CN1627063A - Method for measuring critical parameter of supercritical system - Google Patents
Method for measuring critical parameter of supercritical system Download PDFInfo
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Abstract
This invention provides a test method for critical parameters of single, binary or poly systems, applying a home-made visual high pressure balance pot to test the parameters of single, binary or poly system taking the half volume position at the pot as the base in re-appearance of the critical opalescence and gas-liquid interface, characterizing. This invention provides a method and devices for testing the critical parameter, bubbling point and dew point accurately, and a method for drafting P-T patterns and computing the critical compression factors.
Description
Technical field the present invention relates to the measuring field of supercritical fluids system critical parameters.The present invention relates to a kind of dual criterion that is in half volume position of equilibrium still when reappearing and measure the method for supercritical fluids system critical parameters by critical opalescence phenomenon and liquid-gas interface.Composition by changing system and the critical parameters (critical temperature, emergent pressure and critical density) that content can record corresponding system and bubble point and dewpoint temperature, pressure, density.In addition, can also draw the out-of-phase diagram of corresponding system, the critical compressibility factor of counting system.
Background technology is after Baron Cagniarid dela Tour in 1822 finds the gas-liquid critical point, critical phenomenon and measuring thereof just are subjected to people's attention always, particularly supercritical fluid is widely used in extraction in recent years, supercritical reaction and overcritical preparation chemistry aspect, therefore, different chemical is formed, and the mensuration of the monobasic of different proportionings, binary and multicomponent system critical parameters is just very important.Propose various assay methods from pure material to the potpourri people, recorded the critical properties of some systems by these methods people.But the critical parameters of critical parameters, particularly binary system and multicomponent system still very lack.These all become the unfavorable factor that people carry out the theoretical research and the actual production of critical phenomenon.Based on critical parameters for theoretical research and actual production vital role, under the theoretical direction of Beijing University of Chemical Technology's modern catalyticing research place critical phenomenon, propose a kind of usefulness equilibrium still homemade and that have a visual windows and measured monobasic system, the method for binary system and multicomponent system critical parameters.The critical temperature of supercritical fluids system, emergent pressure method are by experiment measured.The assay method of supercritical fluids system critical parameters is a lot, and direct observational method and indirect predication method etc. are arranged.For direct observational method, be divided into two kinds of critical opalescence observation and interface disappearance methods again.The present invention is in equilibrium still when critical opalescence observation and interface are reappeared two kinds of criterions of half volume position organically combine, thereby can measure the critical parameters of different supercritical fluids system exactly.
When system reaches its critical point, because of its local density in fact not in the restriction that is under pressure, promptly local density can fluctuation mussily in greater than the distance of intermolecular distance, and the fluctuation meeting of density causes strong light scattering, the critical opalescence phenomenon promptly occurs.Because generation near can the be critical point certain zone of critical opalescence phenomenon.So whether the generation by the opalescence phenomenon, we can only tentatively measure the approximate range of critical point, and the corresponding bubble point temperature of system, bubble point pressure, bubble point density and dewpoint temperature, dew-point pressure, dew point density.And, when the apparent density ρ of system less than critical density ρ
cThe time, the interface will occur in the bottom of equilibrium still, when apparent density ρ greater than critical density ρ
cThe time, the interface will occur at the top of equilibrium still, and have only apparent density ρ when system very near critical density ρ
cThe time, when reappearing, liquid-gas interface can be in half volume position of equilibrium still.Like this, on the Preliminary Determination basis of opalescence phenomenon to critical point, half volume position that is positioned at equilibrium still by reappearing of liquid-gas interface just can determine the critical parameters (critical temperature, emergent pressure, critical density) of monobasic, binary or multicomponent system exactly.
In sum, be in the dual criterion of half volume position of equilibrium still during by the reappearing of critical opalescence phenomenon and liquid-gas interface, can measure exactly the critical parameters of monobasic, binary or multicomponent system.The mensuration that relates to the critical parameters of above-mentioned two kinds of criterions does not see that as yet relevant patent reports for work.The experimental provision of concrete mensuration system critical parameters is seen accompanying drawing.
Summary of the invention the objective of the invention is to provide a kind of dual criterion that is in half volume position of equilibrium still when reappearing by critical opalescence phenomenon and liquid-gas interface, and the equilibrium still that adopts self-control and have a visual windows is measured a kind of experimental technique of monobasic, binary or multicomponent system critical parameters.
Main advantage of the present invention is:
1. the present invention uses the critical parameters of making by oneself and having the equilibrium still mensuration system of visual windows, and experimental implementation is simple, and the result is accurate.
2. the present invention reappears half volume position that is in equilibrium still with critical opalescence phenomenon and liquid-gas interface and organically combines, thereby can determine system ground critical parameters more exactly.
3. the present invention has also measured the corresponding bubble point temperature of system, bubble point pressure, bubble point density and dewpoint temperature, dew-point pressure, dew point density when measuring critical parameters (critical temperature, emergent pressure, critical density).
4. the present invention can also draw the out-of-phase diagram of corresponding system on the basis of the critical point of gained, bubble point, dew point, has found out the type that its out-of-phase diagram meets.This all has directive significance for supercritical fluid extraction and the shooting flow precursor reactant that research contains this monobasic, binary or multicomponent system.
5. the present invention has derived the expression formula of critical compressibility factor by basal heat mechanics fundamental relation formula, the critical compressibility factor when can counting system is different forming.
The present invention is mainly by the following technical solutions:
1. the tolerance of volume
At first the cumulative volume of visual still is measured: on the window of visual still, scale is set, pipettes water with 1ml transfer pipet (being accurate to 0.01ml) and inject visual still (band magneton), each one milliliter.Whenever move and once write down a scale, like this, just can on scale, mark the bulking value of different scale representatives exactly.Then, the volume of water is mapped to scale, match obtains straight line, like this, can ask the liquor capacity value exactly by scale, at last piston is moved on to corresponding scale and just can obtain needed volume exactly.
2. the mensuration of bubble point and dewpoint temperature, pressure, density
Second component of accurately measuring or n component are added the self-control of determining volume and have in the high pressure equilibrium still of visual windows, add the supercritical solvent of determining quality by charge pipe with the decrement method then, make system reach definite mole fraction and average density.Equilibrium still places water-bath, oil bath or air bath (specifically deciding according to different systems with any).The system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Along with the reduction of temperature, take place in the autoclave to change mutually, system becomes two-phase by homogeneous phase, record temperature and pressure at this moment, what at this moment obtain is the phase-splitting point, is dew point or bubble point temperature and pressure accordingly.Phase-splitting point when the amount by second component that change to add or n component and supercritical solvent can obtain the different average density of different second components or n component mole fraction.Each tests at least triplicate to guarantee the accuracy of data.
3. critical temperature (T
c), emergent pressure (P
c), critical density (ρ
c) mensuration
On the basis that phase-splitting point is measured, choose some density values in the both sides that current average density with the opalescence phenomenon is pointed out in phase-splitting and repeat above-mentioned experiment, when reappearing, liquid-gas interface is in half volume position of equilibrium still.Temperature, the pressure of this moment is the critical temperature (T under this composition
c), emergent pressure (P
c), corresponding average density is critical density (ρ
c).
Like this, by adding different supercritical solvents and second component or n component, just can measure the critical temperature, emergent pressure, critical density of different multicomponent systems and corresponding bubble point and dewpoint temperature, pressure, density.
4. the drafting of system out-of-phase diagram
Critical temperature (the T of monobasic, binary or the multicomponent system that records by experiment
c) and emergent pressure (P
c) and dew point, bubble point temperature and pressure can draw the out-of-phase diagram of corresponding system.Can also determine the type of the out-of-phase diagram of corresponding system for binary system.
Like this, the critical temperature (T that forms the multicomponent system of different content by difference
c) and emergent pressure (P
c) and dew point, bubble point temperature and pressure can draw out corresponding out-of-phase diagram,
5. critical compression factor Z
c
Compressibility factor can be represented with following formula:
Z=pV/nRT that is Z=pM/T ρ R (1)
Pressure P during critical point
cCan be expressed as:
p
c=KT
c+B
And ρ=ρ
c
So critical compression factor Z
cCan represent with following formula:
Wherein: K, B are the slope and the intercept of the P-T line of gained supercritical fluids system when critical density; T
cBe critical temperature; ρ
cBe critical density; R is a gas law constant; M is mean molecular weight, M
iMolecular weight, x for i kind component in the multicomponent mixture
iMolar content for i kind component in the multicomponent mixture.
The slope of the P-T line the when critical temperature when like this, bringing difference composition different content into, critical density, corresponding critical density and the mean molecular weight of intercept and corresponding system can calculate the corresponding critical compressibility factor of system.
Further specify the present invention below in conjunction with description of drawings and specific embodiment.
Description of drawings:
Fig. 1: high pressure equilibrium still parts sketch, A wherein, B, C are respectively: A: equilibrium still outside drawing, B: equilibrium still sectional view, C: equilibrium still pressed component sectional view
Fig. 2: the experimental provision synoptic diagram, the 1-15 among the figure is respectively: 1: steel cylinder 2: precision pressure sensor, 3: quantity tube, 4: precision digital temperature thermometer, 5: Constant temperature bathtub, 6: stirrer, 7: high pressure visable still, 8: visual window, 9: the precision digital tensimeter, 10: visual light source, 11: bolt, 12: magnetic stirrer, 13: two-port valve, 14: magnetic stir bar, 15: thermopair
Specific embodiment
Embodiment 1: measure the 0.461ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 23.11g under stationary temperature, make that the hutanal mole fraction is 0.984%, the average density of system is 0.695g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, and the temperature of record this moment, pressure are as the critical temperature T of carbon dioxide+hutanal binary system when the hutanal mole fraction is 0.984%
c(311.85K) with emergent pressure P
c(8.23MPa), and critical density ρ
cBe exactly 0.695g/cm
3
Embodiment 2: measure the 0.659ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 23.42g under stationary temperature, make that the hutanal mole fraction is 1.38%, the average density of system is 0.709g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, and the temperature of record this moment, pressure are as the critical temperature T of carbon dioxide+hutanal binary system when the hutanal mole fraction is 1.38%
c(312.35K) with emergent pressure P
c(8.29MPa), and critical density ρ
cBe exactly 0.709g/cm
3
Embodiment 3: measure the 0.899ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 24.68g under stationary temperature, make that the hutanal mole fraction is 1.78%, the average density of system is 0.752g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, and the temperature of record this moment, pressure are as the critical temperature T of carbon dioxide+hutanal binary system when the hutanal mole fraction is 1.78%
c(314.45K) with emergent pressure P
c(8.58MPa), and critical density ρ
cBe exactly 0.752g/cm
3
Embodiment 4: measure the 1.025ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 22.92g under stationary temperature, make that the hutanal mole fraction is 2.18%, the average density of system is 0.703g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, and the temperature of record this moment, pressure are as the critical temperature T of carbon dioxide+hutanal binary system when the hutanal mole fraction is 2.18%
c(316.55K) with emergent pressure P
c(8.73MPa), and critical density ρ
cBe exactly 0.703g/cm
3
Embodiment 5: measure the 0.668ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 18.1g under stationary temperature, make that the hutanal mole fraction is 1.81%, the average density of system is 0.706g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, occur phase interface immediately, write down temperature at this moment, pressure as the carbon dioxide+dewpoint temperature T of hutanal binary system when the hutanal mole fraction is 1.81%
d(315.35K) with dew-point pressure P
d(8.63MPa), and the dew point density p
dBe exactly 0.706g/cm
3
Embodiment 6: measure the 0.816ml hutanal and inject equilibrium still, with the equilibrium still good seal, add the carbon dioxide of 18.80g under stationary temperature, make that the hutanal mole fraction is 2.29%, the average density of system is 0.735g/cm
3, then equilibrium still is placed water bath with thermostatic control, this binary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, occur phase interface immediately, write down temperature at this moment, pressure as the bubble point temperature T of carbon dioxide+hutanal binary system when the hutanal mole fraction is 2.29%
b(315.85K) with bubble point pressure P
b(8.66MPa), and the bubble point density p
bBe exactly 0.735g/cm
3
Embodiment 7: at first with the equilibrium still good seal, add the propylene of 7.6g then under stationary temperature, make that the average density of system is 0.230g/cm
3, then equilibrium still is placed constant temperature oil bath, this monobasic system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Along with the reduction of temperature, take place in the autoclave to change mutually, because the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, and phase interface appears immediately, and at this moment temperature of record, pressure are as the dewpoint temperature T of propylene monobasic system
d(362.65K) with dew-point pressure P
d(4.55MPa), and the dew point density p
dBe exactly 0.230g/cm
3
Embodiment 8: at first with the equilibrium still good seal, add the propylene of 7.7g then under stationary temperature, make that the average density of system is 0.233g/cm
3, then equilibrium still is placed constant temperature oil bath, this monobasic system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, and the temperature of record this moment, pressure are as the critical temperature T of propylene monobasic system
c(364.45K) with emergent pressure P
c(4.71MPa), and critical density ρ
cBe exactly 0.233g/cm
3
Embodiment 9: at first measure 0.1ml ethanol and inject equilibrium still, with the equilibrium still good seal, the propylene that under stationary temperature, adds 7.31g then, and the mixed air of the carbon monoxide of 5.2MPa and hydrogen, make that the ethanol mole fraction is 0.74%, the mole fraction of carbon monoxide and hydrogen is 28.18%, and the average density of system is 0.2550g/cm
3, then equilibrium still is placed constant temperature oil bath, this quaternary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, the temperature of record this moment, pressure as propylene+ethanol+carbon monoxide+hydrogen quaternary system when the ethanol mole fraction be 0.74%, the mole fraction of carbon monoxide and hydrogen is 28.18% o'clock critical temperature T
c(358.45K) with emergent pressure P
c(7.40MPa), and critical density ρ
cBe exactly 0.2550g/cm
3
Embodiment 10: at first measure 0.1ml ethanol and inject equilibrium still, with the equilibrium still good seal, the propylene that under stationary temperature, adds 6.80g then, and the mixed air of the carbon monoxide of 2.68Mpa and hydrogen, make that the ethanol mole fraction is 0.91%, the mole fraction of carbon monoxide and hydrogen is 17.49%, and the average density of system is 0.2243g/cm
3, then equilibrium still is placed constant temperature oil bath, this quaternary system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, under abundant EQUILIBRIUM CONDITION, measure the pressure under the different temperatures.Reduction along with temperature, take place in the autoclave to change mutually, owing to the fluctuation of density produces strong light scattering, the critical opalescence phenomenon appears, phase interface appears immediately, and liquid-gas interface is that half volume position from equilibrium still occurs, the temperature of record this moment, pressure as propylene+ethanol+carbon monoxide+hydrogen quaternary system when the ethanol mole fraction be 0.91%, the mole fraction of carbon monoxide and hydrogen is 17.49% o'clock critical temperature T
c(359.45K) with emergent pressure P
c(7.01MPa), and critical density ρ
cBe exactly 0.2243g/cm
3
Claims (10)
1. measure monobasic for one kind, the experimental technique of binary or multicomponent system critical parameters, it is characterized in that the bubble point of this method elder generation by critical opalescence phenomenon Preliminary Determination system, dew point and critical point, and then half volume position that is in equilibrium still when reappearing by liquid-gas interface is accurately measured critical point, the component of change system can record different monobasics with forming, the critical temperature of binary or multicomponent system, emergent pressure, critical density and corresponding bubble point and dewpoint temperature, pressure, density, by the critical point that records, bubble point and dew point can be drawn the out-of-phase diagram of corresponding system, the corresponding critical compressibility factor of counting system.
2. bubble point, dew point and critical point by critical opalescence phenomenon Preliminary Determination system according to claim 1, its characteristics are that this method comprises the steps: 1) second component that will accurately measure, the 3rd component joins the self-control of determining volume and has in the high pressure equilibrium still of visual windows up to the n component, add the supercritical solvent (first component) of determining quality by charge pipe with the decrement method then, make system reach definite mole fraction and average density; 2) equilibrium still places water-bath, oil bath or air bath, and the system heat temperature raising to supercriticality, is lowered the temperature very lentamente then and is adjusted to constant temperature under the required temperature, measures the pressure under the different temperatures under abundant EQUILIBRIUM CONDITION; 3) along with the reduction of temperature, take place in the autoclave to change mutually, system becomes two-phase by homogeneous phase, record temperature and pressure at this moment, what at this moment obtain is the phase-splitting point, is dew point accordingly, bubble point temperature and pressure; Phase-splitting point when 4) amount by the i component that change to add and supercritical solvent can obtain the different average density of different i component mole fractions, each tests at least triplicate to guarantee the accuracy of data.
3. half volume position that is in equilibrium still when reappearing by liquid-gas interface according to claim 1 is accurately measured critical point, its characteristics are that the concrete steps of this method are: at the bubble point of the system of Preliminary Determination, on the basis of dew point and critical point, choose some density values in the both sides that current average density with the opalescence phenomenon is pointed out in phase-splitting and repeat above-mentioned experiment, when reappearing, liquid-gas interface is in half volume position of reactor, the temperature of this moment, pressure is critical temperature and the emergent pressure under this composition, and corresponding average density is the critical density of system.
4. phase-splitting point according to claim 2 is characterized in that phase-splitting point can be divided into dew point and bubble point: when the equal density subcritical of institute's lining dot density, the temperature that records, pressure and density are dewpoint temperature, dew-point pressure and dew point density; When institute's equal density of lining was higher than critical point density, the temperature that records, pressure and density were bubble point temperature, bubble point pressure and bubble point density.
5. volume according to claim 2, the tolerance that it is characterized in that its volume is as follows: at first, cumulative volume to visual still is measured: on the window of visual still scale is set, pipette water with 1ml transfer pipet (being accurate to 0.01ml) and inject visual still (band magneton), each one milliliter, whenever pipette and once write down a scale, like this, just can on scale, mark the bulking value of different scale representatives exactly, then, the volume of water be mapped to scale, match obtains straight line, like this, can ask the liquor capacity value exactly, at last piston be moved on to corresponding scale and just can obtain needed volume exactly by scale.
6. the out-of-phase diagram of the corresponding system of drafting according to claim 1 is characterized in that the monobasic that recorded by experiment, the critical temperature (T of binary or multicomponent system
c) and emergent pressure (P
c) and dew point and bubble point temperature, pressure can be drawn corresponding monobasic, the out-of-phase diagram of binary or multicomponent system, and the type of definite corresponding system out-of-phase diagram.
7. the critical compressibility factor of the corresponding system of calculating according to claim 1 is characterized in that slope and intercept by the P-T line of gained supercritical fluids system when the critical density, critical temperature (T
c), critical density (ρ
c) and the corresponding mole fraction of system can calculate different systems by the critical compressibility factor computing formula that derivation obtains, the critical compressibility factor (Z that system is different when forming
c).
8. charge pipe according to claim 2 is characterized in that in the experimentation it being quality of measuring the material of adding of poor quality by twice charge pipe in front and back, just feeds in raw material by the decrement method.
9. self-control according to claim 2 also has the high pressure equilibrium still of visual windows, it is characterized in that its temperature and pressure of measuring system is to use accurate temperature sensor and pressure transducer respectively, and both precision are respectively, temperature sensor, 0.01K, pressure transducer, 0.01Mpa; In addition, the temperature of water-bath in the test, oil bath or air bath is to control by the temperature controller of precision, its precision is ± 0.2K, in addition, the usable range of water-bath is 0-100 ℃, and the usable range of oil bath is 0-200 ℃, and the usable range of air bath is 0-280 ℃, be to select water-bath, oil bath or air bath to decide according to concrete system in the experiment, this will see the scope of the critical temperature of system.
10. supercritical solvent according to claim 2 (first component) is characterized in that first component is: carbon dioxide, water, the various alcohols of hydrocarbon (alkane, alkene, alkynes, naphthenic hydrocarbon etc.), various ethers, various aldehydes, various ketone, various lipid, and various heterogeneous ring compounds etc.; Second component is: can be used as the various alcohols of cosolvent, various ethers, various aldehydes, various ketone, various lipid, and various heterogeneous ring compounds and other can be used as compound that cosolvent uses etc.; The n component is: all gases, and as carbon monoxide, hydrogen, nitrogen etc.
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