CN1303419C - Polymer stay time distribution on-line measurement method and system - Google Patents
Polymer stay time distribution on-line measurement method and system Download PDFInfo
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- CN1303419C CN1303419C CNB2004100254076A CN200410025407A CN1303419C CN 1303419 C CN1303419 C CN 1303419C CN B2004100254076 A CNB2004100254076 A CN B2004100254076A CN 200410025407 A CN200410025407 A CN 200410025407A CN 1303419 C CN1303419 C CN 1303419C
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Abstract
The present invention discloses a polymer residence time distribution on-line measurement method and a system. A reference detector monitors an ultraviolet light source and transmits ultraviolet light. A part of optical fibers of an optical fiber probe conveys incident rays from a light source to radiate processed polymers compartmentally added with a tracer agent, and the tracer agent in the processed polymers is excited to generate the corresponding weak light. Another part of optical fibers of the optical fiber probe conveys the generated weak light to a weak light detector, weak light signals are received by the weak light detector, processed by an amplifier and a signal processing unit and sampled by a computer, and the curve figure of the change of residence time distribution analogue signals along with the time is displayed in real time. The present invention realizes polymer residence time distribution on-line measurement and has the advantages of real time, continuity and the like, and furthermore, the minutiae characteristics of residence time distribution can be comprehensively reflected. The present invention can be directly used for the measurement of partial residence time distribution, utilizes weak light measurement to overcome the difficulties of a light reflection method, is convenient to calibrate detection signals and has better self-calibration property than an ultraviolet spectrophotometer.
Description
Technical field
The present invention relates to a kind of polymkeric substance detention period and distributing on-line measurement method and system.
Background technology
Residence time distribution (RTD) has reflected the time history of all materials to be machined in equipment.In Chemical Reaction Engineering, RTD is a basic parameter that characterizes chemical reactor performance, is to determine to optimize blending, an important tool of dispersion and polymerization process condition.For the reaction extrusion, the reaction kinetics of reaction mass is closely related with its residence time in extruder, and then influences mixability, palliating degradation degree, the efficient of chemical reaction and the quality of final products of product.
The measurement that the polymkeric substance residence time distributes is divided into off-line (off-line) method and online (on-line) method is measured.Off-line method is the early stage method that adopts.This method time and effort consuming, test point are discontinuous, and the experimental data point limited amount, the precision that obtain are low, especially are unfavorable for the tail region of RTD curve is carried out analyzing in detail.Have advantages such as real-time, continuity at line method, not only measure fast, and can obtain a large amount of experimental data points.
The development of the online detection of RTD in recent years is very fast.Based on the online test method of the multiple RTD of heterogeneity tracer agent, and the different pick-up unit that is adopted.They adopt MnO based on principles such as radioactivity, ultrasonic reflections, optical reflection, electric conductivity, magnetic, near infrared absorption
2, La
2O
3, filler, carbon black, TiO
2, KNO
3, NaNO
3, tracer agent of different nature such as NaCl, iron powder, coloured dyestuff.Utilize the radioactivity of tracer agent to detect RTD, major defect is the risk that has radiation pollution, and very high to maintenance requirement.Optical reflection method shortcoming is, screw surface also can reflected light, this light signal must be deducted by digital processing, and problem is to make intensity of reflected light that in various degree minimizing be arranged according to the tracer concentration difference, causes the related very difficulty of light signal and tracer concentration.Supersonic reflection method must be provided with an aluminium fender pile between ultrasonic probe and polymer melt, detect and use the die geometry complexity.Electric conductivity, method of magnetic, near infrared absorption method must adopt the tracer agent of special nature, are subject to environmental factor and disturb.
Summary of the invention
The purpose of this invention is to provide a kind of polymkeric substance detention period and distributing on-line measurement method and system.
Monitor the ultraviolet light of ultraviolet source emission 200～700 nano wave lengths by the reference detector, adopt a part of optical fiber of fibre-optical probe to carry incident ray from light source, irradiation is with 0.01～1 gram, 1～10 second compartment of terrain adds the processed polymkeric substance of tracer agent, and the tracer agent in the processed polymkeric substance is stimulated and produces the low-light of corresponding 200～700 nano wave lengths; Another part optical fiber of fibre-optical probe is transferred to fainter light detector with the low-light that produces, receive low level light signal by fainter light detector, through amplifier and signal processing unit,, and show residence time distribution simulation signal change curve in time in real time again by computer sampling.
The polymkeric substance detention period and distributing on-line measurement system: ultraviolet source joins with coupling mechanism, fibre-optical probe, fainter light detector, amplifier, signal processing unit, computing machine successively, and ultraviolet source joins with reference detector, signal processing unit, computing machine successively.
The present invention directly puts into fibre-optical probe Polymer Processing equipment, directly optical excitation can be transferred on the processed fluid, detects low-light emission measure subsequently again, realizes the polymkeric substance detention period and distributing on-line measurement.Can adopt light filter with low-light-level measurement, not only overcome the difficulty that reflection method runs into, eliminate process equipment for example the screw channel bottom and the catoptrical influence of spiral shell edge surface of double screw extrusion machine; Also be convenient to the calibration of detectable signal, better than ultraviolet spectrophotometer self-correcting parasexuality.Show that by online and off-line method test experiments two kinds independently the method for testing consistance is good under the same terms.The online two channel measurement systems of the present invention increase a cover coupling mechanism, fibre-optical probe, fainter light detector and amplifier than system shown in Figure 1, also can be in the on-line measurement of polymkeric substance Local Residence Time Distribution.
Description of drawings
Fig. 1 is a polymkeric substance detention period and distributing on-line measurement system synoptic diagram;
Fig. 2 is a fibre-optical probe structural representation of the present invention;
Fig. 3 is the online two channel measurement system schematic of the present invention;
Fig. 4 is a reproducible proof diagram of the present invention;
Fig. 5 is the linear relationship chart of voltage and tracer concentration;
Fig. 6 is the comparison diagram that the RTD curve that measures of on-line system of the present invention and off-line method obtain.
Embodiment
The present invention is by the ultraviolet light of reference detector supervision ultraviolet source emission 200～700 nano wave lengths, and ultraviolet light is coupled in the silica fibre through coupling mechanism; A part of optical fiber of fibre-optical probe is used for carrying incident ray from light source, irradiation is with 0.01～1 gram, 1～10 second compartment of terrain adds the processed polymkeric substance of tracer agent, and the tracer agent in the processed polymkeric substance is stimulated and produces the low-light of corresponding 200～700 nano wave lengths.Tracer agent adopts anthracene, naphthalene or contains the compound of anthracene, naphthyl, and the advantage of low-light tracer agent is that its sensitivity is very high, only needs seldom to measure just can be detected, and can reduce the interference to system; The group of low-light also can be grafted to and make the big molecule tracer agent more approaching with system character on the macromolecular chain.
Excite the low-light amount and the tracer concentration of generation linear, detect this low-light amount for this reason and can obtain residence time distribution.Another part optical fiber of fibre-optical probe is transferred to fainter light detector with the low-light that produces, receive low level light signal by fainter light detector, through amplifier and signal processing unit,, and show residence time distribution simulation signal change curve in time in real time again by computer sampling.
The ultraviolet wavelength of above-mentioned ultraviolet source emission is 300～600 nanometers, is generally 340～360 nanometers.Tracer agent is stimulated and produces corresponding wavelength is 300～600 nanometers, is generally 400～500 nanometers.
For example adopt method of testing of the present invention in double screw extrusion machine, fibre-optical probe can install on the diverse location of extruder barrel and carry out on-line measurement, and the screw rod section a bit all can measure arbitrarily in theory.Extruder begins test after reaching stable operation, adds tracer agent with quantitative compartment of terrain; With the tested polymkeric substance of the UV-irradiation of specific wavelength, be received in the low-light of the respective specific wavelength that the tracer agent in the tested polymkeric substance sends by fainter light detector, monitor ultraviolet source by the reference detector simultaneously.Low level light signal reads sampled value by computing machine by microcomputer interface behind signal processing unit, real time record RTD experimental data and carry out analyzing and processing.
As shown in Figure 1, ultraviolet source joins with coupling mechanism, fibre-optical probe, fainter light detector, amplifier, signal processing unit, computing machine successively, and ultraviolet source joins with reference detector, signal processing unit, computing machine successively.Ultraviolet source adopts high-pressure sodium lamp or bright lamp etc.; Coupling mechanism is used for the ultraviolet light of ultraviolet source is coupled to silica fibre; Fainter light detector adopts fluorescence detector, is used to detect tracer agent and is stimulated and produces low-light; Amplifier adopts the low noise high-sensitivity amplifier, is used for the amplification of detected low level light signal; Signal processing unit obtains residence time distribution simulation signal according to exciting the low-light amount and the tracer concentration of generation linear with detected low-light amount processing.The reference detector is surveyed the ultraviolet light that ultraviolet source sends, and by the reference circuit light source is implemented monitoring.
As shown in Figure 2, fibre-optical probe has fibre-optical splice 1, light filter 2, heating radiator 3, quartz window 4 successively.Consider the influence of melt high pressure and machine barrel high temperature heat transfer, specialized designs a kind of finned radiator structure, and do heat insulation processing at heat-transfer area, high temperature resistantly reach 310 ℃.The fixed sturcture of quartz window has been done high pressure resistant design, maximum withstand voltage reaching more than the 30Mpa.
As shown in Figure 3, online two channel measurement systems increase a cover coupling mechanism, fibre-optical probe, fainter light detector and amplifier, are convenient to the on-line measurement of polymkeric substance Local Residence Time Distribution.By the ultraviolet light of reference detector supervision ultraviolet source emission specific wavelength, ultraviolet light is divided into two-way.The two-way exciting light is respectively through separately coupling mechanism, fibre-optical probe, and irradiation has the processed polymkeric substance of tracer agent, and the tracer agent in the processed polymkeric substance is stimulated and produces the low-light of respective specific wavelength.The low-light that two fibre-optical probes will produce separately is transferred to fainter light detector, by fainter light detector reception low level light signal separately, again through amplifier and signal processing unit, by computer sampling, and show two-way residence time distribution simulation signal change curve in time in real time, thereby can obtain polymkeric substance Local Residence Time Distribution curve.
The evaluation of polymkeric substance detention period and distributing on-line measurement system reliability comprises following three aspects: the consistance of the linear relationship of reappearance, simulation low level light signal (voltage) and fluorescent tracing agent concentration, the RTD function that measures in line method and off-line method.Reappearance is done repeated experiment evaluation by the tracer agent with same amount under same experimental conditions.Fig. 4 distributes (feed rate 10.7kg/h, screw speed 60rpm) residence time in the on-line measurement TSE-35 of the system type double screw extrusion machine of the present invention, has shown the voltage-time curve of three groups of repeated experiments.They all superpose finely, show good reappearance.
The checking of the linear relationship of voltage and tracer concentration, be to remove under the identical situation of different other conditions of tracer dose, do experiment online and off-line method (ultraviolet spectrophotometry) respectively, and the tracer concentration that the voltage that obtains in line method experiment and the off-line method experiment of identical time point correspondence obtains is compared.Simulation low level light signal (voltage) value and tracer concentration are linearly proportional, and normalized RTD function can calculate according to following formula:
In the formula, V (t
i) be corresponding to t
iRelative voltage value (%) constantly.The relation of tracer concentration as shown in Figure 5 in voltage signal and the polymkeric substance.As shown in Figure 5, in the tracer concentration scope of appointment, both are linearly proportional.
System of the present invention on-line measurement and adopt in the TSE-35 type double screw extrusion machine that the off-line method of ultraviolet spectrophotometer obtains the RTD function more as shown in Figure 6, feed rate 10.7kg/h, 13.9kg/h, screw speed 60rpm, 90rpm.Off-line method is to be to take a sample at the extruding dies place in the time interval with 10s, and sample is that solvent is made into liquid to be measured with toluene, measures tracer concentration by UV751GD ultraviolet/visible spectrophotometer.Fig. 6 shows two kinds, and independently the RTD function consistance that obtains of analytical approach is good.
The main performance index of polymkeric substance detention period and distributing on-line measurement system:
(1) micro light detecting sensitivity: 0.01 μ W;
(2) measuring degree of stability is better than: ± 3%;
(3) precision: ± 2%;
(4) ultraviolet source power: 5-125W;
(5) burst of ultraviolel wavelength: 200-700nm;
(6) 310 ℃ of signal pickup device heatproofs, withstand voltage 30Mpa;
(7) environmental requirement: 0～50 ℃ of temperature, humidity≤90%R.H;
(8) working voltage: AC220 ± 11V, 50Hz/60Hz.
Claims (7)
1. polymkeric substance detention period and distributing on-line measurement method, it is characterized in that: the ultraviolet light that monitors ultraviolet source emission 200～700 nano wave lengths by the reference detector, adopt a part of optical fiber of fibre-optical probe to carry incident ray from light source, irradiation is with 0.01～1 gram, 1～10 second compartment of terrain adds the processed polymkeric substance of tracer agent, and the tracer agent in the processed polymkeric substance is stimulated and produces the low-light of corresponding 200～700 nano wave lengths; Another part optical fiber of fibre-optical probe is transferred to fainter light detector with the low-light that produces, receive low level light signal by fainter light detector, again through amplifier and signal processing unit, by computer sampling, and showing residence time distribution simulation signal change curve in time in real time, said tracer agent adopts anthracene, naphthalene or contains the compound of anthracene, naphthyl.
2. a kind of polymkeric substance detention period and distributing on-line measurement method according to claim 1 is characterized in that the ultraviolet wavelength of said ultraviolet source emission is 300～600 nanometers.
3 a kind of polymkeric substance detention period and distributing on-line measurement methods according to claim 1 and 2 is characterized in that the ultraviolet wavelength of said ultraviolet source emission is 340～360 nanometers.
4. a kind of polymkeric substance detention period and distributing on-line measurement method according to claim 1 is characterized in that said tracer agent is stimulated and produces corresponding wavelength is 300～600 nanometers.
5. according to claim 1 or 4 described a kind of polymkeric substance detention period and distributing on-line measurement methods, it is characterized in that said tracer agent is stimulated and produces corresponding wavelength is 400～500 nanometers.
6. polymkeric substance detention period and distributing on-line measurement system of method design according to claim 1, it is characterized in that: ultraviolet source joins with coupling mechanism, fibre-optical probe, fainter light detector, amplifier, signal processing unit, computing machine successively, and ultraviolet source joins with reference detector, signal processing unit, computing machine successively.
7. a kind of polymkeric substance detention period and distributing on-line measurement system according to claim 6 is characterized in that: said fibre-optical probe has fibre-optical splice (1), light filter (2), heating radiator (3), quartz window (4) successively.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100254076A CN1303419C (en) | 2004-06-17 | 2004-06-17 | Polymer stay time distribution on-line measurement method and system |
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| CNB2004100254076A CN1303419C (en) | 2004-06-17 | 2004-06-17 | Polymer stay time distribution on-line measurement method and system |
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| CN1595113A CN1595113A (en) | 2005-03-16 |
| CN1303419C true CN1303419C (en) | 2007-03-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008094306A2 (en) * | 2006-08-02 | 2008-08-07 | Awareness Technology, Inc. | Luminometer and methods of operation |
| JP4910707B2 (en) * | 2007-01-05 | 2012-04-04 | トヨタ自動車株式会社 | Fuel cell |
| CN101839859B (en) * | 2010-05-20 | 2012-02-22 | 杭州远方光电信息股份有限公司 | Device for testing residence time distribution (RTD) of material |
| CN103364377B (en) * | 2012-04-01 | 2016-04-06 | 中国科学院过程工程研究所 | The measuring method of macroscopic mixing time and application in a kind of strong electrolytic solution |
| CN105334134A (en) * | 2015-10-26 | 2016-02-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for determining residence time of titanium concentrate in high-temperature fluidization reactor |
| CN109366933A (en) * | 2018-11-27 | 2019-02-22 | 武汉轻工大学 | A kind of on-line detecting system of metal-polymer composite processing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5062713A (en) * | 1989-09-06 | 1991-11-05 | The Dow Company | Method for determining the residence time distribution of a polymer extruder |
| US5369483A (en) * | 1993-05-07 | 1994-11-29 | Basf Corporation | Analysis of polymer melt stream |
| JPH08122241A (en) * | 1994-10-26 | 1996-05-17 | Asahi Chem Ind Co Ltd | Residence time distribution measuring method and device |
| WO2002016932A1 (en) * | 2000-08-24 | 2002-02-28 | Samsung General Chemicals Co., Ltd. | Method of estimating the properties of a polymer product |
| CN2706756Y (en) * | 2004-06-17 | 2005-06-29 | 浙江大学 | Polymer residence time distribution on-line measuring system |
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2004
- 2004-06-17 CN CNB2004100254076A patent/CN1303419C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5062713A (en) * | 1989-09-06 | 1991-11-05 | The Dow Company | Method for determining the residence time distribution of a polymer extruder |
| US5369483A (en) * | 1993-05-07 | 1994-11-29 | Basf Corporation | Analysis of polymer melt stream |
| JPH08122241A (en) * | 1994-10-26 | 1996-05-17 | Asahi Chem Ind Co Ltd | Residence time distribution measuring method and device |
| WO2002016932A1 (en) * | 2000-08-24 | 2002-02-28 | Samsung General Chemicals Co., Ltd. | Method of estimating the properties of a polymer product |
| CN2706756Y (en) * | 2004-06-17 | 2005-06-29 | 浙江大学 | Polymer residence time distribution on-line measuring system |
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