WO2018199565A1 - Procédé pour déterminer des conditions de traitement pour éliminer des composés organiques volatils d'un polymère - Google Patents

Procédé pour déterminer des conditions de traitement pour éliminer des composés organiques volatils d'un polymère Download PDF

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WO2018199565A1
WO2018199565A1 PCT/KR2018/004665 KR2018004665W WO2018199565A1 WO 2018199565 A1 WO2018199565 A1 WO 2018199565A1 KR 2018004665 W KR2018004665 W KR 2018004665W WO 2018199565 A1 WO2018199565 A1 WO 2018199565A1
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polymer
volatile organic
organic compounds
amount
blowing
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PCT/KR2018/004665
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English (en)
Korean (ko)
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박제섭
박원찬
최재훈
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주식회사 엘지화학
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Priority claimed from KR1020180045985A external-priority patent/KR102062830B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/605,584 priority Critical patent/US11666858B2/en
Priority to CN201880027208.9A priority patent/CN110545897B/zh
Publication of WO2018199565A1 publication Critical patent/WO2018199565A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/30—Controlling by gas-analysis apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present application relates to a method for determining process conditions for removing volatile organic compounds from a polymer.
  • Volatile Orgainc Compounds are derived from residues of monomers, solvents, or other components used to make polymeric products. Volatile organic compounds remain inside or on the surface of the product even after manufacture, and slowly rise to the surface of the product or release into the air over long periods of time. These volatile organic compounds reduce the quality and color of the product, cause unpleasant odors, and can affect the hormonal system of the human body through various pathways. In view of this, a post treatment is carried out to remove volatile organic compounds from the polymer product.
  • Post-treatment ie, removal of volatile organic compounds from the prepared polymer product
  • Post-treatment may be achieved by, for example, exposing the product to fresh gas or blowing fresh gas into the product.
  • the post-treatment time cannot be set indefinitely.
  • the characteristics of each polymer or volatile organic compound are different, and the amount of volatile organic compounds present in the polymer and its discharge rate are not known. It is not easy.
  • One object of the present application is to provide a method for determining process conditions for removing volatile organic compounds from a polymer.
  • Another object of the present application is to optimize the amount of production of the polymer product, the production period and the time of shipment, etc. by selecting and adjusting the conditions for exposing the polymer product in the gas.
  • the method of the present application is a method of determining the process conditions of blowing a gas to remove volatile organic compounds from the polymer.
  • the method comprises the steps of calculating the diffusion coefficient (D) and equilibrium constant (K) of the polymer; And simulating a process of removing volatile organic compounds based on the calculated diffusion coefficient and equilibrium constant.
  • a method of simulating and interpreting a process of removing a volatile organic compound present in a polymer product from a polymer, and predicting and determining the suitability of a related process may be provided.
  • FIG 3 shows a simulation procedure of a process according to an example according to the present application.
  • FIG. 4 is a graph showing a result of simulating a process of removing volatile organic compounds from a polymer based on the diffusion coefficient and the equilibrium constant experimentally obtained according to an example of the present application.
  • FIG. 5 is a graph showing process results according to changes in diffusion coefficients and equilibrium constants experimentally obtained according to an example of the present application.
  • the present application relates to a method for determining process conditions for blowing a gas to remove volatile organic compounds from a polymer product.
  • the method comprises analyzing the characteristics of the product; And it may include the step of simulating the removal of volatile organic compounds.
  • the product or the polymer product may be referred to as "polymer”, and the characteristics of the product may be "diffusion coefficient” and "equilibrium constant".
  • the diffusion coefficient and equilibrium constant can be analyzed experimentally. For example, the amount of volatile organic compounds may be measured in the headspace of the container for storing the polymer, and the diffusion coefficient and the equilibrium constant may be calculated from the measured values. Details are described below.
  • volatile organic compound and “polymer” are not limited to a specific compound or polymer, and may be referred to as volatile organic compounds in the related art, and such compounds may be released from the surface thereof. It can be used to encompass a polymer.
  • VOC volatile organic compounds
  • TVOC total volatile organic compounds
  • blowing may mean a treatment of causing or blowing a flow of oxygen (O 2 ), nitrogen (N 2 ) or a gas containing the same toward the polymer.
  • O 2 oxygen
  • N 2 nitrogen
  • the temperature of the gas to be blown can be appropriately adjusted, and the flow of gas for blowing can be appropriately raised by those skilled in the art using known methods or equipment.
  • the method comprises the steps of measuring the amount of volatile organic compounds in the headspace of the container for storing the polymer, and calculating the diffusion coefficient and equilibrium constant from the measured value; And simulating a process of removing volatile organic compounds based on the calculated diffusion coefficient and equilibrium constant. Based on the diffusion coefficient and the equilibrium constant means that the diffusion coefficient and the equilibrium constant are used as initial values of the simulation as described below.
  • the type of vessel for storing the polymer is not particularly limited.
  • a container including a body having a predetermined volume and a stopper capable of blocking physical movement of the material between the inside and the outside of the body may be used, such as a known vial. That is, it is sufficient that the container usable in the present application can be opened and closed, and in some cases the interior thereof can be sealed with the external environment.
  • the measurement of the amount of volatile organic compounds is based on the premise that the system defined by the closed container containing the polymer is in equilibrium.
  • the determination of equilibrium can be made by measuring the change in total volatile organic compounds over time several times. For example, if the amount of volatile organic compounds is measured several times from 30 minutes to 5 hours while storing the polymer at a predetermined temperature such as 120 ° C., the amount of volatile organic compounds measured is a constant value as the storage time increases. Will converge on. That is, it can be judged that the equilibrium state has been reached after a certain amount of time of the organic compound.
  • the polymer may be stored in a container in solid form.
  • the container may store a polymer or a polymer product in powder or pellet form (eg, spherical or elliptic spherical).
  • the polymer may be stored in the container by a volume smaller than the volume of the container.
  • the container may secure an inner space that is not occupied by the polymer product, that is, a head space. Accordingly, volatile organic compounds volatilized from the polymer and a predetermined gas (eg, air) may occupy the headspace of the container.
  • a predetermined gas eg, air
  • the method for measuring the amount of volatile organic compounds present in the headspace of the container is not particularly limited.
  • gas chromatography can be used to measure the amount of volatile organic compounds present in the headspace.
  • the unit indicating the amount of volatile organic compounds is not particularly limited.
  • Figure 1 is shown to aid in understanding the experimental method for calculating the diffusion coefficient (D) of the volatile organic compounds contained in the polymer.
  • Fig. 1 two vials are shown, each containing the same amount of pellet-shaped polymers prepared by the same method from the same component.
  • the blowing treatment was performed on the pellet stored in the right vial, and the blowing treatment was not performed on the pellet stored in the left vial.
  • the blowing treatment time for the pellets stored in the right vial is not particularly limited. For example, blowing may occur after the polymer is stored in the container, or blowing may also occur prior to storing the polymer in the container.
  • M 1 is the total amount of volatile organic compounds possessed by the polymer stored in the left vial (sample 1)
  • M 2 is the volatile possessed by the polymer stored in the right vial (sample 2) after the blowing treatment. It means the total amount of organic compounds.
  • the amount of volatile organic compounds volatilized from the polymer stored in the left vial after storing the polymer in the vial for a predetermined time that is, the amount of volatile organic compounds in the gas phase present in the headspace of the vial in Sample 1, A
  • the amount of residual volatile organic compounds (in and / or on the surface) of the solid polymer stored in the left vial may be M 1 -A.
  • the predetermined time at which the polymer is stored to measure the content A may mean a time longer than the minimum time that can be regarded as reaching the equilibrium state described above.
  • the amount of volatile organic compounds present in the headspace of the right vial is B, indicating that the remaining polymers (in and / or on the surface) of the solid polymer in the right vial
  • the amount of volatile organic compounds can be said to be M 2 -B.
  • the contents A and B can be measured on the premise that the two samples have reached equilibrium at the same temperature (t).
  • the equilibrium constant K obtained from each of the vials shown in FIG. 1 is the same.
  • the equilibrium constant K may be obtained through a ratio between the amount of volatile organic compounds in a unit volume of air in the headspace and the amount of volatile organic compounds in a polymer of unit volume.
  • the polymer may have a particle form such as pellets. Accordingly, the following relational expression 1 holds.
  • C g1 is the amount of volatile organic compounds of the unit volume of air in the headspace in Sample 1
  • C s1 means the amount of volatile organic compounds of the unit volume of the polymer in Sample 1.
  • C g2 is the amount of volatile organic compounds of the unit volume of air in the headspace in Sample 2
  • C s2 means the amount of volatile organic compounds of the unit volume of the polymer in Sample 2.
  • V s is the volume of the entire polymer in the vial and V g is the volume of the headspace, ie the volume of air present in the headspace.
  • V s can be obtained from the density and weight of the selected pellets
  • V g can be obtained from the internal volume of the vessel (vial) used, minus V s .
  • Equation 2 Equation 2 and Relation 1 relating to the equilibrium constants described above, it can be seen that the ratio (B / A) of the volatile organic compounds measured in Samples 1 and 2, respectively, is equal to M 2 / M 1 . .
  • the diffusion coefficient (D) can be obtained by the following formula. Details of the formula can be found in the chapter Diffusion in a sphere in The Mathematics of Diffusion (2nd Edition), by J. Crank.
  • the above formula is one in which the formula of the integral form associated with the calculation of the diffusion coefficient is changed to the infinite series form. Therefore, after adding all the calculated values from the value of n to 1 to infinity, it may be accurate to use the above formula. However, if n is an integer greater than about 10 because n 2 is in the denominator. The influence of n value is not large. In other words, in the above formula, the calculation may be performed only for the case where n is 1 to 10.
  • M ⁇ is the total amount of volatile organic compounds that the particles can emit for an indefinite period of time (i.e., reaching equilibrium without blowing), and M t is the particles that release the volatile organic compounds for a specific time through blowing. It is then the total amount of volatile organic compounds the particles have.
  • M ⁇ may correspond to M 1 described above and M t may correspond to M 2 described above.
  • the value of B / A measured in the headspace is equal to the value of M t / M ⁇ .
  • t may be a blowing time in hours
  • a may be a particle size in polymers in mm.
  • FIG. 2 is shown to help understand the equilibrium constant (K) calculation of the volatile organic compounds contained in the polymer.
  • K the equilibrium constant
  • the equilibrium constant K can be obtained through the amount of volatile organic compounds in the headspace measured at each equilibrium, with one sample sequentially reaching two equilibrium states.
  • the polymer containing the volatile organic compound M 0 (eg, a polymer in the form of particles such as pellets) is hermetically stored in one container (eg, a vial), and is placed in a first equilibrium state. Keep it for a certain time so that After a predetermined time elapses, if the amount of volatile volatile organic compounds present in the headspace is A, the amount of volatile organic compounds remaining in the polymer may be referred to as M 0 -A. Thereafter, via a method such as opening the stopper of the vial, the internal gas of the sample is replaced, and the lid is closed again.
  • the opening time is not particularly limited.
  • the amount of volatile organic compounds volatile in the headspace is B, and the amount of volatile organic compounds remaining in the polymer may be M 0 -A-B. .
  • the first and second equilibrium may be formed at the same temperature (t ').
  • the equilibrium constant K obtained in each of the first and second equilibrium states shown in FIG. 2 is the same.
  • the equilibrium constant K may be obtained through a ratio between the amount of volatile organic compounds in a unit volume of air in the headspace and the amount of volatile organic compounds in a polymer of unit volume.
  • V s is the volume of the entire polymer in the vial
  • V g is the volume of the headspace, that is, the volume of air present in the headspace, which are values already known at the time of vial selection and polymer injection. to be.
  • the equilibrium temperatures used to obtain each of the equilibrium constants (K) and diffusion coefficients (D) may be the same or different.
  • both equilibrium constants and diffusion coefficients can be calculated at 60 ° C.
  • the diffusion coefficients and equilibrium constants at 50 ° C. may be inferred and used in the methods herein.
  • the K value at a specific temperature T can be obtained.
  • the equation used can be found in B.Kolb &L.S.Ettre's book, Static Headspace-Gas Chromatography.
  • the value of the equilibrium constant and / or diffusion coefficient may be calculated at a plurality of temperatures.
  • values of equilibrium constants and diffusion coefficients at each temperature are calculated at 0.1 ° C intervals, at 0.5 ° C intervals, at 1 ° C intervals, at 2 ° C intervals, or at 3 ° C intervals.
  • the values calculated at the plurality of temperatures can be suitably used in the steps where such values are needed in the simulation process described below.
  • the method of the present application it is possible to simulate the process of removing volatile organic compounds from the polymer based on the diffusion coefficient and the equilibrium constant calculated in the above manner.
  • the simulation assumes that the blowing process is performed on the polymer in a state where the diffusion coefficient, the equilibrium constant, and the like are known, and confirms the result. After confirming the results, suitability of the process conditions and the like can be interpreted. For example, in the case of simulating a blowing process performed under predetermined conditions, it is possible to confirm how the TVOC changes with time as shown in FIG. 4, and to analyze the suitability of the process conditions through the confirmed results.
  • the blowing process to be simulated is assumed to be a process of blowing a gas having a predetermined temperature into a silo in which the polymer is loaded and stored at a predetermined height. And simulations are made while the energy balances, material balances and / or their changes in the silo are calculated.
  • the polymer loaded and stored in the silo may be in the form of particles, such as pellets.
  • the gas to be blown is higher than the polymer, it may be called hot air.
  • the silo may have a cylindrical or cylindrical shape, and it may be assumed that the silo is not affected except as considered in the present application.
  • a predetermined program can be used. For example, by instructions stored on a computer readable medium executable by a processor, calculations accompanying each step of the simulation can be performed. The results of the simulation can be visually recognized by the implementer of the method of the present application by the display device which is linked with the program for performing each step.
  • the silo and the polymer may be assumed to be divided into n in the loading height direction. For example, if the loading height of the polymer in the silo is 10 m, if the loaded polymer is divided evenly into 100, one unit of the polymer loaded at 10 cm in height may be referred to as equal parts (unit or unit cell). Can be assumed to exist in each layer. That is, it can be assumed that the silo is divided into n layers containing polymers of the same loading height. In addition, it may be assumed that each of the divided silos has an extra space (eg, a head space) in which volatile organic compounds emitted from a polymer may exist. In addition, an energy balance and a material balance may be sequentially calculated for each layer.
  • an extra space eg, a head space
  • the energy balance and the mass balance are calculated while the blown gas passes through the first layer, and the same calculation is performed even when the gas passing through the first layer passes through the second layer continuously.
  • the energy balance and the material balance may be sequentially calculated from the first layer to the nth layer.
  • the energy balance and the material balance calculated in relation to the n-1th layer may be used for the energy balance and the material balance calculation of the nth layer.
  • the simulation may include inputting an initial value including a diffusion coefficient and an equilibrium constant. That is, simulation of the blowing process is made based on predetermined information related to the process conditions. Specifically, for simulating the blowing process, some information related to the process may be input to the program used to perform the present application method as an initial value. As the initial value, the diffusion coefficient and the equilibrium constant, which were previously experimentally calculated, may be used.
  • the size of the polymer e.g. the diameter of the particulate polymer
  • the polymer properties e.g. mass, specific heat and / or density
  • the loading height of the polymer in the silo, the bulk density of the polymer loaded in the silo, the temperature of the polymer, the number of layered silos, the TVOC the polymer contains, and the size of the silo e.g. diameter One or more selected from the group consisting of
  • the size of the silo e.g. diameter One or more selected from the group consisting of
  • the time step means that when the polymer is divided into n layers as described above, the analysis of the first to nth layers (calculation of the material balance and the energy balance) is repeated once without repetition. It means the time during which it takes place. For example, assuming that the number of analysis repetitions from the first to nth layers is 100 and the total analysis time is 100 seconds, the time step means 1 second. In other words, in the case where the analysis according to one time step performed for one second is repeated 100 times, the time required for the total time step, that is, the total analysis time is 100 seconds. In the present application, the above interpretation is made during the time that the gas is blown.
  • the total time at which such an interpretation is performed means the total time at which blowing is performed
  • the time step which is the time at which one analysis is described above, is a concept defined for simulation, in which fresh gas (from the first layer) It can mean the unit time of blowing into the silo (up to nth layer).
  • the total analysis time that is, the total blowing time
  • the total blowing time can be divided into a plurality of time steps. In some cases, it can be seen that gas is introduced into the silo continuously or discontinuously during a time step of one unit.
  • the nth calculated value can affect the calculated value of the n + 1th layer, and the calculated value in the mth time step can affect the calculated value in the m + 1th time step. have. This is explained in more detail in the related section.
  • one time step is preferably set to mean a time of several seconds to several tens of seconds. Also, the shorter the interval between time steps, the better.
  • the simulation is a first step of calculating the changed temperature of the polymer and the changed temperature of the blowing gas by using an energy balance calculation between the polymer and the blowing gas present in the n-th layer; a second step of calculating the amount of volatile organic compounds emitted from the polymer present in the nth layer; And a third step of calculating the amount of volatile organic compounds that migrate from the inside of the polymer present in the nth layer to the surface of the polymer.
  • the first step uses the energy balance calculation between the polymer of the nth layer and the blowing gas, so that 'the elevated temperature of the polymer increased by the gas blown in the nth layer' and 'blowing in the nth layer And then calculating the temperature of the lowered gas (hot air).
  • the blowing gas may be higher than the temperature of the polymer or the air occupying the empty space in the silo assuming that the polymer is stored (description of the description). Only for convenience, the temperature of the gas entering the unit air is not always higher than the temperature of the polymer present in the layer).
  • the hot gas or hot air is blown as described above, since the thermal energy of the hot gas is transferred to the polymer, the temperature of the polymer increases as before blowing, and the temperature of the blown gas decreases. .
  • the energy resin between the polymer (particle) and the gas blown may be expressed as in Equation 5 below.
  • Q is an energy supplied to the polymer by the gas to be blown, and may have a unit such as W or J.
  • H is the convective heat transfer coefficient
  • A is the area of the particle
  • T A is the temperature of the blowing gas
  • T s is the surface temperature of the polymer.
  • the thermal conductivity H of the polymer can be known through known material information or known relationships, where Ts or T A is one of the initial inputs described above.
  • the temperature of the polymer heated by the hot air and the temperature of the hot air lowered after transferring the thermal energy to the polymer may be calculated.
  • the temperature change amount ( ⁇ T) of the polymer can be known, and the polymer increased by hot air when the temperature change amount is added to the Ts value.
  • the final temperature can be seen.
  • the temperature change amount ⁇ T 'of the air can be known, and when the temperature change amount is added to the T A value, the air decreases while blowing.
  • the final temperature can be known.
  • the temperature of the blowing gas dropped in the n-th layer obtained as described above may be used as the temperature of the gas flowing into the (n + 1) -th layer in the same time step.
  • the elevated temperature of the polymer in the n-th layer obtained as described above may be used as the temperature of the polymer present in the n-th layer in the next time step.
  • the second step may be a step of calculating the amount (X) of volatile organic compounds emitted from the polymer in the n-th layer.
  • the equilibrium constant K calculated through the experimental measurement may be used.
  • the amount (X) of the volatile organic compound may be regarded as the amount of the volatile organic compound volatilized from the polymer through blowing as a compound existing on the surface of the polymer.
  • the amount X of the volatile organic compounds discharged is the amount of volatile organic compounds contained in the blowing gas introduced into the nth layer. That is, the amount of volatile organic compounds in the hot air present in the nth layer.
  • the equilibrium constant (K) calculated previously can be used. That is, when hot air is blown, the amount of volatile organic compounds volatilized from the surface of the polymer and contained in the hot air is determined by the equilibrium constant.
  • Equation 6 the amount (X) of the volatile organic compound can be obtained as shown in Equation 6 below.
  • Amount of volatile organic compound (X) ⁇ (VOCs / V s ) / (K) ⁇ x V A )
  • VOCs is the quantity of volatile organic compounds present in the polymer surface
  • V s is the volume of the polymer surface layer
  • V A is the volume of the blowing gas
  • K is the equilibrium constant
  • the polymer may assume that a plurality of spheres having different diameters are formed by being layered, and V s refers to the (inner) volume of the surface of the outermost sphere. In some cases, it is necessary to check the number of particles when calculating the VOCs.
  • the number of particles can be known from the known silo diameters and particle loading heights and the bulk density at which the particles are loaded.
  • the VOCs may be measured values for a sample which is not blown in the experimental diffusion coefficient (D) calculation process described above.
  • K is an initial value known through experimental calculations
  • V A is a hot air, that is, one of the initial values as the flow rate of the gas to be blown
  • V s is also the value of the initial value as the size of the polymer.
  • the K value may be one or more of K values of various temperatures experimentally obtained above, wherein the temperature may be the temperature of the gas blown to the layer.
  • the amount of volatile organic compounds in the gas blown with respect to the n + 1 th layer is increased, based on which the volatile organic compounds in the n + 1 th layer are increased. Calculate compound emissions.
  • the amount (X) of the volatile organic compounds of the gas blown in the n-th hot air can be used as the amount of the volatile organic compounds of the gas flowing into the n + 1-th layer.
  • the volatile organic from the polymer present in the n + 1 th
  • Whether the compound is additionally released (or volatilized) can be determined using the equilibrium constant (K). Specifically, 'the amount of volatile organic compounds of the unit volume of the polymer contained in the n + 1th layer' and 'the amount of volatile organic compounds of the unit volume of gas blown to the n + 1th layer (X) If the equilibrium constant K n +1 obtained through 'is smaller than the equilibrium constant K obtained from the experimentally obtained values, additional polymer emission may occur in the n + 1 th layer.
  • the third step may be a step of calculating the amount (Y) of volatile organic compounds moving from the inside of the polymer present in the n-th layer to the surface of the polymer.
  • the concentration gradient of the volatile organic compound between the inside and the surface of the polymer is generated, thereby moving the volatile organic compound inside the polymer to the surface of the polymer.
  • the amount of volatile organic compounds moving from the polymer to the polymer surface can be calculated based on the diffusion coefficient (D).
  • D diffusion coefficient
  • the amount (Y) of volatile organic compounds moving from the inside of the polymer to the surface of the polymer can be calculated by the following equation 7, which is a diffusion governing equation in the spherical polymer (particle).
  • Equation 7 t is time, D is diffusion coefficient, r is radius of polymer (particle), and C is concentration.
  • the D value may be one or more of D values of various temperatures experimentally obtained above, wherein the temperature may be the temperature of the gas blown to the layer.
  • the amount of volatile organic compounds (Y) at the surface of the polymer obtained as described above may be used as the amount of volatile organic compounds (VOCs) at the surface of the polymer used in connection with the formula (6) in the next time step.
  • the amount of volatile organic compounds (Y) at the polymer surface has little effect on the n + 1 th layer.
  • the simulation results can be analyzed through the average (Y avg ) of the amount of volatile organic compounds on the surface of the polymer present in each layer after the total analysis time is over. For example, for each time step, the arithmetic mean value Y avg of the amount of volatile organic compounds measured in the layer is obtained, and the decrease of the value Y avg with the increase of the time step is confirmed. As a result, the degree of reduction of the volatile organic compounds according to the blowing conditions can be compared (see FIG. 4).
  • the method may further include determining appropriateness or validity of the process conditions and reflecting them in the process conditions based on the simulation result. For example, if the result according to the input initial value is appropriate as the current situation, the conditions inputted as the initial value may be determined as the conditions of the actual blowing process. Otherwise, the simulation may be performed again by inputting another condition. .
  • Figure 4 shows the results of a simulation of the process of removing volatile organic compounds from the polymer based on the diffusion coefficient and the equilibrium constant experimentally obtained as described above.
  • the process of obtaining the diffusion coefficient and equilibrium constant on which the simulation is based, and the analysis of the simulation results are as follows.
  • the vial between the first and second equilibrium states is provided so that two equilibrium states can be sequentially achieved for one vial sample storing a predetermined amount of pellet-type polymer.
  • Internal gas was replaced once.
  • the amount of volatile organic compounds in the headspace measured at each equilibrium was measured by gas chromatography at 60 ° C. Since the weight of the pellets used was 2 g and the density of the polymer constituting the pellets was 1,070 kg / m 3 , the volume V s (about 1.87 ml) of the pellets could be obtained from them.
  • the volume of the headspace that is, the volume V g of gas (air) was used by subtracting V s (about 1.87 ml) from the volume of 20 ml of the vial used.
  • TVOC values measured in the first and second equilibrium states and the equilibrium constant K obtained according to Equation 2 are shown in Table 1 below.
  • the known VDA277 method was used to measure the amount of volatile organic compounds (TVOC).
  • pellet-shaped polymers particle size: 3 mm
  • the volatile organic matter in the headspace measured at each equilibrium.
  • the amount of compound was measured via gas chromatography at 60 ° C.
  • the blowing treatment associated with Sample 2 was for 2 hours.
  • the size of the vial and the volume and weight of the polymer are the same as described above.
  • D was calculated using the formula described above. Specifically, the M t / M ⁇ value of the formula was replaced by the B / A value, the size of the particles (3 mm) was substituted for a, and 2 hours were substituted for t for the blowing time. For reference, when the formula is applied, the values from the case where n is 1 day to the case where 10 is summed.
  • Blowing gas temperature 70 °C, flow rate 1,000 kg / hr, specific heat 1000 J / kgK, convection heat transfer coefficient 2 W / m 2 K
  • Silos height 4.5 m, diameter 1.5 m, bulk dnsity 500 kg / m 3
  • the simulation associated with FIG. 4 records how the amount of volatile organic compounds changes in a plurality of silos as the blowing time of the polymer particles (pellets) loaded in the silo increases. Based on a reference controlled to have a pellet temperature and a blowing (hot wind) flow rate, the results of the case where the pellet temperature was changed (Case 1) and the flow rate of the hot wind (Case 2) were compared. .
  • the Y-axis value is calculated by reducing the ratio of the amount of the initial volatile organic compound according to the blowing time, and the X-axis means the blowing time.
  • FIG. 5 also shows the results of simulating the process of removing volatile organic compounds from the polymer based on the diffusion coefficient and the equilibrium constant experimentally obtained as described above.
  • the diffusion coefficient values and the equilibrium constant values of the Reference are the same as those of the Reference used in the simulation of FIG. Specifically, in the simulation of FIG. 5 (a), the results were compared between the case of increasing the diffusion coefficient twice (Case 3) and the case of increasing the equilibrium constant (Case 4) (other blowing conditions are the same). If the diffusion coefficient is increased, Case 3 shows that the reduction of volatile organic compounds is greater even if the blowing time is the same.

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Abstract

La présente invention concerne un procédé pour déterminer des conditions de traitement pour éliminer des composés organiques volatils d'un produit polymère par soufflage. Selon le procédé de la présente invention, du temps et de l'énergie peuvent être économisés.
PCT/KR2018/004665 2017-04-24 2018-04-23 Procédé pour déterminer des conditions de traitement pour éliminer des composés organiques volatils d'un polymère WO2018199565A1 (fr)

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US16/605,584 US11666858B2 (en) 2017-04-24 2018-04-23 Method for determining process conditions to remove volatile organic compounds from polymer
CN201880027208.9A CN110545897B (zh) 2017-04-24 2018-04-23 确定从聚合物中去除挥发性有机化合物的工艺条件的方法

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KR10-2017-0052045 2017-04-24
KR20170052045 2017-04-24
KR10-2018-0045985 2018-04-20
KR1020180045985A KR102062830B1 (ko) 2017-04-24 2018-04-20 휘발성 유기화합물을 고분자로부터 제거하는 공정조건의 결정 방법

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CN112098552A (zh) * 2020-09-07 2020-12-18 北京理工大学 一种测定建材中挥发性有机物初始浓度和分配系数的多联舱法

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US20030200796A1 (en) * 2000-02-02 2003-10-30 Pawliszyn Janusz B. Analytical devices based on diffusion boundary layer calibration and quantitative sorption
JP2005279570A (ja) * 2004-03-30 2005-10-13 Mitsubishi Heavy Ind Ltd 揮発性有機化合物の処理装置及び処理方法
JP2009279523A (ja) * 2008-05-22 2009-12-03 Toohoo Kako Kk Ｖｏｃ除去装置
US20110201765A1 (en) * 2006-08-25 2011-08-18 Chevron Phillips Chemical Company, Lp Method and apparatus for managing volatile organic content in polyolefin
KR20120132419A (ko) * 2011-05-27 2012-12-05 주식회사 엘지화학 휘발성 유기화합물 제거용 ｓｃｃ

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Publication number Priority date Publication date Assignee Title
US20030200796A1 (en) * 2000-02-02 2003-10-30 Pawliszyn Janusz B. Analytical devices based on diffusion boundary layer calibration and quantitative sorption
JP2005279570A (ja) * 2004-03-30 2005-10-13 Mitsubishi Heavy Ind Ltd 揮発性有機化合物の処理装置及び処理方法
US20110201765A1 (en) * 2006-08-25 2011-08-18 Chevron Phillips Chemical Company, Lp Method and apparatus for managing volatile organic content in polyolefin
JP2009279523A (ja) * 2008-05-22 2009-12-03 Toohoo Kako Kk Ｖｏｃ除去装置
KR20120132419A (ko) * 2011-05-27 2012-12-05 주식회사 엘지화학 휘발성 유기화합물 제거용 ｓｃｃ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112098552A (zh) * 2020-09-07 2020-12-18 北京理工大学 一种测定建材中挥发性有机物初始浓度和分配系数的多联舱法
CN112098552B (zh) * 2020-09-07 2021-07-09 北京理工大学 一种测定建材中挥发性有机物初始浓度和分配系数的多联舱法

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