EP3941617A1 - Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung - Google Patents
Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischungInfo
- Publication number
- EP3941617A1 EP3941617A1 EP20712362.1A EP20712362A EP3941617A1 EP 3941617 A1 EP3941617 A1 EP 3941617A1 EP 20712362 A EP20712362 A EP 20712362A EP 3941617 A1 EP3941617 A1 EP 3941617A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oligomer
- monomer mixture
- line
- composition
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 173
- 239000000178 monomer Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000011155 quantitative monitoring Methods 0.000 title claims abstract description 18
- 238000004497 NIR spectroscopy Methods 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000012569 chemometric method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920005903 polyol mixture Polymers 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 2
- 238000009434 installation Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 15
- 239000003380 propellant Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- -1 TDI or monomeric MDI Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- 238000000491 multivariate analysis Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
- B01J3/044—Pressure vessels, e.g. autoclaves in the form of a loop
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0033—Optimalisation processes, i.e. processes with adaptive control systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2435—Loop-type reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N2021/8411—Application to online plant, process monitoring
Definitions
- the invention relates to a method for the quantitative monitoring of
- composition of an oligomer / monomer mixture containing a plurality of mixture components in particular a polyol mixture or a
- the invention also relates to a device for quantitative monitoring of the composition of an oligomer / monomer mixture and to a system for producing a polymer product.
- the processor trusts the product specifications of the manufacturer of the raw materials and the dosing accuracy of their own systems. Deviations from the target value due to incorrect mixing, storage or metering of individual components often remain undetected and in the negative case lead to material scrap or fluctuations in product quality.
- the object is achieved with a method for quantitative monitoring of the composition of an oligomer / monomer mixture containing a plurality of mixture components, in particular a polyol mixture or an isocyanate mixture, in that the quantitative composition of the polymer mixture is measured by means of an NIR spectroscopy measuring unit using a chemometric method , whereby the liquid pressure in the quantitatively monitored oil igomer / monomer mixture P L is > 3 bar.
- An oligomer / monomer mixture within the meaning of the present invention can contain predominantly oligomers (also residues of monomers), a mixture of oligomers and monomers in different proportions or predominantly monomers (but also residues of oligomers) in each case together with additives . In this respect, it is not a question of pure oligomer or monomer mixtures.
- the components of the oligomer / monomer mixture are selected to take part in a polymerization reaction, in particular a polyaddition or polycondensation reaction.
- an oligomer / monomer mixture within the meaning of the invention can be an oligomer mixture formed by a polyol with additives, which reacts with an isocyanate or an isocyanate mixture in a polyaddition reaction to form a polyurethane material.
- the oligomer / monomer mixture within the meaning of the invention can be an oligomer mixture formed by oligomeric isocyanate, for example oligomeric MDI, together with additives, which reacts with a polyol or a polyol mixture to form a polyurethane material.
- An oligomer / monomer mixture in the context of the invention can also be a monomer mixture formed by a monomeric isocyanate such as TDI or monomeric MDI, together with additives. Mixtures of monomeric and oligomeric MDI are also possible.
- the particular advantage of using NIR spectroscopy for quantitative monitoring of the composition of an oligomer / monomer mixture is that the measurement can be carried out with high precision while a production plant is in operation.
- the measurement can be carried out at pressures> 3 bar, so that it is also suitable for quantitative monitoring of Oil / monomer mixtures in pressurized vessels or lines are suitable. At these pressures, among other things, the occurrence of gas bubbles in the oil / monomer mixture to be examined, which lead to increased signal noise, is minimized.
- gas is introduced into the igomer / monomer mixture via the agitator or the igomer / monomer mixtures are processed using what is known as gas loading, as is sometimes done in the production of polyurethane materials.
- NIR spectroscopy is a widely used analytical method that is used both in the laboratory and in online operations. Areas of application are, for example, the continuous analysis of wine (W02007 / 006099 A 1), bitumen (US 7067811B2) or insulin (US7755051B2). In addition, NIR spectroscopy is used to determine particle sizes (US2015 / 0293005) or OH numbers (EP 3 179 232 A1).
- N1R techniques for special measuring tasks is also known from: WO 00/02035 (determination of organic acid in organic polymer), US 005717209 (spectral analysis of hydrocarbons), US 006228650; WO 99/31485 (control of the separation of chemical components in an alkylation process using an acid catalyst), US 6339222; WO 00/68664 (determination of ionic species in pulp liquor), DE 10005130A1 (control of polymer processes, determination of NCO in PU)
- NIR spectroscopy with chemometric evaluation methods for special measurement tasks is also known per se from the prior art, e.g. B. DE 21 39 269, WO 97/41420, WO 98/29787, WO 99/31485, JP 11350368, JP 2000146835, JP 2000298512, WO 2002/04394, WO 2002/12969, U.S. Patent 5,707,870, U.S. Patent 5,712,481, and WO 2000/68664.
- Chemometric evaluation methods are based, for example, on the Partial Least Square (PLS) method, such as B. in Raphael Vieira "In-line and In Situ Monitoring of Semi-Batch Emulsion Copolymerizations Using Near-Infrared Spectroscopy” J Applied Polymer Science, Vol. 84, 2670-2682 (2002). Further information on chemometric evaluation methods can be found in T. Rohe "Near Infrared (NIR) spectroscopy for inline monitoring of polymer extrusion processes "Talanta 50 (1999) 283-290 or C.
- NIR Near Infrared
- the liquid pressure in the quantitatively monitored oligomer / monomer mixture P L is > 3 bar. According to a first further embodiment of the invention, it is provided that the liquid pressure in the quantitatively monitored oligomer / monomer mixture P L is > 20 bar and particularly preferably> 120 bar.
- Such high pressures are used, for example, in the production of polyurethane, in which the reactants are mixed by means of countercurrent injection.
- the NIR spectroscopy is carried out in a wavelength range of 700-3000 nm, preferably 780-2500 nm and particularly preferably 1000-2250 nm.
- the NIR spectroscopy can be carried out as a transmission measurement, in particular as an online transmission measurement, the beam source and the detector element being arranged opposite one another.
- the distance between the beam source and the detector element can be 1 to 20 mm. This ensures that, on the one hand, a sufficient amount of the oligomer / monomer mixture is irradiated in order to obtain a sufficient signal-to-noise ratio. On the other hand, too great a weakening of the intensity of the NIR radiation is avoided.
- “Online transmission measurement” in the sense of the present invention is understood to mean that the measurement can be carried out online, ie without taking a sample, but for example in an ongoing process, in particular a production process.
- An NIR measuring cell can be preferred be integrated into a line with which the oil / monomer mixture is fed to a reactor. Alternatively, a measuring probe can be integrated into the system's storage tank.
- the measurement by means of NIR spectroscopy can also be carried out as a transflexion measurement, the result of the oligomer / monomer mixture being irradiated twice by reflecting the measuring beam on a reflective surface.
- the NIR spectroscopy measuring unit is a diode array spectrometer or an FT-IR spectrometer.
- An FT spectrometer is particularly preferred as the NIR spectroscopy measuring unit, the quantitative composition of the oligomer / monomer mixture being measured quasi continuously.
- a particularly close-meshed monitoring of the composition of the oligomer / monomer mixture can be achieved, so that almost real-time information on the quantitative composition of the monitored oligomer / monomer mixture is available.
- the method according to the invention can be used at different positions, for example in a production line or also in a laboratory environment.
- the oil igomer / monomer mixture is stored in a pressurized vessel or is conducted in a pressurized line, preferably in a circulation line, the individual mixture components of the oil / monomer mixture are each fed via feed lines to the vessel or the line.
- the measured values of the quantitative monitoring of the composition of the oligomer / monomer mixture are particularly suitable for regulating the composition.
- the Measured values from the NIR spectroscopy measuring unit are transmitted to a control unit, with the control unit transmitting a control signal to a metering unit arranged in at least one feed line in the event of a deviation from a target composition of the oligomer / monomer mixture.
- a particularly advantageous application of the method according to the invention consists in the quantitative monitoring of the composition of several oligomer / monomer mixtures which are mixed with one another and thereby react with one another for the purpose of producing, for example, a certain polymer product.
- a first oligomer / monomer mixture and at least one second oligomer / monomer mixture can be provided, the first oligomer / monomer mixture being introduced into a mixing and reaction unit via a first line and the at least one second oligomer / monomer mixture being introduced via at least one second line is introduced into the mixing and reaction unit, the first oligomer / monomer mixture and the at least one second oligomer / monomer mixture being mixed there and reacting with one another to form a polymer product, the composition of the first oligomer / monomer mixture and / or the the quantitative composition of the second oligomer / monomer mixture is / are quantitatively monitored by means of the NIR spectroscopy measuring unit.
- a further aspect of the present invention relates to a method for producing a polymer product, in particular a polyurethane product, from a first oligomer / monomer mixture and at least one second oligomer / monomer mixture according to one of claims 10 or 11.
- the advantages of this method are those mentioned above Advantages accordingly.
- Another aspect of the present invention relates to a device for quantitative monitoring of the composition of an oligomer / monomer mixture containing a plurality of mixture components, the device having at least one container or at least one line for storing or guiding the oligomer / monomer mixture at a liquid pressure of P L > 3 bar, wherein the device further comprises a NIR spectroscopy measuring unit, wherein the device is set up for quantitative monitoring of the composition of the oligomer / monomer mixture according to the method according to one of claims 1 to 12.
- a control unit is provided in the device, the control unit being designed such that it sends a control signal in the event of a quantitative deviation of the composition of the oligomer / monomer mixture stored or carried in the container or the at least one line from a target composition transmitted to a metering unit arranged in at least one feed line to the container or to the line.
- Another aspect of the present invention relates to a plant for the production of a polymer product, in particular a polyurethane material, comprising: a mixing and reaction unit for mixing a first oligomer / monomer mixture and at least one second oligomer / monomer mixture,
- the first line is designed to introduce the first oligomer / monomer mixture at a liquid pressure P L > 3 bar into the mixing and reaction unit and / or the at least one second line is designed to add the at least one second oligomer / monomer mixture a fluid pressure P L > 3 bar to be introduced into the mixing and reaction unit, at least one NIR spectroscopy measuring unit being provided, the at least one NIR spectroscopy measuring unit being designed to determine the quantitative composition of the first oligomer / monomer mixture in the first line and / or the to monitor the quantitative composition of the at least one second oligomer / monomer mixture in the at least one second line according to the method according to any one of claims 1 to 12.
- Another aspect relates to a method for determining the propellant concentration in an oligomer / monomer mixture.
- a reference mixture for example a system comprising a polyol, activators, catalysts and possibly other components, but without a blowing agent.
- This NIR spectrum can be referred to as the basic spectrum.
- a defined propellant content is then added to the reference mixture (for example 2% by weight) and an NIR spectrum is recorded again.
- the propellant content is successively increased (2%, 4%, 6%, ...) and further NIR spectra are recorded.
- the basic spectrum is subtracted from each individual spectrum of the mixture with a defined, increasing propellant content, forming a difference spectrum or residual which shows the spectral influence of the propellant.
- a specialized chemometric method can then be developed that can be used to determine unknown propellant contents.
- the NIR spectrum without propellant is first determined from a mixture of unknown composition and stored in an evaluation computer, for example. If this mixture is then, for example, in a system or a container with an unknown propellant content, an NIR spectrum can also be recorded from this mixture. Again, the basic spectrum of this mixture (ie without propellant) is subtracted from the NIR spectrum, which characterizes the mixture with an unknown propellant concentration, for example with the aid of the evaluation computer, and the specialized chemometric method can be used can be applied to the difference spectrum for the purpose of precise determination of the propellant content in the mixture of unknown composition.
- Suitable blowing agents are, for example, cyclopentane or mixtures of cyclopentane and isopentane, as well as n-pentane or the class of hydrofluoroolefins.
- Fig. 2 parts of a device for quantitative monitoring of the composition of a polyol mixture in a highly schematic view.
- the system 100 comprises two containers 1, 2 in which a polyol (container 1) and additives such as activator, catalyst or others and an isocyanate (container 2) and additives are stored as raw materials of the polyurethane material.
- Container 1 is connected to a mixing and reaction unit 3 via a first line 1 a.
- the container 2 is also connected to the mixing and reaction unit 3 via a second line 2a.
- the two reactant streams react in the mixing and reaction unit 3 and the reaction mixture is passed via an outlet pipe 3a into a mold (not shown), where it forms the desired rigid polyurethane foam.
- a pump unit 11a, 21a for conveying the respective material flows is arranged in the first line 1a and the second line 2a. Furthermore, the first and the second line la, 2a are each as a circulation line with one each Return lines 1b, 2b from the mixing and reaction unit 3 to the containers 1, 2 are formed. In both lines la, lb there is a pressure of P L > 3 bar, in the present case 130 bar (countercurrent injection).
- Additives / blowing agents for producing the rigid polyurethane foam are added to the polyol transported in line la. These can, for example, be propellants or catalysts.
- the lines 1c, 1d fed by the containers 4, 5, each of which also include pump units 11c, 1 1d, are shown here by way of example. It goes without saying that, depending on the application, a significantly larger number of additives can also be added to the polyol and / or the isocyanate.
- the test cell 72 of an NIR spectroscopy measuring unit 7 (see FIG. 2) is integrated into the line la.
- the NIR spectroscopy measuring unit is provided only on the isocyanate side (line 2a) or on both sides of the mixing and reaction unit.
- the composition of the polyol mixture can be quantitatively monitored with the NIR spectroscopy measuring unit 7 directly at the entrance to the mixing and reaction unit 3 and the output signal of the NIR spectroscopy measuring unit 7 can be monitored via a control unit (not shown) to keep the composition of the polyol mixture constant.
- the material from the containers 1, 2 can be recirculated via the lines la, lb, 2a, 2b and provided with additives such as, for example, via the line lc, ld until the desired composition is in the containers 1, 2 is set.
- FIG. 2 shows the test cell 72 of an NIR spectroscopy measuring unit 7 with an enlarged detail X.
- the test cell 72 comprises the section of the line 1a from FIG. 1 and two opposing probes 72a, 72b connected thereto.
- Probe 72a functions as a beam source, by means of which an NIR measurement signal is radiated into the polyol mixture flowing through line 1a.
- the NIR measurement signal is generated by a corresponding NIR radiation source and guided via optics into a fiber optic cable, via which it reaches the measurement probe 72a.
- the NIR measurement signal radiated into the line 1a through which the polyol mixture flows is attenuated as a function of the wavelength by absorption and possibly also scattering (see detail X).
- the attenuated signal is then detected by the measuring probe 72b, which is sensitive to NIR radiation, as a detector element and, for example, passed via a further fiber optic cable to a spectrometer structure 73, for example in the form of an interferometer.
- the distance between the probe 72a (beam source) and the probe 72b (detector element) can be set in a wide range, for example between 1 and 20 mm, depending on the absorption and scattering behavior of the mixture flowing through the line 1a.
- the spectrum 74 obtained in the spectrometer structure 73 can then be sent to an electronic evaluation and display unit (not shown).
- the measurement signal recorded by means of the NIR spectroscopy measurement unit 7 is particularly suitable for a control loop in which the quantitative composition of the polyol mixture of the line 1 a, 1 b is monitored. If, for example, the NIR spectroscopy measuring unit 7 detects an insufficient proportion of a mixture component, for example the additive from the container 4, then a control signal is sent to the corresponding pump unit 11c, which causes a higher dosage of this additive until the correct proportion of the additive is in the Polyol mixture is measured again by the NIR spectroscopy measuring unit 7.
- the particular advantage of the measuring method is that the measurements can take place quasi-continuously, so that corresponding deviations from the target composition can be compensated very quickly by the control system.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Automation & Control Theory (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19164232.1A EP3711852A1 (de) | 2019-03-21 | 2019-03-21 | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung |
PCT/EP2020/058008 WO2020188116A1 (de) | 2019-03-21 | 2020-03-23 | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3941617A1 true EP3941617A1 (de) | 2022-01-26 |
Family
ID=65894919
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19164232.1A Ceased EP3711852A1 (de) | 2019-03-21 | 2019-03-21 | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung |
EP20712362.1A Withdrawn EP3941617A1 (de) | 2019-03-21 | 2020-03-23 | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19164232.1A Ceased EP3711852A1 (de) | 2019-03-21 | 2019-03-21 | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung |
Country Status (4)
Country | Link |
---|---|
US (1) | US20220168701A1 (de) |
EP (2) | EP3711852A1 (de) |
CN (1) | CN113557083A (de) |
WO (1) | WO2020188116A1 (de) |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2933553A1 (de) * | 1979-08-18 | 1981-03-26 | Bayer Ag, 51373 Leverkusen | Verfahren und einrichtung zum herstellen von formteilen aus einem mehrkomponentenreaktionsgemisch |
US5151474A (en) * | 1990-02-16 | 1992-09-29 | The Dow Chemical Company | Process control method for manufacturing polyolefin |
US5712481A (en) | 1990-04-09 | 1998-01-27 | Ashland Inc | Process and apparatus for analysis of hydrocarbon species by near infrared spectroscopy |
EP0778938B1 (de) | 1994-09-01 | 2002-12-11 | E.I. Du Pont De Nemours And Company | Verfahren zur neutralisation von säuren in einer polymerlösung |
US5532487A (en) * | 1994-11-23 | 1996-07-02 | E. I. Du Pont De Nemours And Company | Near-infrared measurement and control of polyamide processes |
US5717209A (en) | 1996-04-29 | 1998-02-10 | Petrometrix Ltd. | System for remote transmission of spectral information through communication optical fibers for real-time on-line hydrocarbons process analysis by near infra red spectroscopy |
US6072576A (en) | 1996-12-31 | 2000-06-06 | Exxon Chemical Patents Inc. | On-line control of a chemical process plant |
US6228650B1 (en) | 1997-12-17 | 2001-05-08 | Phillips Petroleum Company | Acid catalyst regeneration control |
JPH11350368A (ja) | 1998-06-09 | 1999-12-21 | Yokogawa Electric Corp | 白液連続測定装置 |
US6300633B1 (en) | 1998-07-06 | 2001-10-09 | Bayer Corporation | In-line method for determining the residue content of an isocyanate and apparatus useful therefor |
JP3620572B2 (ja) | 1998-11-10 | 2005-02-16 | 横河電機株式会社 | アルカリ濃度分析装置 |
US6339222B1 (en) | 1998-11-12 | 2002-01-15 | Kvaerner Canada Inc. | Determination of ionic species concentration by near infrared spectroscopy |
US6552221B1 (en) | 1998-12-18 | 2003-04-22 | Millenium Petrochemicals, Inc. | Process control for acetic acid manufacture |
JP3959887B2 (ja) | 1999-04-14 | 2007-08-15 | 三井化学株式会社 | 近赤外分析によるプラントの運転制御方法 |
CA2271221C (en) | 1999-05-05 | 2007-12-18 | Kvaerner Canada Inc. | Determination of ionic species concentration by near infrared spectroscopy |
FR2794760B1 (fr) * | 1999-06-11 | 2001-08-17 | Rhodianyl | Procede de fabrication de polyamides |
DE10005130A1 (de) | 2000-02-04 | 2001-08-16 | Basf Coatings Ag | Vorrichtung und Verfahren zur Kontrolle von Polymerisationsreaktionen |
US7191037B2 (en) | 2000-08-07 | 2007-03-13 | Mitsui Chemicals, Inc. | Method for controlling production process |
CA2503610C (en) | 2002-11-06 | 2011-08-02 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Nir spectroscopy method for analyzing chemical process components |
DE10322439A1 (de) * | 2003-05-19 | 2004-12-09 | Bayer Ag | Verfahren und Vorrichtung zur Bestimmung der Isomerenzusammensetzung bei Isocyanat-Herstellprozessen |
US20060097173A1 (en) | 2003-10-15 | 2006-05-11 | Sanofi-Aventis Deutschland | Method and device for the quantitative analysis of solutions and dispersions by means of near infrared spectroscopy |
DE102004013258A1 (de) * | 2004-03-18 | 2005-10-20 | Bayer Ag | Verfahren zur Herstellung von Polyamid |
AU2005100565B4 (en) | 2005-07-12 | 2006-02-02 | The Australian Wine Research Institute | Non-destructive analysis by VIS-NIR spectroscopy of fluid(s) in its original container |
ITMI20131916A1 (it) * | 2013-11-19 | 2015-05-20 | Versalis Spa | Metodo per monitorare un parametro di controllo di una reazione di polimerizzazione e relativo apparato per attuare detto metodo |
US9389161B2 (en) | 2014-04-09 | 2016-07-12 | Exxonmobil Chemical Patents Inc. | On-line FT-NIR method to determine particle size and distribution |
DE102015223789A1 (de) * | 2015-10-07 | 2017-04-13 | Sms Group Gmbh | Online Analytik mittels Nahinfrarotspektroskopie-Analytik NIR insbesondere zur Herstellung von Polyaluminiumchloridhydroxid |
EP3179232A1 (de) | 2015-12-09 | 2017-06-14 | Purinova Sp. z o.o. | Verfahren zur bestimmung der hydroxylzahl in flüssigkeiten aufweisend einer säurezahl welche grösser ist als die hydroxylzahl |
EP3263620B1 (de) * | 2016-06-30 | 2019-03-13 | Polytex Sportbeläge Produktions-GmbH | Pu-fussboden-herstellung für eine sportfeld |
-
2019
- 2019-03-21 EP EP19164232.1A patent/EP3711852A1/de not_active Ceased
-
2020
- 2020-03-23 US US17/437,190 patent/US20220168701A1/en not_active Abandoned
- 2020-03-23 EP EP20712362.1A patent/EP3941617A1/de not_active Withdrawn
- 2020-03-23 WO PCT/EP2020/058008 patent/WO2020188116A1/de active Application Filing
- 2020-03-23 CN CN202080022265.5A patent/CN113557083A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CN113557083A (zh) | 2021-10-26 |
US20220168701A1 (en) | 2022-06-02 |
EP3711852A1 (de) | 2020-09-23 |
WO2020188116A1 (de) | 2020-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5532487A (en) | Near-infrared measurement and control of polyamide processes | |
DE69911059T2 (de) | Prozesssteuerungsverfahren bei der herstellung von essigsäure | |
DE69837814T2 (de) | Verfahren zur on-line analyse eines sauren katalysators für ein verfahren zur umwandlung von kohlenwasserstoffen | |
EP2825926B1 (de) | Verfahren zur regelung der viskosität eines mindestens zwei komponenten mit unterschiedlicher viskosität enthaltenden gemischs | |
EP1480033B1 (de) | Verfahren zur Bestimmung der Isomerenzusammensetzung bei Isocyanat-Herstellprozessen | |
Khettry et al. | Real‐time analysis of ethylene vinyl acetate random copolymers using near infrared spectroscopy during extrusion | |
DE102011007011A1 (de) | Analysegerät zur automatisierten Bestimmung einer Messgröße einer Flüssigkeitsprobe | |
EP3941617A1 (de) | Verfahren und vorrichtung zur quantitativen überwachung der zusammensetzung einer oligomer-/monomermischung | |
US9636629B2 (en) | Real-time online determination of caustic in process scrubbers using near infrared spectroscopy and chemometrics | |
DE10005130A1 (de) | Vorrichtung und Verfahren zur Kontrolle von Polymerisationsreaktionen | |
EP1445246A2 (de) | Verfahren zur Überwachung und Führung von Nitrierprozessen mit Hilfe von Online-Spektrometern | |
DE102007021324B4 (de) | Vorrichtung und Verfahren zur Bestimmung des Mischungsverhältnisses eines aus zwei oder mehreren Einzelkomponenten bestehenden Mediums | |
EP0694781A1 (de) | Verfahren zur Kontrolle von Polykondensations- oder Polyadditionsreaktionen | |
DE202007006508U1 (de) | Vorrichtung zur Bestimmung des Mischungsverhältnisses eines aus zwei oder mehreren Einzelkomponenten bestehenden Mediums | |
DE19960586B4 (de) | Verfahren und Einrichtung zur Messung von Kenngrössen einer Probe durch Spektralanalyse | |
EP3359490B1 (de) | Online analytik mittels nahinfrarotspektroskopie-analytik nir zur herstellung von polyaluminiumchloridhydroxid | |
WO2002088860A2 (de) | Vorrichtung zur steuerung von chemischen syntheseprozessen | |
AT515958B1 (de) | Kunststoffherstellung auf Basis eines diskontinuierlich polymerisierenden Monomers | |
DE19502134A1 (de) | Qualitätssichernde Bewertung der Innenoberfläche von fluorbehandelten PE-Behältern mit einer physikalischen Meßmethode | |
EP4042147A1 (de) | Vorrichtung und verfahren zur identifikation von stoffen in der fluidzusammensetzung | |
Chryssikos et al. | USE OF FT-NIR SPECTROSCOPY FOR ON-LINE MONITORING OF | |
EP1577335A1 (de) | Verfahren zur Herstellung von Polyamid | |
DD273175A3 (de) | Verfahren zur Sicherung der Qualität von Polyurethan-Thermoplasten | |
Liu et al. | Online monitoring of amine concentration in the processing of amine/epoxy-based thermosets | |
Kadenkin | Near-Infrared Spectroscopy: Quantitative analysis according to ASTM E1655 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20211021 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20231003 |