CN111849026A - Method and system for producing rPET bottle grade polyester chip - Google Patents
Method and system for producing rPET bottle grade polyester chip Download PDFInfo
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- CN111849026A CN111849026A CN202010879721.XA CN202010879721A CN111849026A CN 111849026 A CN111849026 A CN 111849026A CN 202010879721 A CN202010879721 A CN 202010879721A CN 111849026 A CN111849026 A CN 111849026A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method and a system for producing rPET bottle grade polyester chips. The method comprises the following steps: the method comprises an esterification step, a pre-polycondensation step, a final polycondensation step and a solid-phase polycondensation step, wherein in the esterification step, raw materials comprising waste PET bottle fragments, terephthalic acid and ethylene glycol are added into an esterification device, the waste PET bottle fragments are subjected to alcoholysis reaction, and the terephthalic acid and the ethylene glycol are subjected to esterification reaction simultaneously. The invention has the advantages of low investment, simple technical route, lower requirement on raw materials and good product quality; on the former polyester bottle piece apparatus for producing, utilize the ethylene glycol of one of the production polyester bottle raw materials to carry out the alcoholysis to the waste polyester bottle piece, realized the closed circulation of ethylene glycol, and then made the esterification reaction cauldron play a cauldron dual-purpose function, can utilize waste PET polyester bottle to produce the PET polyester chip that satisfies the native material national standard level through the invention.
Description
Technical Field
The invention belongs to the technical field of cyclic utilization of bottle-grade polyester chips, and particularly relates to a method and a system for producing rPET (r-polyethylene terephthalate) bottle-grade polyester chips by using waste polyester chips as raw and auxiliary materials.
Background
The technology for recycling polyester PET bottles from bottles mainly comprises three recycling technologies, namely a physical method, a chemical method and a semi-chemical physical method, wherein the bottle grade slices produced by the physical method and the semi-chemical/physical method have the problems that the quality is far lower than that of original raw material slices, the physical method has strict requirements on raw materials relatively, most of the internal impurities of the bottles after being crushed, such as PP/PVC/PE, some metals, rubber, label glue and the like, cannot be effectively removed, the internal legal regulations cannot be used due to the fact that various impurities and toxic and harmful substances brought by waste polyester bottle slices cannot be effectively removed, foreign countries can only be mixed with the original PET bottle grade slices for use, and the original PET bottle grade slices cannot be completely replaced; the semi-chemical physical method is also influenced by the influence, although the influence is slightly smaller than that of the physical method, the quality of the primary particles is difficult to control except impurities, such as color value, viscosity and the like; the existing world chemical method rPET production process is also to melt and extrude from a subsequent process and add fragments, has higher requirements on raw materials of products, and has larger influence on the quality of the produced rPET products.
Therefore, a method and a system which have low requirements on the quality of the raw materials of the waste polyester bottles and can recycle the waste polyester bottles to produce the polyester chips reaching the primary PET bottle level are urgently needed.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a method and system for producing rPET bottle grade polyester chip.
The method for producing the rPET bottle grade polyester chip utilizes an alcoholysis principle, and adopts ethylene glycol to alcoholyze the waste polyester bottle chips under certain reaction conditions, so that the rPET bottle grade polyester chip meeting the requirements of customers is produced through a small amount of modification on the basis of the existing production system of the original PET bottle grade polyester chip.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of producing rPET bottle grade polyester chip comprising:
an esterification step, a pre-polycondensation step, a final polycondensation step, and a solid-phase polycondensation step, wherein,
in the esterification step, raw materials comprising waste PET polyester bottle fragments, terephthalic acid and ethylene glycol are added into an esterification device, the waste PET polyester bottle fragments are subjected to alcoholysis reaction, and meanwhile, the terephthalic acid and the ethylene glycol are subjected to esterification reaction;
and (3) sequentially carrying out pre-polycondensation, final polycondensation and solid-phase polycondensation on the product obtained in the esterification step to obtain the rPET bottle grade polyester chip.
The rPET bottle grade polyester chip in the invention is a bottle grade polyester chip which is produced and manufactured by taking recycled waste PET bottle chips as one of raw materials.
The invention adds the fragments into the foremost esterification kettle (i.e. esterification device) of the primary bottle-grade polyester production flow, leads the fragments to be polymerized after full alcoholysis is obtained by using the prior esterification conditions (different from the alcoholysis by independently using EG or methanol) in the esterification kettle under the environment of BHET and EG, ensures the product quality, the alcoholysis efficiency and the esterification efficiency, simultaneously leads the impurities such as PP/PE/PVC to enter waste gas and waste water after being decomposed by using the long retention time of the primary bottle-grade polyester chips and simultaneously leads the reaction temperature to be higher than the decomposition temperature of the impurities, removes the system, simultaneously filters and removes the high-precision melt filter carried by the primary bottle-grade chips when producing the metal/rubber/other infusible solid impurities, and ensures that the impurities do not carry into the product.
The addition amount of the scrap PET bottle chips is mainly determined according to the requirements on the product quality, the influence of the chips on the production process and the quality of the chips. In general, scrap PET bottles can be added in an amount of up to 50% (i.e., 50% or less) or even more based on the total mass of rPET bottle grade polyester chips, and the applicant has verified through experiments that it is feasible to add 10 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt% scrap to bottles for carbonated products. On the premise of controlling the quality of the chips, the use amount of the waste PET bottle chips is controlled to be below 50 wt%, and all indexes of the produced rPET bottle grade polyester chips are far superior to the national standard requirements, so that the product quality of the original raw material is achieved.
In the above method, as a preferred embodiment, the scrap PET polyester bottle chips are subjected to a metal impurity rejection process before entering the esterification apparatus.
In the above process, as a preferred embodiment, the scrap PET polyester bottle chips added in the esterification step have the following quality standards: the content of any impurity of PP, PE, PVC, metal and rubber is below 100ppm, preferably 50 ppm.
In the above process, as a preferred embodiment, the molar ratio of ethylene glycol and terephthalic acid added in the esterification step is 1.5 to 2.0, more preferably 1.55 to 1.85. The addition of ethylene glycol and terephthalic acid in this molar ratio allows better alcoholysis of the chips in the esterification apparatus, while also ensuring a high esterification rate of ethylene glycol and terephthalic acid.
In the above process, as a preferred embodiment, the esterification step includes a primary esterification and a secondary esterification step, raw materials including waste PET bottle chips, terephthalic acid and ethylene glycol are fed into a first esterification apparatus (esterification one pot) for primary esterification, the waste PET bottle chips undergo a primary alcoholysis reaction in the first esterification apparatus, and the terephthalic acid and the ethylene glycol undergo a primary esterification reaction in the first esterification apparatus; and then conveying the materials in the first esterification device to a second esterification device (an esterification second kettle) for secondary esterification and secondary alcoholysis reaction. More preferably, the molar ratio of ethylene glycol to terephthalic acid fed to the first esterification apparatus is in the range of from 1.5 to 2.0, more preferably in the range of from 1.55 to 1.85. The waste PET polyester chips are completely alcoholyzed into the BHET monomer required by the subsequent polymerization through two-step esterification, so that the problem that complete alcoholysis cannot be carried out in an esterification kettle is solved. The dosage of the ethylene glycol is not high enough, and the alcoholysis can be normally carried out, but the esterification rate is too high, so that the normal operation of the subsequent tackifying reaction is hindered; the amount of ethylene glycol should not be too low, which may cause insufficient alcoholysis degree and insufficient esterification rate, and may also prevent the normal proceeding of tackifying reaction in the subsequent polycondensation process.
In the above process, as a preferred embodiment, in the esterification step, a part of the added ethylene glycol may be replaced by diethylene glycol, and/or a part of the added terephthalic acid may be replaced by isophthalic acid.
The amount of diethylene glycol (DEG) added is determined according to the content requirement of diethylene glycol in the final synthesized rPET bottle grade polyester chip, the DEG content requirement of different polyester chips is slightly different, see Table 1, and the DEG content in the bottle grade polyester chip is 0.8-1.6% by mass in general. Since ethylene glycol generates diethylene glycol during the reaction and the waste PET polyester chips also contain a small amount of diethylene glycol, the added mass of diethylene glycol is preferably 0-0.3% of the total mass of the bottle-grade polyester chips.
The proper amount of isophthalic acid (IPA) is added to shorten the esterification reaction time, reduce the regularity of PET macromolecular arrangement, reduce the crystallization speed and processing temperature, improve the processing performance during injection molding and bottle blowing, improve the transparency of bottles and the like, the addition amount of the isophthalic acid is preferably 0-3.4% of the total mass of the finally obtained bottle-grade polyester chips, the specific amount is determined according to the application of the finally obtained polyester chips and the IPA content in waste PET chips in raw materials, and in addition, the addition amount is added to ensure that the IPA content in the finally obtained PET bottle-grade polyester chips meets the requirements of virgin material chips and is added according to the chip mass flow of the produced polyester chips.
In the esterification step of the method of the present invention, there are various methods for adding raw materials including waste PET polyester bottle chips, terephthalic acid and ethylene glycol to an esterification apparatus, and the various raw materials may be added to an esterification reactor one by one, or a part or all of the various raw materials may be mixed in advance and then added to the esterification reactor. Preferably, the waste PET polyester bottle chips, terephthalic acid and part of the ethylene glycol are mixed to prepare a slurry, and then the slurry is added into an esterification device, wherein the molar ratio of the ethylene glycol to the terephthalic acid in the slurry is 1.0-1.6 (such as 1.0-1.1, 1.0-1.2, 1.0-1.3, 1.2-1.4, 1.3-1.4, 1.4-1.5, 1.3-1.5, 1.25-1.55 and 1.3-1.55); when a portion of the terephthalic acid is replaced with phthalic acid and a portion of the ethylene glycol is replaced with diethylene glycol, the ratio of the molar amounts of ethylene glycol and diethylene glycol to the molar amounts of isophthalic acid and terephthalic acid in the slurry is 1.0 to 1.6 (such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.0 to 1.1, 1.0 to 1.2, 1.0 to 1.3, 1.2 to 1.4, 1.3 to 1.4, 1.4 to 1.5, 1.3 to 1.5, 1.25 to 1.55, 1.3 to 1.55) and can be expressed as:
m (EG + DEG) is the sum of the mass of EG (ethylene glycol) and DEG (diethylene glycol) in the slurry;
m (PTA + IPA) is the sum of the mass of PTA (terephthalic acid) and IPA (isophthalic acid) in the slurry.
The molar ratio of the alcohol to the phthalic acid in the slurry is controlled to be 1.0-1.6, and the chips can be conveyed to the esterification kettle to ensure that the chips are subjected to better alcoholysis in the esterification kettle. When the molar ratio of alcohol to phthalic acid in the slurry is controlled to be 1.3-1.5, all substances in the slurry can be smoothly conveyed to the esterification kettle, so that the recycling of rPET fragments is maximized, esterification and alcoholysis are completed in the two-stage esterification kettle, the rPET fragments are thoroughly alcoholyzed into BHET monomers required by subsequent polymerization, the terephthalic acid and ethylene glycol are esterified to generate the BHET monomers, the final alcoholysis rate can reach more than 99%, the esterification rate reaches more than 96%, and the problem that complete alcoholysis cannot be performed in the esterification kettle is solved on the basis of ensuring the smooth proceeding of the esterification reaction. The preparation of the slurry can be completed in a slurry kettle or can be completed through other equipment.
In the above method, as a preferred embodiment, in the esterification step, the remaining ethylene glycol is fed solely to the esterification apparatus, and more preferably, the remaining ethylene glycol is fed solely to the esterification one-pot. Namely: the molar ratio of the remaining ethylene glycol to terephthalic acid in the slurry fed to the esterification apparatus is in the range of from 0.2 to 1.0 (e.g., 0.25, 0.3, 0.35, 0.3, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.8, 0.85, 0.9, 0.95), preferably from 0.25 to 0.35; when part of the terephthalic acid is replaced by isophthalic acid, the molar ratio of the remaining ethylene glycol to the sum of terephthalic acid and isophthalic acid in the slurry fed to the esterification apparatus is in the range of from 0.2 to 1.0, preferably from 0.25 to 0.35.
In the above method, as a preferred embodiment, a catalyst and a first additive are further added to the slurry.
In the above method, the catalyst used can be a catalyst conventional in the field of polyester preparation, and as a preferred embodiment, the catalyst is ethylene glycol antimony (CAT); more preferably, the content of antimony in the bottle-grade polyester chip is 140ppm to 230ppm (the adding amount of the ethylene glycol antimony is determined by the content of metallic antimony in the finally prepared polyester chip), and more preferably is 165-215ppm, and the content of CAT in the preferable range can promote the polycondensation reaction, increase the tackifying rate, and further avoid poor tackifying effect of the chip caused by adding rPET chips. For smooth transportation and automatic control of solid materials, the catalyst is more preferably prepared into a solution by using a small amount of raw material glycol before the slurry is prepared.
In the above method, as a preferred embodiment, the first additive includes a bluing agent, and the amount of the bluing agent is added according to the color value requirement of the final product. Preferably, the content of the blue agent in the bottle grade polyester chip is 0.4-1.9ppm, and the adding amount of the blue agent is determined according to the content of the blue agent in the bottle grade polyester chip; the slice turns yellow after the waste PET chips are added, and the content of the bluing agent is kept in the optimal range of the invention, so that the quality of the produced rPET bottle grade slice product can reach the national standard requirement of the primary material slice; for smooth conveying and automatic control of solid materials, more preferably, the blue reagent is prepared into a solution by using a small amount of raw material glycol before the slurry is prepared.
In the method, the esterification step can adopt the prior primary esterification, secondary esterification or tertiary esterification, and the like, and the preferred scheme of the invention is adopted, wherein the primary esterification comprises the step of conveying the slurry into a first esterification device, wherein the waste PET polyester bottle fragments are subjected to alcoholysis to form the bis-hydroxyethyl terephthalate (BHET), and meanwhile, the terephthalic acid and the ethylene glycol react to generate the bis-hydroxyethyl terephthalate (BHET). The esterification rate of the first esterification is about 90 percent, and the alcoholysis rate reaches more than 90 percent; the esterification rate of the second esterification is more than 96 percent, and the alcoholysis rate is 99 percent.
The reaction conditions of the first esterification in the embodiment of the invention can adopt the first esterification conditions of the preparation process of the primary PET polyester slice finished by the conventional two-time esterification in the field, for example, the reaction materials in the first esterification device are heated to 250-270 ℃ for reaction, the pressure of the first esterification device is controlled to be 0-0.18MPa (gauge pressure) in the reaction process, and the reaction time is 3-7 h. The invention utilizes the process condition of the primary polyester first esterification reaction to carry out alcoholysis on the fragments, can reduce the amount of EG added into the first esterification device, and can ensure the esterification rate while carrying out alcoholysis.
In the above method, as a preferred embodiment, the second esterification comprises conveying the primary esterification product to a second esterification apparatus, and simultaneously adding a second additive and a stabilizer to the second esterification apparatus, wherein after the first esterification, the incompletely reacted terephthalic acid and ethylene glycol are further esterified to generate dihydroxy ethyl terephthalate, and the incompletely alcoholyzed waste PET polyester chips are further alcoholyzed to generate dihydroxy ethyl terephthalate.
The reaction conditions of the secondary esterification in the embodiment of the invention can adopt the secondary esterification conditions of the preparation process of the primary PET polyester chip by conventional two-time esterification in the field, for example, the reaction materials in the second esterification device are heated to 255-275 ℃ for reaction, the pressure of the second esterification device is controlled to be 0-0.18KPa in the reaction process, and the reaction time is 1-3 h.
In the above method, as a preferred embodiment, the second additive is a red pigment and/or carbon black, and the specific usage amount is determined according to the color value requirement of the final polyester product. For ease of transport, automated control is preferably achieved, and more preferably, the agent is first formulated into a solution with a small amount of feed glycol prior to addition to the second esterification reactor.
In the above method, as a preferred embodiment, the stabilizer is phosphoric acid, more preferably, the content of phosphorus in the bottle grade polyester chip is 6-20ppm, and the specific addition amount of the stabilizer is mainly adjusted according to the content of the stabilizer in the rPET chips and the tackifying reaction requirement after adding the chips. In order to mix the materials more uniformly and facilitate the transportation, the phosphoric acid is preferably prepared into a solution with a small amount of raw ethylene glycol before being fed into the second esterification reactor.
In the above method, as a preferred embodiment, the first esterification and the second esterification further comprise subjecting the ethylene glycol evaporated in the esterification process and the generated water to a rectification step for dehydration (i.e. entering a rectification tower for rectification and dehydration), and then recycling the ethylene glycol and the generated water as raw materials into the first esterification apparatus and/or the second esterification apparatus.
In the above method, as a preferred embodiment, the pre-polycondensation comprises sending part of the ethylene glycol and the produced water in the pre-polycondensation scraper hot well directly to a collection device for the slurry blending step without a rectification step. If all the ethylene glycol subjected to the rectification step is recycled to the slurry blending step, the slurry blending cannot be carried out at normal temperature due to too high temperature, the molar ratio is not adjusted, slurry configuration faults can be caused seriously, and according to the actual condition of polyester production, part of EG originally sent to the rectification tower is not steamed at high temperature in the rectification tower and directly enters an ethylene glycol collecting tank or an EG storage tank. More preferably, the ethylene glycol in the precondensed scraper hot well is 1.5-2.5m3The flow is sent to an EG storage tank at a flow rate of/h, the temperature of part of glycol is low, the problem of high temperature of the rectified glycol can be solved, and the method is suitable for preparing slurry.
Carrying out pre-polycondensation and final polycondensation on the secondary esterification product in sequence to obtain a PET melt; the PET melt conforms to the basic slice indexes of various indexes of bottle-grade polyester slices, and the indexes such as viscosity, terminal carboxyl, color value, DEG/IPA and the like conform to the index requirements of the basic slice. The pre-polycondensation and the final polycondensation are both polycondensation reactions, and are both subjected to reaction under the conditions of temperature, stirring, vacuum and the like, volatile gas is removed, the viscosity is increased, the intrinsic viscosity of the product of the pre-polycondensation reaction is (0.28-0.32) dl/g, the intrinsic viscosity of the product of the final polycondensation reaction is (0.56-0.65) dl/g, and the reaction conditions of the pre-polycondensation and the final polycondensation can adopt corresponding process conditions of conventional primary PET polyester chips, and are not described in detail here.
In the above method, as a preferred embodiment, the step of final polycondensation and the step of solid-phase polycondensation further includes: underwater slicing the PET melt, drying and screening to obtain a basic slice. Specifically, the PET melt is cut into granular slices by an underwater granulator, then the granular slices are dried by a centrifugal machine, the unqualified slices in shape are removed by a vibrating screen, and the qualified basic slices are conveyed to a basic slice intermediate bin by a slice conveying system to be used by a solid phase polycondensation device.
In the above process, as a preferred embodiment, the solid-phase polycondensation step includes: and (3) crystallizing, preheating and carrying out solid phase polycondensation treatment on the basic slices in sequence to obtain bottle-grade polyester slices. Specifically, the basic slices are processed by a crystallizer, a preheater and a main reactor to improve crystallinity, tackify, remove aldehyde and the like, and finally qualified bottle-grade PET polyester slices are produced. The reaction conditions of crystallization, preheating and solid-phase polycondensation treatment can adopt corresponding process conditions of conventional virgin PET polyester chips, and are not described in detail herein.
The invention also provides a system for producing rPET bottle grade polyester chips, which comprises:
the device comprises a slurry preparation device, a waste PET (polyethylene terephthalate) polyester chip conveying device and a control device, wherein the slurry preparation device is connected with the waste PET polyester chip conveying device, and the waste PET polyester chip conveying device conveys waste PET polyester chips to the slurry preparation device;
the esterification device is connected with the slurry output port of the slurry preparation device and is used for receiving the slurry and completing esterification;
the pre-polycondensation reaction device is connected with the material outlet of the esterification device and is used for finishing the pre-polycondensation of the esterification product;
the final polycondensation reaction device is connected with a material outlet of the pre-polycondensation reaction device and is used for finishing final polycondensation of a pre-polycondensation product;
the basic slice preparation device is connected with the material outlet of the final polycondensation reaction device and is used for preparing basic slices meeting the solid-phase polycondensation requirement;
the solid-phase polycondensation device is connected with the material outlet of the basic slice preparation device and is used for finishing solid-phase polycondensation;
the ethylene glycol collecting device is connected with a discharge port of the mixture of the ethylene glycol and the water of the pre-polycondensation reaction device and is used for collecting part of the ethylene glycol evaporated from the pre-polycondensation reaction device and the generated water, and a rectifying device is further arranged at the discharge port of the mixture of the ethylene glycol and the water of the pre-polycondensation reaction device and is used for rectifying and dehydrating part of the ethylene glycol evaporated from the pre-polycondensation reaction device.
In the above system, as a preferred embodiment, the slurry preparation apparatus further comprises a terephthalic acid feed pipe, an ethylene glycol feed pipe, a catalyst feed pipe, and a first additive supply pipe.
In the above system, as a preferred embodiment, the esterification apparatus includes a first esterification apparatus and a second esterification apparatus connected to a material outlet of the first esterification apparatus, and the material outlet of the second esterification apparatus is connected to the material inlet of the pre-polycondensation reaction apparatus.
In the above system, as a preferred embodiment, a melt filter for filtering the PET melt discharged from the final polycondensation reaction apparatus is provided between the final polycondensation reaction apparatus and the base chip preparation apparatus.
In the above system, as a preferred embodiment, the basic chip preparation device includes a cutting device and a chip collecting hopper communicated with a discharge port of the cutting device.
The device comprises a pre-polycondensation reaction device, a final polycondensation reaction device, a melt filter, a flow regulating valve and a slice collecting hopper, wherein a prepolymer discharge pump is arranged between the pre-polycondensation reaction device and the final polycondensation reaction device, a melt output pump is arranged between the final polycondensation reaction device and the melt filter, the flow regulating valve is arranged between the first esterification device and the second esterification device and between the pre-polycondensation reaction device and two adjacent devices in the final polycondensation reaction device, and the slice collecting hopper is communicated with the solid phase polycondensation device through a buffer bin.
The invention has the beneficial effects that: the invention has the advantages of low investment, simple technical route, lower requirement on raw materials and good product quality; on the original polyester bottle chip production device, the ethylene glycol used as one of the raw materials for producing the polyester bottles is used for carrying out alcoholysis on waste polyester bottle chips, so that the closed circulation of the ethylene glycol is realized, and the esterification reaction kettle has a one-kettle dual-purpose function.
Drawings
FIG. 1 is a system or flow diagram for producing rPET bottle grade polyester chip according to one embodiment of the present invention.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The materials, methods, and examples herein are illustrative only and, unless otherwise specified, should not be construed as limiting. Only suitable methods and materials are described herein, and methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. The invention provides a method for producing rPET bottle grade polyester chips, wherein fragments are added into an esterification kettle for alcoholysis, so that one-kettle dual-purpose of the esterification kettle is realized.
Referring to fig. 1, a system diagram for producing rPET bottle grade polyester chip is provided according to an embodiment of the present invention. The device comprises a melt polymerization part, a basic slice preparation device and a solid phase polycondensation part, wherein the melt polymerization part comprises a slurry preparation device, a first esterification device, a second esterification device, a pre-polycondensation reaction device and a final polycondensation reaction device, and the solid phase polycondensation part comprises a crystallizer, a preheater, a main reactor and the like. The heat sources of the apparatus of the melt polymerization section and the apparatus of the solid phase polycondensation section are provided by a heat medium system. The connection relationship of the devices or components is described in detail below.
The slurry preparation device is used for preparing slurry conveyed to the first esterification device, a waste PET (polyethylene terephthalate) polyester chip conveying device is connected onto the slurry preparation device, the waste PET polyester chip conveying device conveys waste PET polyester chips to the slurry preparation device, and the slurry preparation device is also communicated with a terephthalic acid feed pipe, an ethylene glycol feed pipe, an isophthalic acid feed pipe, a diethylene glycol feed pipe, a catalyst feed pipe and a first additive feed pipe.
And the first esterification device is connected with the slurry output port of the slurry preparation device and is used for receiving the slurry and finishing the first esterification and alcoholysis. The ethylene glycol steamed out from the first esterification device enters a rectifying tower for rectifying and dehydrating, and then returns to the esterification device for recycling.
And the second esterification device is connected with the material output port of the first esterification device and is used for the second esterification and alcoholysis of the materials. The ethylene glycol steamed out in the second esterification device enters a rectifying tower for rectifying and dehydrating, and then returns to the esterification device for recycling.
And the pre-polycondensation reaction device is connected with a material outlet of the second esterification device and is used for finishing the pre-polycondensation of the esterification product.
And the final polycondensation reaction device is connected with a material outlet of the pre-polycondensation reaction device and is used for finishing final polycondensation of the pre-polycondensation product.
And the basic slice preparation device is connected with a material outlet of the final polycondensation reaction device and is used for preparing the basic slices meeting the solid-phase polycondensation requirement. The basic slice preparation device comprises a material cutting device and a slice collecting hopper communicated with a material outlet of the material cutting device.
The solid-phase polycondensation device is connected with the material outlet of the basic slice preparation device and is used for finishing solid-phase polycondensation; the solid phase polycondensation device comprises a crystallizer, a preheater and a main reactor which are connected in sequence, the crystallizer is connected with a material outlet of the basic slice preparation device, and the main reactor is connected with the cold-dynamic conveying system to finally obtain a finished product.
And the ethylene glycol collecting device is connected with a discharge port of the ethylene glycol and water mixture of the pre-polycondensation reaction device and is used for collecting part of ethylene glycol evaporated from the pre-polycondensation reaction device and generated water, and the discharge port of the ethylene glycol and water mixture of the pre-polycondensation reaction device is also connected with the rectifying device or the rectifying tower and is used for rectifying and dehydrating part of ethylene glycol evaporated from the pre-polycondensation reaction device. Namely, a part of the mixture of the ethylene glycol and the water discharged from the pre-polycondensation reaction device enters the rectifying tower, and a part of the mixture enters the ethylene glycol collecting device. The ethylene glycol from the rectifying tower can be directly recycled to the first esterification device and the second esterification device. Ethylene glycol in the ethylene glycol collection device is reused in the slurry preparation device as required for preparing slurry.
And a melt filter is arranged between the final polycondensation reaction device and the basic slice preparation device and is used for filtering the PET melt discharged by the final polycondensation reaction device.
A prepolymer discharge pump is arranged between the pre-polycondensation reaction device and the final polycondensation reaction device, a melt output pump is arranged between the final polycondensation reaction device and the melt filter, a flow regulating valve is arranged between two adjacent devices in the first esterification device, the second esterification device, the pre-polycondensation reaction device and the final polycondensation reaction device, and the slice collecting hopper is communicated with the solid phase polycondensation device through a buffer bin.
The reagents and starting materials used in the following examples are all commercially available products.
In one embodiment of the invention, the production process for preparing the bottle-grade PET polyester chip from the waste PET bottle fragments comprises the following steps: CAT (ethylene glycol antimony catalyst, before using, make solution with a small amount of ethylene glycol), blue degree agent (before using, make solution with a small amount of ethylene glycol), IPA (isophthalic acid), diethylene glycol and waste PET fragments of recycling use quantitative with Purified Terephthalic Acid (PTA), Ethylene Glycol (EG) raw materials add slurry kettle (namely slurry preparation facilities), wherein CAT (catalyst), DEG (diethylene glycol), blue degree agent, etc. pump quantitative feed slurry kettle, IPA (isophthalic acid) use bag packaging way put into feed bin after quantitative add slurry kettle by measurement, and waste PET bottle fragments as produce rPET bottle grade polyester chip raw materials, also use bag packaging way put into, through gas transport enter storage feed bin, through measurement, wind send back quantitative slurry kettle, add slurry kettle at the same time, make slurry suspension feed after slurry stirring and mixing, then send into the first esterification apparatus with slurry transport pump, carrying out alcoholysis and esterification reactions under the conditions of certain temperature, pressure and retention time, then conveying the mixture into a second esterification device through a pressure difference or a second slurry conveying pump, simultaneously adding additives such as a stabilizer (phosphoric acid, which is prepared into a solution by using ethylene glycol before use), a red agent (which is prepared into a solution by using ethylene glycol before use), carbon black and the like, carrying out further alcoholysis and esterification reactions to generate BHET, and completely simulating the production of primary bottle-grade polyester chips by using Pure Terephthalic Acid (PTA) and Ethylene Glycol (EG) as raw materials in the subsequent production process; BHET is conveyed to a pre-polycondensation and final polycondensation reaction kettle, devolatilization and tackifying are carried out under certain temperature and vacuum conditions, PET melt is finally produced, and in a solid phase polycondensation device, a basic slice is subjected to crystallization degree improvement, tackifying, dealdehydizing and other treatments through a crystallizer, a preheater and a main reactor, and finally qualified rPET bottle grade polyester slice is produced. The qualified rPET bottle grade polyester chip provided by the invention is a polyester chip meeting the requirements of the national standard GB4806.6-2016 of primary materials.
The quality detection method of the polyester chip prepared by the embodiment of the invention is referred to the national standard GB/T17931-2018. Some of the raw material products (raw material product refers to raw material PET bottle grade polyester chip prepared by using terephthalic acid and ethylene glycol as raw materials instead of waste PET bottle fragments as one of the raw materials) have the following indexes in Table 1.
TABLE 1
The process of the invention is illustrated below by means of specific preparation examples. The quality of the recycled waste PET scrap used in the following examples refers to table 2 below, and the steps not specified in the examples are the preparation method of virgin PET bottle grade polyester chip in the art.
TABLE 2
Example 1
The preparation method of the bottle grade polyester chip of the embodiment is as follows:
(1) preparation of slurry: adding CAT (ethylene glycol antimony catalyst which is prepared into solution by using a small amount of ethylene glycol before use), a blue reagent which is prepared into solution by using a small amount of ethylene glycol before use, IPA (isophthalic acid), diethylene glycol (DEG), recycled rPET fragments, Purified Terephthalic Acid (PTA) and Ethylene Glycol (EG) raw materials into a slurry kettle, stirring and mixing uniformly to obtain slurry, wherein the molar ratio of the alcohol to the acid in the slurry is 1.45 (namely the ratio of M (EG + DEG)/62.07 to M (PTA + IPA)/166.13 is 1.45), the addition amount of the recycled rPET chips is 10% of the mass of the bottle-grade polyester chips, the dosage of IPA is 2.12% of the mass of the bottle-grade polyester chips, the dosage of diethylene glycol enables the concentration of the diethylene glycol in the bottle-grade polyester chips to be 0, the dosage of the blue reagent enables the concentration of the blue reagent in the bottle-grade polyester chips to be 1.65PPM, and the dosage of the ethylene glycol antimony catalyst enables the content of antimony in the bottle-grade polyester chips to be 197 PPM. The slurry tank temperature is typically maintained at a temperature between 40 and 70 deg.f;
(2) first esterification and alcoholysis: and (2) conveying the slurry obtained in the step (1) to a first esterification kettle (namely a first esterification device), and then additionally adding ethylene glycol into the first esterification kettle, wherein the molar ratio of the added ethylene glycol to acid in the slurry is 0.3, and the heat preservation and pressure maintaining time is 6 hours at 258 ℃ and under the reaction pressure of 0.28bar (gauge pressure). The ethylene glycol evaporated in the esterification process and the generated water are rectified and dehydrated by a rectifying tower and then used in the esterification step.
(3) Second esterification and alcoholysis: and (3) conveying the reaction product obtained in the step (2) to a second esterification kettle (namely a second esterification device), and simultaneously adding an erythroid agent, carbon black and phosphoric acid (a small amount of raw material ethylene glycol is prepared into a solution before use) into the second esterification kettle, wherein the usage amount of the erythroid agent is that the concentration of the erythroid agent in the bottle-level polyester slices is 0.26PPM, the usage amount of the carbon black is that the concentration of the carbon black in the bottle-level polyester slices is 6.48PPM, the usage amount of the phosphoric acid is that the concentration of the phosphorus in the bottle-level polyester slices is 15PPM, the temperature of the second esterification reaction is 263 ℃, the reaction pressure is 44mbar (gauge pressure), and the reaction time is 2.5 hours.
(4) Pre-polycondensation: and conveying the product of the second esterification to a pre-polycondensation reaction kettle for pre-polycondensation, wherein the reaction temperature is 265 ℃ and 270 ℃, the reaction pressure is 1.0-1.3 kPa, the reaction time is 1.5h, the polycondensation conversion rate is 92%, and the intrinsic viscosity is 0.30 dl/g.
(5) Final polycondensation: conveying the product of the pre-polycondensation to a final polycondensation reaction kettle for final polycondensation to obtain a PET melt, wherein the reaction temperature is 275-.
(6) Preparation of basal sections: filtering the PET melt, then sending the PET melt into a slicing machine for underwater slicing, drying and screening out slices with unqualified shapes to obtain basic slices;
(7) crystallization, preheating treatment and solid phase polycondensation: and finally producing qualified rPET bottle grade polyester chips after the basic chips are subjected to crystallization degree improvement, viscosity increase, aldehyde removal and other treatments of a crystallizer, a preheater and a main reactor.
The quality of the bottle grade polyester chip prepared by the method of this example was measured, and the product quality was as follows in table 3.
TABLE 3
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (10)
1. A method of producing rPET bottle grade polyester chip, comprising:
an esterification step, a pre-polycondensation step, a final polycondensation step, and a solid-phase polycondensation step, wherein,
in the esterification step, raw materials comprising waste PET polyester bottle fragments, terephthalic acid and ethylene glycol are added into an esterification device, the waste PET polyester bottle fragments are subjected to alcoholysis reaction, and meanwhile, the terephthalic acid and the ethylene glycol are subjected to esterification reaction;
and (3) sequentially carrying out pre-polycondensation, final polycondensation and solid-phase polycondensation on the product obtained in the esterification step to obtain the rPET bottle grade polyester chip.
2. The method according to claim 1, wherein the scrap PET bottle chips are added in an amount of 50% or less of the total mass of rPET bottle grade polyester chips;
preferably, the scrap PET polyester bottle chips are subjected to metal impurity removal treatment before entering an esterification device;
the quality standards of the added scrap PET polyester bottle chips are as follows: the content of any impurity of PP, PE, PVC, metal and rubber is below 100ppm, preferably 50 ppm.
3. The process according to claim 1, characterized in that in the esterification step the molar ratio of ethylene glycol and terephthalic acid added is between 1.5 and 2.0, more preferably between 1.55 and 1.85.
4. The process of claim 1, wherein the esterification step comprises a primary esterification and a secondary esterification step, and the raw material comprising scrap PET polyester bottle chips, terephthalic acid and ethylene glycol is fed into the first esterification apparatus for the primary esterification, the scrap PET polyester bottle chips are subjected to an alcoholysis reaction in the first esterification apparatus, and the terephthalic acid and the ethylene glycol are subjected to an esterification reaction in the first esterification apparatus; then conveying the material in the first esterification device to a second esterification device for carrying out secondary esterification and secondary alcoholysis reaction;
preferably, the molar ratio of ethylene glycol to terephthalic acid fed to the first esterification unit is in the range of from 1.5 to 2.0, more preferably in the range of from 1.55 to 1.85;
preferably, the reaction materials in the first esterification device are heated to the temperature of 250-270 ℃ for reaction, the pressure in the first esterification device is controlled to be 0-0.18MPa in the reaction process, and the reaction time is controlled to be 3-7 h;
preferably, the reaction materials in the second esterification device are heated to 255-275 ℃ for reaction, the pressure in the second esterification device is controlled to be 0-0.18KPa during the reaction process, and the reaction time is 1-3 h.
5. Process according to any one of claims 1 to 4, characterized in that, in the esterification step, part of the ethylene glycol added is replaced by diethylene glycol and/or part of the terephthalic acid added is replaced by isophthalic acid.
6. The process according to any one of claims 1 to 5, wherein the scrap PET bottle chips, terephthalic acid and a part of ethylene glycol are mixed to prepare a slurry, and then the slurry is fed into the esterification apparatus, wherein the molar ratio of ethylene glycol to terephthalic acid in the slurry is 1.0 to 1.6; when part of the terephthalic acid is replaced by phthalic acid and part of the ethylene glycol is replaced by diethylene glycol, the ratio of the molar amounts of ethylene glycol and diethylene glycol to the molar amounts of isophthalic acid and terephthalic acid in the slurry is from 1.0 to 1.6, preferably from 1.25 to 1.55, more preferably from 1.3 to 1.5;
the remaining ethylene glycol is fed solely to the esterification unit, more preferably the remaining ethylene glycol is fed solely to the esterification kettle, and when part of the terephthalic acid is replaced by isophthalic acid, the molar ratio of the remaining ethylene glycol to the sum of the terephthalic acid and isophthalic acid in the slurry fed to the esterification unit is 0.2 to 1.0, preferably 0.25 to 0.35;
preferably, a catalyst and a first additive are also added into the slurry;
the catalyst is ethylene glycol antimony; preferably, the content of antimony in the bottle grade polyester chip is 140ppm to 230 ppm;
the first additive comprises a blue agent, and preferably, the content of the blue agent in the bottle-grade polyester chip is 0.4-1.9 ppm.
7. The process according to any one of claims 4 to 6, wherein the secondary esterification step comprises feeding the product of the primary esterification step to a second esterification unit, to which second additives, stabilizers, are simultaneously added, the unreacted terephthalic acid and ethylene glycol after the first esterification are further esterified to form bishydroxyethyl terephthalate, and the incompletely alcoholyzed waste PET polyester chips are further alcoholyzed to form bishydroxyethyl terephthalate;
the second additive is a redness agent and/or carbon black;
the stabilizer is phosphoric acid, and preferably, the content of phosphorus in the bottle grade polyester chips is 6-20 ppm.
8. The method of any of claims 1-7, wherein the precondensation comprises sending a portion of the ethylene glycol and produced water in a precondensation wiper heat well directly to a collection device for the slurry formulation without a rectification step;
preferably, the secondary esterification product is subjected to pre-polycondensation and final polycondensation in sequence to obtain a PET melt; the intrinsic viscosity of the product of the pre-polycondensation reaction is (0.28-0.32) dl/g, and the intrinsic viscosity of the product of the final polycondensation reaction is (0.56-0.65) dl/g;
preferably, the final polycondensation and the solid phase polycondensation step further comprise therebetween: underwater slicing the PET melt, drying and screening to obtain a basic slice.
Preferably, the solid phase polycondensation step comprises: and (3) crystallizing, preheating and carrying out solid phase polycondensation treatment on the basic slices in sequence to obtain bottle-grade polyester slices.
9. A system for producing rPET bottle grade polyester chip, the system comprising:
the device comprises a slurry preparation device, a waste PET (polyethylene terephthalate) polyester chip conveying device and a control device, wherein the slurry preparation device is connected with the waste PET polyester chip conveying device, and the waste PET polyester chip conveying device conveys waste PET polyester chips to the slurry preparation device;
the esterification device is connected with the slurry output port of the slurry preparation device and is used for receiving the slurry and completing esterification;
the pre-polycondensation reaction device is connected with the material outlet of the esterification device and is used for finishing the pre-polycondensation of the esterification product;
the final polycondensation reaction device is connected with a material outlet of the pre-polycondensation reaction device and is used for finishing final polycondensation of a pre-polycondensation product;
the basic slice preparation device is connected with the material outlet of the final polycondensation reaction device and is used for preparing basic slices meeting the solid-phase polycondensation requirement;
the solid-phase polycondensation device is connected with the material outlet of the basic slice preparation device and is used for finishing solid-phase polycondensation;
the ethylene glycol collecting device is connected with a discharge port of the mixture of the ethylene glycol and the water of the pre-polycondensation reaction device and is used for collecting part of the ethylene glycol evaporated from the pre-polycondensation reaction device and the generated water, and a rectifying device is further arranged at the discharge port of the mixture of the ethylene glycol and the water of the pre-polycondensation reaction device and is used for rectifying and dehydrating part of the ethylene glycol evaporated from the pre-polycondensation reaction device.
10. The system of claim 9, wherein the slurry preparation apparatus is further in communication with a terephthalic acid feed conduit, an ethylene glycol feed conduit, a catalyst feed conduit, and a first additive supply conduit;
preferably, the esterification device comprises a first esterification device and a second esterification device connected with a material outlet of the first esterification device, and the material outlet of the second esterification device is connected with a material inlet of the pre-polycondensation reaction device;
preferably, a melt filter is arranged between the final polycondensation reaction device and the basic slice preparation device and is used for filtering the PET melt discharged by the final polycondensation reaction device;
preferably, the basic slice preparation device comprises a cutting device and a slice collection hopper communicated with a discharge hole of the cutting device.
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