CN1487002A - Method of controlling inert gas purification degree in solid polymerization of polyester resin - Google Patents
Method of controlling inert gas purification degree in solid polymerization of polyester resin Download PDFInfo
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Abstract
The present invention is the method of controlling inert gas purity in solid polymerization of polyester resin. During the catalyst oxidation process to purify, DCS is used in the operation and processing of mechanism model and system model to compare with the practical contents of carbohydrate, CO and O2 detected from the total output pipeline of catalyzing bed, and after analysis and modification, the output signal is fed back to flow rate displaying controller FIC, so as to realize via the control valves the control of added oxygen or oxygen containing gas. The control mode possesses self-regulation function, and can reach very purity of purified inert gas, within 1 ppm. The present invention makes it possible to produce high quality and high viscosity polyester product.
Description
Technical Field
The invention relates to purification treatment of inert gas in a polyester resin solid phase condensation process, in particular to a method for controlling the purification degree of the inert gas in the polyester resin solid phase condensation process.
Technical Field
The solid-phase polymerization of polyester resins is generally carried out under an inert gas atmosphere. During the solid phase polymerization, small molecules such as hydrocarbon and the like are generated, and along with the progress of the reaction, the small molecules are gradually enriched in a recycled inert gas system, and need to be continuously purified and removed from the gas, so that the solid phase polymerization reaction can be continuously maintained, and the polymerization degree of the polyester resin is improved to a required degree. The inert gas is usually nitrogen, and the purification of the inert gas is usually carried out by a method of "catalytic oxidation". In this process, nitrogen, containing small-molecule impurity gases, is generally heated to about 350 ℃, introduced into a catalytic bed packed with platinum or platinum/palladium carriers, and oxygen or an oxygen-containing gas (generally air) is introduced. Under the action of catalyst, the organic small molecules in the mixed gas are combusted to generate water and CO2And then water molecules are removed through a drying step of the next stage. CO 22Also chemically inert, does not require special handling and is maintained at reasonable levels with nitrogen as the entire system loses gas and fresh nitrogen is added.
The key to the catalytic oxidation process is the control of the amount of oxygen-containing gas added. The addition amount is too small, the organic micromolecular gas can not be fully reacted, and the organic micromolecular gas circularly enter a solid phase polycondensation reaction system, so that the reaction rate is reduced; when the addition amount is too much, the redundant oxygen enters a solid-phase polymerization system of the polyester resin along with the recycling of the inert gas, so that the polyester resin generates side reaction, the color of the final product turns yellow, and the quality is influenced. The existing control methods mainly comprise two types:
① an oxygen content sensor is installed on the gas pipeline at the outlet of the catalytic bed to test the residual oxygen content in the gas after catalytic oxidation reaction, and the measured value is used as a feedback value to control the adding amount of the oxygen-containing gas before entering the catalytic bed, thereby controlling the residual oxygen content in the purified gas to be kept in a certain range.
② A probe is installed on the gas pipeline at the outlet of the catalyst bed to measure the content of carbon monoxide micromolecules, and the amount of oxygen-containing gas is controlled by taking the measured value as a reference standard.
The practical application shows that the ① control method is adopted, the oxygen content in the purified nitrogen can reach 250ppm to the maximum, although small molecules of hydrocarbon are basically removed, the side effect caused by the higher oxygen content seriously influences the quality of the final product, while the ② control method mainly detects a byproduct, namely carbon monoxide, in the oxidation reaction as a control parameter, the content of the hydrocarbon in the nitrogen can notbe detected or can not be completely removed, and the control method has poor control precision and large fluctuation and can not reach the satisfactory purification effect.
With the expansion of the application field of high-viscosity polyester products, the requirements of users on the product quality are more and more strict, which puts new requirements on the production process conditions of the high-viscosity polyester. The method is especially important as an inert gas purification process which has a great influence on the product quality in the solid-phase polymerization process. Theoretically, the purer the inert gas after purging, the more advantageous the solid phase polymerization process is if the oxygen content and the hydrocarbon content of the gas are both zero.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for controlling the purification degree of inert gas in the solid-phase polymerization process of polyester resin, so that the oxygen content and the small molecular content of hydrocarbon in the purified inert gas are simultaneously reduced to the minimum, a better purification effect is achieved, the efficiency of a purification process is ensured, redundant oxygen is prevented from entering a reaction system, and the product quality is better improved.
The purpose of the invention is realized by the following technical scheme:
a method for controlling the purification degree of inert gas in the solid phase polymerization process of polyester resin, the mixed gas which takes the inert gas as the main component and is led from the gas outlet of a solid phase polymerization reactor is heated and then enters the inlet pipeline of a catalytic bed, the inlet pipeline is also connected with the input pipeline of oxygen or oxygen-containing gas through a flow display controller FIC and a control valve thereof, the outlet of the catalytic bed is provided with a general gas output pipeline, the catalytic bed is filled with oxidation catalyst, the temperature is kept between 250 ℃ and 350 ℃, so that hydrocarbon in the mixed gas after the solid phase polymerization reacts with the led oxygen under the action of the high temperature and the catalyst, the method is characterized in that: arranging a hydrocarbon, carbon monoxide and oxygen content detection device on a gas output main pipeline of a catalytic bed, wherein an output signal of the detection device is Fx, and arranging a computer processing device of a mechanism model and a system model; when the system works, the Fx is input into the system model, the system model analyzes and processes the set value and the collection value of the system parameter, the output signal of the mechanism model and the actual detection signal Fx together to obtain an output signal, the output signal is fed back to the flow display controller FIC, and then the control on the adding amount of oxygen or oxygen-containing gas is realized through the control valve.
The object of the invention can be further realized by the following preferred technical scheme:
in the method for controlling the purification degree of the inert gas in the solid-phase polymerization process of the polyester resin, the mechanism model is analyzed and processed by adopting a Distributed Control System (DCS), an empirical formula is obtained by utilizing a fuzzy mathematical theory and a test, a set of mechanism model is established, the actual load and all relevant process parameters in the solid-phase polymerization production process are automatically collected, the quality index parameters of the raw materials are manually input and adjusted, the raw materials are all applied to the mechanism model, and various hydrocarbons generated and released in the solid-phase polymerization reaction process are subjected to the mechanism modelTotal amount of substance released FCHReaction rate FvAnd diffusion rate FkCarrying out operation processing on the three major factors; said FCH＝f(IV0，IVn，Mr，Px) The intrinsic viscosity IV of the raw materials is taken into account0Intrinsic viscosity IV of the final productnMolecular weight distribution Mr and productionRaw material formula Px(ii) a Said Fv＝f(Ca，Mr，Po，PCH，Tc) The catalyst content C is mainly taken into accountaMolecular weight distribution Mr, oxygen content PoHydrocarbon content PCHAnd reaction temperature Tc(ii) a Said Fk＝f(Tc，Vn，Mr，IV，Pn) Mainly considering the reaction temperature TcVolume V of polyester resin chipnMolecular weight distribution Mr, intrinsic viscosity IV and inert gas partial pressure Pn. The implementation is programmed according to the following functional modules: define IV0、PxMr, given IVnCalculating to obtain the total hydrocarbon release amount FCHWill FCHInputting into a mechanism model; will influence FvGiven parameter CaMr and process parameter Po、PCH、TcComparing and calculating to obtain the reaction rate FvWill FvInputting into a mechanism model; will influence FkGiven parameters Mr, IV, VnAnd a process parameter Tc、PnComparing and calculating to obtain diffusion rate FkWill FkInputting into a mechanism model; mechanism model rejoining FCH、FvAnd FkAnd carrying out comprehensive operation and outputting an operation result.
In the above control method for controlling the inert gas purification degree in the solid-phase polymerization process of polyester resin, the system model is analyzed and processed by a distributed control system DCS, and the system model Fs ═ F (T, P, τ, F)c，Po，PCH) The output of the principal acceptance mechanism model, and the reaction temperature T, the inert gas pressure P, the reaction residence time T, and the inert gas flow F in the solid-phase polymerization stagecOxygen content PoHydrocarbon content PCHAnd analyzing and processing the signals together to obtain an output signal Fs. The Fs signal is fed back to the flow display controller FIC, which in turn controls the oxygen or oxygen-containing gas addition via the control valve, and is compared with Fx, which determines a correction factor k for the system model, which is used to adjustAnd (4) system model parameters. The implementation is programmed according to the following functional modules: the main module adopts a multivariable predictive control and constraint control processing model, and the output result of the mechanism model is directly input into the main module; in the absence of manpowerUnder the condition of intervention, T, P, tau and F are automatically collected according to a certain periodc、Po、PCHProcess parameter variables, on one hand, the parameters are optimized by an upper computer in a multivariate variable off-line mode, the optimization results are input into a main module, on the other hand, the traditional single variable operation processing is carried out, one part of the processing results are directly fed back to the main module, the other part of the processing results are subjected to basic PID (proportion integration differentiation) adjustment through a proportional, integral and differential adjuster, theadjustment results are input into related technological processes for adjustment, and new T, P, tau and F are obtainedc、Po、PCHProcess parameters, which are input to the primary module again; and the main module integrates the information of the four sources to carry out operation processing, obtains an output result, sends the output result to an upper computer to be stored and operated, and compares and optimizes the output result with the actually detected contents Fx of hydrocarbon, carbon monoxide and oxygen to obtain a system model output signal Fs.
In the above control method for controlling the purging degree of inert gas in the solid-phase polymerization process of polyester resin, the initial setting value of the correction factor k is 1.
The aforementioned control method for controlling the purging degree of the inert gas in the solid-phase polymerization process of the polyester resin, wherein the inert gas is nitrogen or contains nitrogen; the oxygen-containing gas is air; the oxidation catalyst is Pt and Pd supported on alumina; the hydrocarbon comprises ethylene glycol C2H6O2Acetaldehyde C2H4O。
In the method for controlling the degree of purification of inert gas in the solid-phase polymerization of polyester resin, the purified gas from the catalytic bed is wholly or partially recycled to the pre-drying treatment section of the solid-phase polymerization reactor to remove water generated in the purification treatment.
According to the technical scheme, a mechanism model and a system model are established by researching a catalytic oxidation purification treatment mechanism of inert gas in a polyester resin solid-phase polymerization process, and a control method is checked and corrected by actually detecting the contents of hydrocarbon, carbon monoxide and oxygen in the purified gas, so that the purification degree of the mixed gas mainly containing the inert gas is better controlled.
Drawings
Fig. 1 is a schematic view of the main process for implementing the control method of the present invention.
FIG. 2 is a functional block diagram of the programming of the mechanism model functional modules of the present invention.
FIG. 3 is a functional block diagram of the system model functional module programming of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to fig. 1 to 3.
The small hydrocarbon molecules produced in the solid-phase polymerization process of polyester are mainly glycol (C)2H6O2) And acetaldehyde (C)2H4O) and the like, and simultaneously, a part of organic matter micromolecules such as free acetaldehyde and the like carried in the basic raw materials are released in the solid-phase polymerization process, and the purpose of purification is to remove all hydrocarbon impurities in a catalytic oxidation mode. The invention finds an effective catalytic oxidation control method through researches on the formula and reaction of melt polymerization, solid-phase polymerization reaction, catalytic oxidation reaction and other mechanisms and related experiments.
The main factors influencing the positive and side reactions of the polyester solid-phase polymerization process are as follows: the intrinsic viscosity of the basic raw material, the content of terminal carboxyl groups, the temperature of solid-phase polymerization, the flow rate of circulating nitrogen, the residence time, the intrinsic viscosity of a final product, the content of terminal carboxyl groups, the production load and the like. In addition, free acetaldehyde in the base raw material is released through the solid-phase polymerization process, and the release effect is related to the temperature and the flow rate of circulating gas of each system in the solid-phase polymerization production process. On the basis of theoretical research, the invention finds the relationship of the factors on the solid-phase polymerization reaction speed, the reaction degree, the hydrocarbon generation amount, the free acetaldehyde release speed, the side reaction degree, the diffusion speed inside and outside the small-molecular polyester chip in the reaction process and the like by carrying out a large number of experiments on the polyester solid-phase polymerization process, and establishes an empirical formula and a mechanism model.
1. Mechanism model: including the total amount of hydrocarbon released, the reaction rate and the diffusion rate.
① Total Hydrocarbon Release FCH＝f(IV0，IVn，Mr，Px)
Wherein: fCH-the total amount of hydrocarbons released; IV0-the intrinsic viscosity of the feedstock; IVn-the intrinsic viscosity of the final product; mr-molecular weight distribution; px-a production recipe.
② reaction Rate Fv＝f(Ca，Mr，Po，PCH，Tc)
Wherein: fv-the rate of reaction; ca-a catalyst content; mr-molecular weight distribution; po-oxygen content; pCH-a hydrocarbon content; t isc-reaction temperature.
③ diffusion Rate Fk＝f(Tc，Vn，Mr，IV，Pn)
Wherein: fk-the diffusion rate; t isc-the reaction temperature; vn-the slice volume; mr-molecular weight distribution; IV-viscosity; pnInert gas partial pressure.
The main component of the hydrocarbon impurities is ethylene glycol (C)2H6O2) And acetaldehyde (C)2H4O), their reaction formula for complete oxidative combustion is as follows:
On the basis of the basic theory and the related tests, an empirical formula is obtained by using a fuzzy mathematical theory and the tests, a set of catalytic oxidation control mathematical model is established, the actual load and all related process parameters in the solid-phase polymerization production process are automatically acquired, the quality indexes of raw materials and other parameters are manually input and adjusted, the parameters are all applied to a mechanism model, and the quantity, the reaction rate and the diffusion rate of various hydrocarbons generated and released in the solid-phase polymerization reaction process are calculated through the mechanism model. When implemented, is programmed according to the functional modules of fig. 2.
2. And (3) system model: fs ═ F (T, P, τ, F)c，Po，PCH)
Wherein: Fs-System model output; t-solid phase polymerization temperature; p-inert gas pressure; τ-residence time in solid phase polymerization; fc-a flow of inert gas; po-oxygen content; pCH-hydrocarbon content.
On the basis of a mechanism model, firstly, according to the stoichiometric proportion of oxygen required by the oxidation combustion of each hydrocarbon component, obtaining a mechanism model processing result and inputting the mechanism model processing result into a system model; and then, the contents of hydrocarbon, carbon monoxide and oxygen in the inert gas after catalytic oxidation are actually detected by utilizing a soft measurement technology of an advanced control mode, input and output information of the process are fully utilized and input to a system model for comprehensive operation, the operation result is compared with actual detection data, and a correction factor k of the system model is adjusted in time to achieve the aim of accurately controlling the adding amount of the oxygen or the oxygen-containing gas. When implemented, is programmed according to the functional modules of fig. 3.
By adopting the technical scheme of the invention, the purification degree of the inert gas in the solid-phase polymerization process of the polyester resin can be effectively controlled. The purification control mode has a self-regulation function, can enable the purified inert gas to achieve high purity, basically cannot detect hydrocarbon impurities or residual oxygen in the inert gas, and can control the actual amount and deviation within 1 ppm. Therefore, the invention solves the technical problem of low purity of the purified inert gas in the solid-phase polymerization production of the polyester resin in the prior art, provides reliable guarantee for producing high-quality and high-viscosity polyester products, meets the requirements of the production process, and simultaneously reduces the energy consumption in the purification process of the inert gas.
The control method provided by the invention does not increase the production investment and the operation cost, has reliable control mode and stable operation, and can greatly improve the quality of high-viscosity polyester products.
Example (v):
in the solid phase polymerization production line of industrial polyester resin, nitrogen is used as inert medium gas, polyester resin with intrinsic viscosity of 0.63dl/g is used as raw material, and high-viscosity polyester product with intrinsic viscosity of about 0.87dl/g is produced. In the process, nitrogen is purified by a catalytic oxidation method and is completely recycled; the oxygen-containing gas selects air as an oxidation medium; the catalyst adopts Pt and Pd loaded on gamma-alumina, and the nitrogen after the solid phase polymerization is purified by heating to 328 ℃ by an electric heater. The oxygen content in air was set to 19% and the k value was set to 1 in advance. And the system model carries out self-restraint adjustment according to an actual detection result and controls the adding amount of air. The method achieves stable control in three periods after one disturbance occurs, the fluctuation range of the residual oxygen amount in the purified nitrogen is reduced to 0-0.3 ppm, and the content of hydrocarbon can not be basically detected.
Comparative example 1:
for the same production device, nitrogen purification is controlled according to the method provided by the patent application document CN1139587A, after the operation is stable, hydrocarbon can not be basically detected in the purified nitrogen, but the residual oxygen amount is about 13.5 ppm.
Comparative example 2(s):
for the same production device, nitrogen purification is controlled according to the method provided by the CN1309582A patent application document, the air addition is controlled according to 99 percent of times of stoichiometric, after the operation is stable, residual oxygen can not be basically detected in the purified nitrogen, but the content of hydrocarbon is about 8 ppm.
The above examples and comparative results are given in the following table:
Claims (6)
1. a method for controlling the purification degree of inert gas in the solid phase polymerization process of polyester resin, the mixed gas which takes the inert gas as the main component and is led from the gas outlet of a solid phase polymerization reactor is heated and then enters the inlet pipeline of a catalytic bed, the inlet pipeline is also connected with the input pipeline of oxygen or oxygen-containing gas through a flow display controller FIC and a control valve thereof, the outlet of the catalytic bed is provided with a general gas output pipeline, the catalytic bed is filled with oxidation catalyst, the temperature is kept between 250 ℃ and 350 ℃, so that hydrocarbon in the mixed gas after the solid phase polymerization reacts with the led oxygen under the action of the high temperature and the catalyst, the method is characterized in that: arranging a hydrocarbon, carbon monoxide and oxygen content detection device on a gas output main pipeline of a catalytic bed, wherein an output signal of the detection device is Fx, and arranging a computer processing device of a mechanism model and a system model; when the system works, the Fx is input into the system model, the system model analyzes and processes the set value and the collection value of the system parameter, the output signal of the mechanism model and the actual detection signal Fx together to obtain an output signal, the output signal is fed back to the flow display controller FIC, and then the control on the adding amount of oxygen or oxygen-containing gas is realized through the control valve.
2. The method for controlling the degree of purging inert gas during solid phase polymerization of polyester resin according to claim 1, wherein:
the mechanism model adopts a Distributed Control System (DCS) to analyze and process, an empirical formula is obtained by using a fuzzy mathematical theory and a test, a set of mechanism model is established, the actual load and all relevant process parameters in the solid-phase polymerization production process are automatically acquired, the quality index parameters of the raw materials are manually input and adjusted and are all applied to the mechanism model, and the mechanism model is used for analyzing and processing the actual load and all the relevant process parameters in the mechanism modelTotal amount of various hydrocarbons F released and generated during solid phase polymerizationCHReaction rate FvAnd diffusion rate FkCarrying out operation processing on the three major factors;
said FCH＝f(IV0，IVn，Mr，Px) The intrinsic viscosity IV of the raw materials is taken into account0And finallyIntrinsic viscosity IV of the productnMolecular weight distribution Mr and production raw material formula Px(ii) a Said Fv＝f(Ca，Mr，Po，PCH，Tc) The catalyst content C is mainly taken into accountaMolecular weight distribution Mr, oxygen content PoHydrocarbon content PCHAnd reaction temperature Tc(ii) a Said Fk＝f(Tc，Vn，Mr，IV，Pn) Mainly considering the reaction temperature TcVolume V of polyester resin chipnMolecular weight distribution Mr, intrinsic viscosity IV and inert gas partial pressure Pn；
The implementation is programmed according to the following functional modules: define IV0、PxMr, given IVnCalculating to obtain the total hydrocarbon release amount FCHWill FCHInputting into a mechanism model; will influence FvGiven parameter CaMr and process parameter Po、PCH、TcComparing and calculating to obtain the reaction rate FvWill FvInputting into a mechanism model; will influence FkGiven parameters Mr, IV, VnAnd a process parameter Tc、PnComparing and calculating to obtain diffusion rate FkWill FkInputting into a mechanism model; mechanism model rejoining FCH、FvAnd FkAnd carrying out comprehensive operation and outputting an operation result.
3. The method for controlling the degree of purging inert gas during solid-phase polymerization of polyester resin according to claim 1 or 2, wherein:
the system model adopts a Distributed Control System (DCS) system for analysis and processing, and the system model Fs is equal tof(T，P，τ，Fc，Po，PCH) The output of the principal acceptance mechanism model, and the reaction temperature T, the inert gas pressure P, the reaction residence time T, and the inert gas flow F in the solid-phase polymerization stagecOxygen content PoHydrocarbon content PCHAnalyzing and processing the signals to obtain an output signal Fs;
the Fs signal is fed back to the flow display controller FIC on one hand, so that the control of the adding amountof oxygen or oxygen-containing gas is realized through a control valve, and on the other hand, the Fs signal is compared with Fx, so that a correction factor k of the system model is determined, and the correction factor k is used for adjusting parameters of the system model;
the implementation is programmed according to the following functional modules: the primary module employs multivariate predictive control and constraint control processesThe output result of the mechanism model is directly input into the main module; t, P, tau and F are automatically collected according to a certain period without manual interventionc、Po、PCHProcess parameter variables, on one hand, the parameters are optimized by an upper computer in a multivariate variable off-line mode, the optimization results are input into a main module, on the other hand, the traditional single variable operation processing is carried out, one part of the processing results are directly fed back to the main module, the other part of the processing results are subjected to basic PID (proportion integration differentiation) adjustment through a proportional, integral and differential adjuster, the adjustment results are input into related technological processes for adjustment, and new T, P, tau and F are obtainedc、Po、PCHProcess parameters, which are input to the primary module again; and the main module integrates the information of the four sources to carry out operation processing, obtains an output result, sends the output result to an upper computer to be stored and operated, and compares and optimizes the output result with the actually detected contents Fx of hydrocarbon, carbon monoxide and oxygen to obtain a system model output signal Fs.
4. The method for controlling the degree of purging inert gas during solid-phase polymerization of polyester resin according to claim 3, wherein: the initial setting value of the correction factor k is 1.
5. The method for controlling the degree of purging inert gas during solid-phase polymerization of polyester resin according to claim 1, wherein: the inert gas is nitrogen or contains nitrogen; the oxygen-containing gas is air; the oxidation catalyst is Pt and Pd supported on alumina; the hydrocarbon comprises ethylene glycol C2H6O2Acetaldehyde C2H4O。
6. The method for controlling the degree of purging inert gas during solid-phase polymerization of polyester resin according to claim 1, wherein: the purified gas coming out of the catalytic bed is totally or partially recycled to the pre-drying section of the solid phase polymerization reactor to remove the water produced during the purification treatment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106947069A (en) * | 2017-04-19 | 2017-07-14 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN109386360A (en) * | 2017-08-11 | 2019-02-26 | 通用汽车环球科技运作有限责任公司 | The method for determining the oxidation susceptibility of oxidation catalyzer device |
| CN110471384A (en) * | 2019-08-27 | 2019-11-19 | 恒力石化（大连）有限公司 | A kind of PTA device advanced control system |
| CN112270074A (en) * | 2020-10-14 | 2021-01-26 | 深圳数设科技有限公司 | Method and device for constructing model of product prototype |
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2003
- 2003-07-30 CN CNA031322018A patent/CN1487002A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947069A (en) * | 2017-04-19 | 2017-07-14 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN106947069B (en) * | 2017-04-19 | 2019-06-04 | 中国石化仪征化纤有限责任公司 | A kind of small-sized solid phase experimental provision |
| CN109386360A (en) * | 2017-08-11 | 2019-02-26 | 通用汽车环球科技运作有限责任公司 | The method for determining the oxidation susceptibility of oxidation catalyzer device |
| CN109386360B (en) * | 2017-08-11 | 2021-02-05 | 通用汽车环球科技运作有限责任公司 | Method for determining the oxidation behavior of an oxidation catalyst device |
| CN110471384A (en) * | 2019-08-27 | 2019-11-19 | 恒力石化（大连）有限公司 | A kind of PTA device advanced control system |
| CN112270074A (en) * | 2020-10-14 | 2021-01-26 | 深圳数设科技有限公司 | Method and device for constructing model of product prototype |
| CN112270074B (en) * | 2020-10-14 | 2023-12-26 | 苏州数设科技有限公司 | Product prototype model construction method and device |
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