysis is 40minutes~90minutes.

Preferably, the temperature range of the alcoholysis in the second alcoholysis tank is <NUM>~<NUM>, and the time range of the alcoholysis is 40minutes~90minutes.

Further, the different categories of the alcoloysis catalysis are also important factors to the alcoloysis reaction. According to massive researches, potassium carbonate and zinc acetate are the preferred alcoholysis catalysts for polyester alcoholysis.

The inventor has further discovered through a lot of research that the form of the waste polyester material has a greater impact on the process of feeding through the heating of the screw. Therefore, the waste polyester material to be depolymerized is processed through densification technology to depolymerize the waste polyester material. The waste polyester material is processed into <NUM>-<NUM>×<NUM>-<NUM> uniform granular material, which will make the material easy to transport. The densification technology can use conventional technologies, such as semi-melt friction densification, melt granulation densification, etc., to pretreat waste polyester materials. This means that one or a mixture of two or more of waste polyester bottle flakes, polyester films, polyester fibers, and waste textiles can be used as raw materials, and uniform particles processed by densification technology can be used as raw materials, or they can be directly purchased after processing Uniform pellets of waste polyester materials as raw materials.

Other and further features, advantages, and benefits of the invention will become apparent in the following description taken in conjunction with the following drawings. It is to be understood that the foregoing general description and following detailed description are exemplary and explanatory but are not to be restrictive of the invention. The accompanying drawings are incorporated in and constitute a part of this application and, together with the description, serve to explain the principles of the invention in general terms. Like numerals refer to like parts throughout the disclosure.

The objects, spirits, and advantages of the preferred embodiments of the present invention will be readily understood by the accompanying drawings and detailed descriptions, wherein:
<FIG>illustrates a schematic diagram of a method for recycling continuous alcoholysis of a waste polyester material of the present invention.

In order to describe in detail the technical content, structural features, achieved objectives and effects of the instant application, the following detailed descriptions are given in conjunction with the drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the application.

With reference to <FIG>, which illustrates a schematic diagram of a method for recycling continuous alcoholysis of a waste polyester material.

The raw material is uniform waste polyester particles with an average particle size ≤<NUM> and a moisture content is ≤<NUM>%. The waste polyester particles are fed into a screw extruder <NUM> from a high-level storehouse <NUM> through a rotary feeder <NUM> for melting, and are filtered by a filter unit <NUM> with a pore size of <NUM> to remove infusible impurities, and then continuously entered into a first alcoholysis tank <NUM> in a molten state. The melting temperature of the screw extruder <NUM> is <NUM>.

The molten material is continuously fed into the first alcoholysis tank <NUM> at a speed of <NUM>/h, and the conveying amount of the molten material is adjusted by the rotational speed of the screw extruder <NUM>. The rotary speed is controlled by the liquid level of the first alcoholysis tank <NUM> to achieve a relatively stable liquid level of the first alcoholysis tank <NUM>, wherein the liquid level element-rotary speed value can be set by a central control system.

The EG in an EG storage tank <NUM> and the alcoholysis catalyst in an alcoholysis catalyst storage tank <NUM> are transported into the first alcoholysis tank <NUM> through a metering pump <NUM> and a metering pump <NUM> respectively. The rotary speed of the metering pumps <NUM> and <NUM> and the rotary speed of a waste polyester screw <NUM> will be adjusted using a fixed ratio. The feed rate of the EG is <NUM>/h. In the mixed solution of the alcoholysis catalyst (potassium carbonate) and the alcoholysis agent (ethylene glycol), the potassium carbonate concentration is <NUM>%, and the potassium carbonate solution is fed in the speed of <NUM>/h.

The first alcoholysis tank <NUM> contains <NUM> of alcoholysis materials of the same composition. The waste polyester material is continuously fed into the first alcoholysis tank <NUM> in a molten state, and then stirred by a stirrer <NUM>, and mixed with the original materials, the newly introduced EG, and the newly introduced alcoholysis catalyst evenly, so that the homogeneous alcoholysis. The alcoholysis temperature is <NUM>, and the material residence time (alcoholysis time) is 60minutes.

The material in the first alcoholysis tank <NUM> is filtered by a delivery pump <NUM> and a filter unit <NUM> with a pore size of <NUM> and then is continuously fed into a second alcoholysis tank <NUM> to continue alcoholysis. The rotational speed of the delivery pump <NUM> is controlled by the liquid level of the second alcoholysis tank <NUM> to ensure that the liquid level in the second alcoholysis tank <NUM> remains relatively stable. The temperature in the second alcoholysis tank <NUM> is <NUM>, and the alcoholysis time is <NUM> minutes. After sampling and analysis, the content of the monomer BHET of the alcoholysis product is <NUM>%, and the total content of the monomers, dimers, trimers and tetramers is <NUM>%.

The alcoholysis product in the second alcoholysis tank <NUM> is continuously and quantitatively added to a transesterification tank <NUM>. Methanol, transesterification catalyst and alcoholysis product are put into the transesterification tank <NUM> in a fixed ratio. The alcoholysis material and methanol are transesterified in the presence of a catalyst to generate crude DMT. The weight ratio of methanol to the alcoholysis product can be converted into the initial waste polyester material: methanol=<NUM>:<NUM>. For the transesterification reaction carried out in the presence of the catalyst, the reaction temperature is <NUM> and the reaction time is 70minutes.

The alcoholysis catalyst is potassium carbonate. The amount of potassium carbonate is <NUM>% of the amount of the waste polyester material. Potassium carbonate is added in the form of EG solution. The catalyst concentration in the EG solution is <NUM>%.

The above-mentioned transesterification product enters into a DMT crystallizer, and the temperature is lowered to below <NUM>, and the DMT crystals will be precipitated. Filter to obtain crude DMT cake and filtrate. The crude DMT cake can be washed with methanol multiple times to obtain a DMT cake. The DMT cake is purified by a short-flow distillation system under the conditions of <NUM> kPa vacuum and <NUM> to obtain pure DMT. The purity of DMT recovered by above recovery method is <NUM>%, and the recovery rate is <NUM>%.

The waste polyester was recycled by the same continuous alcoholysis method as in Embodiment <NUM>, except that the transesterification catalyst was a methanol solution of potassium carbonate, and the potassium carbonate concentration was <NUM>%. The purity of DMT obtained by this method is <NUM>%, and the recovery rate is <NUM>%.

The waste polyester was recycled by the same continuous alcoholysis method as in Example <NUM>, except that the raw material was waste polyester film, which was processed into fragments of <NUM>-<NUM>×<NUM>-<NUM>. The purity of DMT obtained by this method is <NUM>%, and the yield is <NUM>%.

The raw material is waste polyester pellets, the average particle size is less than or equal to <NUM>, and the moisture content is less than or equal to <NUM>%.

The difference from Embodiments <NUM>-<NUM> is that the way for the materials required for the alcoholysis reaction to enter the alcoholysis tank is the mode of intermittent feeding. In the first alcoholysis tank <NUM> containing <NUM> of alcoholysis materials of the same composition, <NUM> of EG, <NUM> of <NUM>% potassium carbonate solution are put into the first alcoholysis tank <NUM>, and <NUM> of waste polyester pellets are put under stirring and gradually heated to <NUM> for alcoholysis reaction, the reaction time at <NUM> was 60minutes. Sampling and analysis of the alcoholysis product BHET monomer content is <NUM>%, the total content of the monomer, dimer, trimer and tetramer is <NUM>%.

After being filtered by the filter unit <NUM> in the first alcoholysis tank <NUM>, it will enter the transesterification tank <NUM> at one time, and the remaining <NUM> in the first alcoholysis tank <NUM> is used for the next alcoholysis. The filtering accuracy of the filter unit <NUM> is <NUM>. In the transesterification tank <NUM>, <NUM> of methanol and a transesterification catalyst are added, and the transesterification reaction is carried out in the presence of the catalyst. The reaction temperature is <NUM>° C and the reaction time is <NUM> minutesutes. The catalyst is potassium carbonate. The amount of potassium carbonate is <NUM>% of the waste polyester. Potassium carbonate is added in the form of an EG solution. The catalyst concentration in the EG solution is <NUM>%.

The above-mentioned transesterification product enters the DMT crystallizer, and the temperature of the material is lowered to below <NUM>, and the DMT crystals will be precipitated. After filtration, a crude DMT cake and filtrate are obtained. The crude DMT cake can be washed with methanol multiple times to obtain the DMT cake. The DMT cake undergoes the purification procedure through the short-flow rectification system under the conditions of a vacuum of <NUM> kPa and a temperature of <NUM>° C to obtain pure the DMT. The purity of the obtained DMT is <NUM>%, and the recovery rate is <NUM>%.

The raw material is waste polyester particles with an average particle size smaller or equal to <NUM>. The moisture content is smaller or equal to <NUM>%. Comparative Example <NUM> is similar to Comparative Example <NUM>, and both adopt intermittent feeding method for alcoholysis reaction.

Put <NUM> of EG, <NUM> <NUM>% potassium carbonate solution into the first alcoholysis tank <NUM> containing <NUM> of alcoholysis materials of the same composition, put <NUM> of polyester pellets under stirring, and gradually raise the temperature to <NUM> for alcoholysis. For the reaction, the reaction time at <NUM> is <NUM> minutes. Sampling and analysis of the alcoholysis product monomer BHET content is <NUM>%, the total content of the monomer, dimer, trimer and tetramer is <NUM>%.

After the material in the first alcoholysis tank <NUM> is filtered by the filter unit <NUM> with a pore size of <NUM>, it enters the transesterification tank <NUM> in a single operation, and the remaining <NUM> in the first alcoholysis tank <NUM> is used for the next alcoholysis. The filter accuracy of the filter program <NUM> is <NUM>. In the transesterification tank <NUM>, <NUM> of methanol and a transesterification catalyst are added, and the transesterification reaction is carried out in the presence of the catalyst. The reaction temperature is <NUM>° C, and the reaction time is <NUM> minutes. The catalyst is potassium carbonate. The amount of potassium carbonate is <NUM>% of the waste polyester. Potassium carbonate is added in the form of an EG solution. The catalyst concentration in the EG solution is <NUM>%.

The above-mentioned transesterification product enters the DMT crystallizer, and the temperature of the material is lowered to below <NUM>, and the DMT crystals will be precipitated. After filtration, a crude DMT cake and filtrate will be obtained. The crude DMT cake can be washed multiple times with methanol to obtain the DMT cake. The DMT cake undergoes the purification procedure through the short-flow rectification system under the conditions of a vacuum of <NUM> kPa and a temperature of <NUM> to obtain pure DMT. The purity of the pure DMT obtained was <NUM>%, and the recovery rate was <NUM>%.

Claim 1:
A method for recycling a waste polyester material by continuous alcoholysis, comprising:
(a) material pretreatment: dewatering and deoxidizing the waste polyester material to obtain a raw waste polyester material;
(a1) melting and first filtration: melting the raw waste polyester material to obtain a molten waste polyester material, and proceeding with a first filtration process of the molten waste polyester material;
(b) alcoholysis: continuously and simultaneously feeding the molten waste polyester material, an alcoholysis agent, and an alcoholysis catalyst into a first alcoholysis tank (<NUM>) for a first alcoholysis to obtain a first melt; wherein the first melt is continuously fed to a second alcoholysis tank (<NUM>) for a second alcoholysis, so as to obtain an alcoholysis product, wherein the first alcoholysis tank and the second alcoholysis tank are connected to each other in series;
(b1) second filtration: proceeding with a second filtration process of the first melt before it is fed into the second alcoholysis tank; and
(c) transesterification: feeding the alcoholysis product, a transesterification agent, and a transesterification catalyst into a transesterification tank (<NUM>) for a transesterification reaction to obtain crude dimethyl terephthalate (DMT), and then performing crystallization, separation and purification of the crude DMT.