# US 10,765,964 B2 · Process to mitigate unwanted formation of popcorn polymers using acoustic emission signals > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,765,964 B2 - Document ID: US10765964B2 - Status: Granted - Kind: B2 - Application number: 16/077,001 - Filed: 2017-02-07 - Published: 2019-01-31 - Granted: 2020-09-08 - Earliest claimed: 2016-02-10 - Assignees: Total Research & Technology Feluy - Applicants: Total Research & Technology Feluy - Inventors: Jean-Pierre Thoret Bauchet - Web page: https://patentgrep.com/patent/US10765964B2 ## CPC - B01D 3/42: Regulation; Control - B01D 3/34: with one or more auxiliary substances - C07C 7/04: by distillation - G01N 29/14: using acoustic emission techniques {(echo of particles G01N29/046; measuring mechanical vibrations or acoustic waves in solids in general G01H1/00)} - G01N 29/42: by frequency filtering {or by tuning to resonant frequency} - G01N 29/4427: {with stored values, e.g. threshold values} - B01J 2219/00254: Formation of unwanted polymer, such as "pop-corn" - C08F 2400/02: Control or adjustment of polymerization parameters - G01N 2291/0251: Solidification, icing, curing composites, polymerisation - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract Process to monitor unwanted formation of a polymer, having internal mechanical strain, wherein said formation of polymer generates acoustic emissions due to the sudden break of the polymer, wherein the number of said acoustic emissions increases over time when there is formation of said unwanted polymer formation, wherein said acoustic emissions is detected by a resonant piezo electric transducer having a resonant frequency centred on the second harmonic of said acoustic emission. ## Claims ### Claim 1 A process to mitigate the unwanted popcorn formation of a cross-linked polymer having internal mechanical strain comprising the steps of: a) providing an installation in which unwanted popcorn formation of a cross-linked polymer may occur, with at least one resonant piezo electric transducer being attached outside of the installation; b) counting the acoustic emissions generated by the cross-linked polymer formation originating by the sudden break of the polymer with the at least one resonant piezo electric transducer and comparing the number of acoustic emissions counted per unit of time with at least one predefined threshold; and c) intervening on the installation in order to limit the unwanted popcorn formation of a cross-linked polymer when the number of acoustic emissions counted per unit of time of step b) is higher than the at least one predefined threshold; wherein the step of counting the acoustic emissions is done by detecting a second harmonic of the acoustic emissions. ### Claim 2 (depends on 1) The process according to claim 1 wherein the step b) of counting the acoustic emissions includes monitoring the increase of the number of acoustic emissions counted per unit of time. ### Claim 3 (depends on 1) The process according to claim 1 wherein a resonant frequency, V/μbar, calibrated with ASTM E976, of the resonant piezo electric transducer is in the range of 140 to 180 kHz. ### Claim 4 (depends on 1) The process according to claim 1 wherein the resonant piezo electric transducer measures the second harmonic of the acoustic emissions being in the range of 140 to 180 kHz or being in the range of the resonant frequency of the resonant piezo electric transducer. ### Claim 5 (depends on 1) The process according to claim 1 wherein the step b) of counting the acoustic emissions includes filtering and amplifying the signal obtained by the resonant piezo electric transducer during the measurement of the acoustic emissions. ### Claim 6 (depends on 1) The process according to claim 1 wherein the resonant piezo electric transducer has an operating frequency range of at least more than two times the frequency of the second harmonic or has a operating frequency range from 1 to 450 kHz. ### Claim 7 (depends on 1) The process according to claim 1 further comprising the steps performed after step a) of: a1) attaching the at least one resonant piezo electric transducer outside the installation a2) checking the coupling of the installation with the at least one resonant piezo electric transducer. ### Claim 8 (depends on 1) The process according to claim 1 wherein the resonant piezo electric transducer is permanently attached to the installation and that the counting the acoustic emissions emitted during the unwanted formation of popcorn is performed on a continuous way. ### Claim 9 (depends on 1) The process according to claim 1 wherein the step c) of intervening on the installation includes one or more of the following: injecting at least one additive able to limit the formation of unwanted popcorn; isolating and washing the part of the installation where unwanted popcorn formation was detected or removing the unwanted popcorn present; stopping the installation in order to mechanically or manually remove or washing the unwanted popcorn; or locating on the installation where the number the acoustic emission is the maximum and nearby injecting at least one additive able to limit the formation of unwanted popcorn polymers. ### Claim 10 (depends on 9) The process according to claim 9 wherein the additive able to limit unwanted popcorn formation of a cross-linked polymer is chosen among compounds having 2,2,6,6-tetramethylpiperidine group at a concentration of 1 to 5 wt ppm; or phenolic stabilizer being at a concentration of 200 to 1000 wt ppm; or group of molecules being hydroxylamine compounds being at a concentration of 50 to 500 wt ppm; or di-lower akylhydroxylamine or: 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl at a concentration of 1 to 5 wt ppm or 4-tert-Butylcatechol at a concentration of 200 to 1000 wt ppm or di ethyl hydroxylamine at a concentration of 50 to 500 wt ppm or any combination of thereof and wherein the concentration is based on the total weight of the stream in which the unwanted popcorn formation of cross-linked polymer may occur and is measured at the point of injection of the additive. ### Claim 11 (depends on 1) The process according to claim 1 wherein the unwanted popcorn formation of a cross-linked polymer is derived from 1,3-butadiene, isoprene, dimethyl-2,3-buta-1,3-diene, chloroprene, bromoprene, styrene containing impurities, divinylbenzene and styrene containing traces of divinylbenzene. ### Claim 12 (depends on 1) The process according to claim 1 wherein the resonant piezo electric transducer is connected to a conditioner unit comprising at least one filtering mean and an operational preamplifier and wherein in the conditioner unit there is at least one adjustable threshold level or a plurality of cascaded threshold levels. ### Claim 13 (depends on 10) The process according to claim 10 wherein the injection of at least one additive able to limit the formation of unwanted popcorn polymers is performed when the number of acoustic emissions counted per unit of time reaches the predefined threshold and that the concentration of the additive injected is further increased when the number of acoustic emissions counted per unit of time reaches a second predefined threshold higher than the predefined threshold and that isolating and washing the part of the installation where unwanted popcorn formation was detected or removing the unwanted popcorn present or the stopping the installation in order to mechanically or manually remove or washing the unwanted popcorn is performed when the number of acoustic emissions counted per unit of time reaches a second predefined threshold higher than the first predefined threshold. ### Claim 14 (depends on 1) The process according to claim 1 wherein the step b) of counting the acoustic emissions is performed using multiple resonant piezo electric transducers located where unwanted popcorn formation of a cross-linked polymer may occur.