CN102087195B - Full-automatic microfiltration membrane aperture distribution tester as well as automatic measuring method and application thereof - Google Patents
Full-automatic microfiltration membrane aperture distribution tester as well as automatic measuring method and application thereof Download PDFInfo
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- CN102087195B CN102087195B CN2010105729880A CN201010572988A CN102087195B CN 102087195 B CN102087195 B CN 102087195B CN 2010105729880 A CN2010105729880 A CN 2010105729880A CN 201010572988 A CN201010572988 A CN 201010572988A CN 102087195 B CN102087195 B CN 102087195B
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Abstract
The invention discloses a full-automatic microfiltration membrane aperture distribution tester as well as an automatic measuring method and application thereof. The full-automatic microfiltration membrane aperture distribution tester comprises a gas supply cylinder, a gas buffer tank and a test membrane cell for fixing and sealing a microfiltration membrane, wherein the gas supply cylinder, the gas accumulator tank and the test membrane cell are successively connected via a pipeline. The full-automatic microfiltration membrane aperture distribution tester is characterized in that a motor-driven flow regulating valve is arranged between the gas supply cylinder and the gas buffer tank; the gas buffer tank is provided with a pressure probe; an outlet on the microfiltration membrane penetration side of the test membrane cell is provided with a gas flow probe; the signal output end of the pressure probe and the signal output end of the gas flow probe are connected with a data acquisition module for collecting pressure and flow signals in real time; the signals are transmitted by the communication module and a computer controller; the signal output end of the computer controller is connected with the signal input end of the motor-driven flow regulating valve; and the motor-driven flow regulating valve is under real-time feedback control. According to the full-automatic microfiltration membrane aperture distribution tester, the measuring condition can be automatically controlled in real time, measuring data is collected, data is processed in real time, and the assessment requirement on the performance of various sieve-pore filtration membranes can be satisfied.
Description
Technical field
The present invention relates to a kind of Membrane Pore Size Analyzer, especially relate to a kind of full-automatic micro-filtration membrane pore diameter distribution analyzer and assay method and application automatically thereof.
Background technology
The pore size filter of micro-filtration membrane is generally the 0.01-10 micron; Be one type of important sieve aperture selectivity filter membrane, it is big to have a flux, and upstream side pressure requires low advantage; Be widely used in industries such as chemical industry, medicine, food, water treatment, environmental protection, electronics industries; Its separating property is influenced by pore property parameter such as the average pore size and the pore diameter distribution etc. of film mainly, and pore diameter distribution is meant the apertures at different levels that exist in material percent by quantity or volume calculation, and good film requires the membrane aperture narrowly distributing; Pore diameter range inner membrance inner via hole narrower is many; Flux is big, thus in the film effectively via count and pore size distribution data thereof be the important parameters of evaluated for film performance quality, need accurately to measure.
(application number is 01273986.3 to China's utility model patent Membrane Pore Size Analyzer; Granted publication number is CN 2508242Y) a kind of Membrane Pore Size Analyzer of measuring membrane aperture based on bubble point-flow velocity method disclosed; Comprise the air feed bottle, pressure balancing tank, test pool and the flowmeter that connect successively; Have advantage simple in structure, easy to use, but this Membrane Pore Size Analyzer needs the manual control condition determination, need the artificial measurement data such as pressure, flow of gathering to be used for the isoparametric calculating of average pore size simultaneously; Exist error big, shortcomings such as operation inconvenience.
Summary of the invention
Technical matters to be solved by this invention provides a kind ofly can be controlled condition determination automatically and gather measurement data, full-automatic micro-filtration membrane pore diameter distribution analyzer that data are handled in real time and automatic assay method and the application that is used to measure the micro-filtration membrane pore diameter distribution thereof.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of full-automatic micro-filtration membrane pore diameter distribution analyzer; Comprise air feed bottle, gas buffer jar and be used for fixing the test membrane cisterna of sealed micro filter membrane; Described air feed bottle, described gas buffer jar and described test membrane cisterna are connected through pipeline successively; Be provided with electric flow control valve between described air feed bottle and the described gas buffer jar; Described gas buffer jar is provided with pressure probe; The outlet of the micro-filtration membrane per-meate side of described test membrane cisterna is provided with gas flow probe, the signal output part of described pressure probe and described gas flow probe be used for gathering in real time pressure P signal and gas flow F
SThe data acquisition module of signal links to each other, described data acquisition module through communication module with pressure P signal that collects and gas flow F
SSignal is transferred in the computer control, and the signal output part of described computer control is connected with the signal input part of described electric flow control valve and described electric flow control valve is carried out real-time FEEDBACK CONTROL.
Be provided with reduction valve between described air feed bottle and the described gas buffer jar, be provided with first controlled valve that is used to control the turnover of film gas between described test membrane cisterna and the described gas flow probe.
Also be provided with between described gas buffer jar and the described test membrane cisterna and described pipeline and the fluid-through tube road that connects; Pipeline between described gas buffer jar and the described test membrane cisterna is provided with breather valve; Described fluid-through tube road is provided with logical hydraulic control valve; Also be provided with liquid between described test membrane cisterna and described first controlled valve and flow out bypass, the outlet that described liquid flows out bypass is provided with liquid flowmeter, and the upper end of described gas buffer jar is provided with inlet; The lower end is provided with liquid outlet; Described inlet is provided with liquid inlet control valve, and described liquid outlet is provided with out hydraulic control valve, and described liquid flows out bypass and is provided with the second switch valve that is used to control the turnover of film liquid.
Described micro-filtration membrane is flat sheet membrane, hollow-fibre membrane or tubular membrane, and the material of described micro-filtration membrane is macromolecular material or inorganic material.
Described test membrane cisterna comprises can fasten the last membrane cisterna and following membrane cisterna that forms sample chamber each other; Described upward membrane cisterna and described membrane cisterna down have the guide hole that is connected; Described sample chamber is through described guide hole and described pipeline connection; Be provided with the packoff that is used to seal described sample chamber between described last membrane cisterna and the described following membrane cisterna; Described flat sheet membrane places described sample chamber, and outward flange is pressed between described last membrane cisterna and the described following membrane cisterna, and the side that sees through of described flat sheet membrane is provided with the porous gasket that is used for compensator or trimmer pressure.
Described test membrane cisterna comprises that mutual fastening forms the last membrane cisterna and following membrane cisterna of sample chamber; Described upward membrane cisterna and described membrane cisterna down have the guide hole that is connected; Described sample chamber is through described guide hole and described pipeline connection; Be provided with the packoff that is used to seal described sample chamber between described last membrane cisterna and the described following membrane cisterna; The space that described hollow-fibre membrane or described tubular membrane are passed between tool hole circle flat board and the described tool hole circle flat board is filled with encapsulant, and described tool hole circle flat board places described sample chamber, and outward flange is pressed on the described membrane cisterna and described down between the membrane cisterna of going up.
The described membrane cisterna periphery wall of going up is provided with locating slot, and described membrane cisterna down and the described contacted end face of membrane cisterna of going up are provided with the locating piece that is used with described locating slot.
Described test membrane cisterna also comprises upper press cover and the lower cover that is used to compress described last membrane cisterna of sealing and described following membrane cisterna; It is fixing that described upper press cover and described lower cover are connected through one or both modes in screw thread, flange, clip and the bolt, and described upper press cover and described lower cover respectively have a passage to be connected with described pipeline.
The automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer comprises the steps:
(1) micro-filtration membrane to be tested is soaked in advance put into test membrane cisterna sealing and fixing behind the infiltrate, the maximum that in the control program of computer control, preestablishes micro-filtration membrane is born pressure P
0With the admission pressure V that gathers way;
(2) electric flow control valve, breather valve and first controlled valve are opened, the gas in the air feed bottle gets into the gas buffer jar successively and tests in the membrane cisterna through electric flow control valve;
The gas flow Fs signal in real time that the relevant pressure P that pressure P signal in the gas buffer jar that (3) will record with pressure probe and gas flow probe record sees through micro-filtration membrane down collects in the data acquisition module; Through communication module pressure P signal that collects and gas flow Fs signal are transferred in the computer control, form pressure P-gas flow Fs data one to one;
(4) computer control is with the pressure P signal that collects and the gas flow F under the relevant pressure P
SSignal is a foundation; With the preset admission pressure V that gathers way is controlled target; Calculate the aperture of electric flow control valve in real time; The aperture of the electric flow control valve that calculates gained fed back on the electric flow control valve in real time carry out, pilot-gas surge tank internal pressure gathers way and is the preset admission pressure V that gathers way;
(5) according to pressure P signal of gathering and the gas flow F under the relevant pressure P
SThe signal measuring pore diameter distribution:
A. with the pressure P substitution transmembrane pressure computing formula of measuring in the step (3)
; Obtain transmembrane pressure
; Wherein Pa is the gaseous tension that sees through the gas vent side of film, and Py is gas buffer jar and the pressure differential of measuring the film on the suction side;
B. with the transmembrane pressure that obtains
substitution formula
, obtain the membrane aperture r that newly opens under this transmembrane pressure;
C. according to the gas flow Fs that measures in the step (3) under the relevant pressure P that obtains; Calculate the gas flow recruitment
under transmembrane pressure
and the adjacent transmembrane pressure; Membrane aperture r is reached
substitution Hagen-Poiseuille equation:
; Obtain effective number of through-holes n of the aperture r under the relevant pressure P; Wherein σ is the surface tension of infiltrate; θ is the contact angle between infiltrate and the material; N is that the aperture is effective via count of r, and η is that gas viscosity, l are effective through hole length of film;
D. show aperture measure of spread result, i.e. effective gas flow
under hole area
and the aperture r-respective aperture under number of through-holes n, the aperture r-respective aperture under the aperture r-respective aperture;
(6) when reaching preset maximum, pressure P bears pressure P
0Or pressure P-when gas flow Fs is linear, closing electric flow control valve automatically, the storing measurement result gets into step (7), otherwise, repeat above-mentioned steps (3);
(7) finish to measure, close the breather valve and first by-pass valve control.
The application of full-automatic micro-filtration membrane pore diameter distribution analyzer, described full-automatic micro-filtration Membrane Pore Size Analyzer can be used for measuring pore diameter distribution, average pore size, gas flux and the liquid flux of micro-filtration membrane.
Compared with prior art; The invention has the advantages that: the present invention's full-automatic micro-filtration membrane pore diameter distribution analyzer and assay method and application automatically thereof; Can control condition determination in real time automatically and gather measurement data through computing machine and self controlled element; Data are handled in real time, and the mensuration result shows in real time, stores and print with the form of chart and pore size distribution curve, also can have access to the data of measuring before.This instrument both can have been measured pore diameter distribution, average pore size, gas flux and the liquid flux of the flat sheet membrane of macromolecule or ceramic quality; Also can measure the above-mentioned performance parameter of hollow-fibre membrane, tubular membrane; Basically can satisfy evaluation requirement, for a kind of practical and convenient microporous barrier performance evaluation equipment that provides is studied and used to film to all kinds of sieve aperture property filter membrane performances.
Because the side that sees through of flat sheet membrane is provided with porous gasket, can be used for cushioning gas or the fluid pressure through flat sheet membrane; Because last membrane cisterna periphery wall is provided with locating slot, following membrane cisterna and the contacted end face of last membrane cisterna are provided with the locating piece that is used with locating slot, can be used for fixing upper and lower membrane cisterna, and membrane cisterna relatively rotates about avoiding, and influence film properties and measure; Be used to compress upper press cover and the lower cover that membrane cisterna and following membrane cisterna are gone up in sealing because the test membrane cisterna also comprises, it is fixing that upper press cover and lower cover are connected through one or both modes in screw thread, flange, clip and the bolt, the sealing that can further guarantee to test membrane cisterna.
Description of drawings
Fig. 1 is the graph of a relation of pressure-gas permeation amount;
Fig. 2 is the structural representation of the full-automatic micro-filtration membrane pore diameter distribution of the present invention analyzer;
Fig. 3 is the FB(flow block) of the automatic assay method of micro-filtration membrane pore diameter distribution analyzer of the present invention;
Fig. 4 is a structural representation of going up membrane cisterna of the present invention;
Fig. 5 is the structural representation of membrane cisterna down of the present invention;
Fig. 6 is the dull and stereotyped structural representation of the tool hole circle that is provided with tubular membrane of the embodiment of the invention 2;
Fig. 7 is the dull and stereotyped structural representation of the tool hole circle that is provided with hollow-fibre membrane of the embodiment of the invention 2.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
One, test philosophy of the present invention
The present invention is based on effective through hole distribution that bubble point-flow velocity method is measured micro-filtration membrane, and this method at first makes full of liquid in the fenestra, increases the transmembrane pressure of film both sides gas more gradually.According to there being following relational expression between Laplace law transmembrane pressure Δ p and the aperture r:
; Wherein σ is the surface tension of infiltrate; θ is the contact angle between infiltrate and the material; The aperture can not be blown logical by gas less than the fenestra of the full of liquid of r; Gas can not see through film from these fenestras; Have only the aperture can be blown logical by gas more than or equal to the fenestra of r; Gas sees through from the macropore of opening, and transmission rates is followed the Hagen-Poiseuille equation:
.Transmembrane pressure along with film both sides gas during measurement increases gradually; The aperture of full of liquid is according to Laplace law corresponding opening under different pressure from big to small in the film; Gas flow through film increases gradually, and to the last after minimum hole also was opened, the gas permeation amount only is proportional to pressure by the Hagen-Poiseuille equation to be increased; This moment, the pore size determination process finished, and typical pressure-the gas permeation discharge curve is as shown in Figure 1.
According to above-mentioned principle, sequentially determining sees through the gas flow F of film under different transmembrane pressures
S, calculate the contribution △ F of the fenestra of the certain pore size of newly opening to gas flow
S, and then calculate the via count under every kind of aperture, thus measure pore diameter distribution.Utilize this method can record in the film actual through hole (number) and distribute, measuring process is to not damage of film, can repeated measurement, thus estimate the performance of microporous barrier preferably.
Two, specific embodiment
Embodiment 1
The full-automatic micro-filtration membrane pore diameter distribution of the present invention analyzer; As shown in Figure 2; Comprise air feed bottle 1, gas buffer jar 2 and be used for fixing the test membrane cisterna 3 of sealed micro filter membrane; Air feed bottle 1, gas buffer jar 2 and test membrane cisterna 3 are connected through pipeline 4 successively, are provided with electric flow control valve 5 between air feed bottle 1 and the gas buffer jar 2, and gas buffer jar 2 is provided with pressure probe 6; The outlet of test membrane cisterna 3 micro-filtration membrane per-meate side is provided with gas flow probe 7, the signal output part of pressure probe 6 and gas flow probe 7 be used for gathering in real time corresponding pressure P signal and gas flow F
SThe data acquisition module of signal links to each other, data acquisition module through communication module with pressure P signal that collects and gas flow F
SSignal is transferred in the computer control 8, and the signal output part of computer control 8 is connected with the signal input part of electric flow control valve 5 and electric flow control valve 5 is carried out real-time FEEDBACK CONTROL.
In this specific embodiment, as shown in Figure 2, be provided with reduction valve 9 between air feed bottle 1 and the gas buffer jar 2; Be provided with first controlled valve 14 that is used to control the turnover of film gas between test membrane cisterna 3 and the gas flow probe 7; Gas buffer jar 2 and test also are provided with between the membrane cisterna 3 and pipeline 4 and the fluid-through tube road 11 that connects; Pipeline 4 between gas buffer jar 2 and the test membrane cisterna 3 is provided with breather valve 12; Fluid-through tube road 11 is provided with logical hydraulic control valve 13; Liquid flows out bypass 10 between the test membrane cisterna 3 and first controlled valve 14, and the endpiece that this liquid flows out bypass 10 is provided with liquid flowmeter 16 (also can adopt graduated cylinder to calculate and pass through the film fluid flow); The upper end of gas buffer jar 2 is provided with inlet, and the lower end is provided with liquid outlet, and inlet is provided with liquid inlet control valve 21, and liquid outlet is provided with out hydraulic control valve 22; This liquid flows out bypass 10 and is provided with second by-pass valve control 15 that is used to control the turnover of film liquid.
In this specific embodiment, micro-filtration membrane is a flat sheet membrane, like Fig. 4, shown in Figure 5; Test membrane cisterna 3 comprises can fasten the last membrane cisterna 32 and following membrane cisterna 33 that forms sample chamber 31 each other, and last membrane cisterna 32 has the guide hole that is connected with following membrane cisterna 33, and wherein sample chamber 31 is cylindrical; Be communicated with exterior line 4 through guide hole 38, be provided with the packoff that is used for sealed sample chamber 31 between last membrane cisterna 32 and the following membrane cisterna 33, flat sheet membrane places sample chamber 31; Outward flange is pressed between membrane cisterna 32 and the following membrane cisterna 33; Wherein sample chamber 31 is cylindrical, is communicated with exterior line 4 through guide hole 38, and being provided with through side of flat sheet membrane is used to cushion through the gas of flat sheet membrane or the porous gasket 34 of fluid pressure; Porous gasket 34 adopts the sintered porous plate of stainless steel; Last membrane cisterna 32 has the through hole that is connected with following membrane cisterna 33, and last membrane cisterna 32 periphery walls are provided with locating slot 35, and following membrane cisterna 32 is provided with the locating piece 36 that is used with locating slot 35 with last membrane cisterna 33 contacted end faces.
In this specific embodiment; Test membrane cisterna 3 also comprises upper press cover and the lower cover that is used to compress last membrane cisterna 32 of sealing and following membrane cisterna 33; Upper press cover and lower cover are fixing through being threaded; Upper press cover and lower cover are provided with the clip that is used to compress upper press cover and described lower cover, and upper press cover and lower cover respectively have a passage and the (not shown) that is connected into and out of pipeline 4.
In this specific embodiment; The end face that last membrane cisterna 32 contacts with following membrane cisterna 33 is provided with the end face that annular groove 34 or lower cover contact with upper press cover and is provided with annular groove 37, and above-mentioned packoff is the grommet type seals (not shown) of inlay card in annular groove 37.
The automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer, as shown in Figure 3, comprise the steps:
(1) micro-filtration membrane to be tested is soaked in advance put into test membrane cisterna 3 sealing and fixing behind the infiltrate, the maximum that in the control program of computer control 8, preestablishes micro-filtration membrane is born pressure P
0With the admission pressure V that gathers way;
(2) electric flow control valve 5, breather valve 12 and first controlled valve 14 are opened, the gas in the air feed bottle gets into gas buffer jar 2 successively and tests in the membrane cisterna 3 through electric flow control valve 5;
Pressure P signal in the gas buffer jar 2 that (3) will record with pressure probe 6 collects in the data acquisition module through the gas flow Fs signal in real time of micro-filtration membrane down with the relevant pressure P that gas flow probe 7 records; Through communication module pressure P signal that collects and gas flow Fs signal are transferred in the computer control 8, form pressure P-gas flow Fs data one to one;
(4) computer control 8 is with the pressure P signal that collects and the gas flow F under the relevant pressure P
SSignal is a foundation; Aperture-flow performance parameter in conjunction with electric flow control valve 5; With the preset admission pressure V that gathers way is controlled target; Calculate in real time the aperture of electric flow control valve 5, the aperture of the electric flow control valve 5 that calculates gained is fed back on the electric flow control valve 5 in real time carry out, pilot-gas surge tank 2 internal pressures gather way and are the preset admission pressure V that gathers way;
(5) according to pressure P signal of gathering and the gas flow F under the relevant pressure P
SThe signal measuring pore diameter distribution:
A. with the pressure P substitution transmembrane pressure computing formula of measuring in the step (3)
; Obtain transmembrane pressure
; Wherein Pa is the gaseous tension that sees through the gas vent side of film; Be generally atmospheric pressure; Py is gas buffer jar and the pressure differential of measuring the film on the suction side, is instrument constant;
B. according to the Laplace law; Transmembrane pressure Δ p newly opens under the pressure reduction therewith and has following relational expression between the membrane aperture r:
; With the transmembrane pressure that obtains
substitution formula
, obtain the membrane aperture r that newly opens under this transmembrane pressure;
C. according to the gas flow Fs that measures in the step (3) under the relevant pressure P that obtains; Calculate the gas flow recruitment
(promptly being the gas flow of the through hole of r) under transmembrane pressure
and the adjacent transmembrane pressure through the aperture; Membrane aperture r is reached
substitution Hagen-Poiseuille equation:
; Obtain effective number of through-holes n of the aperture r under the relevant pressure P; Wherein σ is the surface tension of infiltrate; θ is the contact angle between infiltrate and the material; N is that the aperture is effective via count of r, and η is that gas viscosity, l are effective through hole length of film;
D. show aperture measure of spread result, i.e. effective gas flow
under hole area
, the aperture r-respective aperture under number of through-holes n, the aperture r-respective aperture under the aperture r-respective aperture;
(6) when reaching preset maximum, pressure P bears pressure P
0Or pressure P-when gas flow Fs is linear, closing electric flow control valve 5 automatically, the storing measurement result gets into step (7), otherwise, repeat above-mentioned steps (3);
Number pressure is fixed, closes breather valve door (7) and finishes to measure, and closes the breather valve 12 and first by-pass valve control 14.
In this specific embodiment; The infiltrate of micro-filtration membrane select boiling point higher not volatile, membrane material is had good wetting property but can not dissolve again simultaneously or the liquid of swelling membrane material; Like isopropyl alcohol, normal butyl alcohol equal solvent; But be not limited to above-mentioned solvent, in principle membrane material had good wetting property but can not dissolve again simultaneously or the liquid of swelling membrane material all belongs to this patent protection domain.
Full-automatic micro-filtration membrane pore diameter distribution analyzer of the present invention can be used for measuring pore diameter distribution, average pore size, gas flux and the liquid flux of micro-filtration membrane.
The full-automatic micro-filtration membrane pore diameter distribution of the present invention analyzer; As shown in Figure 2; Comprise air feed bottle 1, gas buffer jar 2 and be used for fixing the test membrane cisterna 3 of sealed micro filter membrane; Air feed bottle 1, gas buffer jar 2 and test membrane cisterna 3 are connected through pipeline 4 successively, are provided with electric flow control valve 5 between air feed bottle 1 and the gas buffer jar 2, and gas buffer jar 2 is provided with pressure probe 6; The outlet of test membrane cisterna 3 micro-filtration membrane per-meate side is provided with gas flow probe 7, the signal output part of pressure probe 6 and gas flow probe 7 be used for gathering in real time corresponding pressure P signal and gas flow F
SThe data acquisition module of signal links to each other, data acquisition module through communication module with pressure P signal that collects and gas flow F
SSignal is transferred in the computer control 8, and the signal output part of computer control 8 is connected with the signal input part of electric flow control valve 5 and electric flow control valve 5 is carried out real-time FEEDBACK CONTROL.
In this specific embodiment, as shown in Figure 2, be provided with reduction valve 9 between air feed bottle 1 and the gas buffer jar 2; Be provided with first controlled valve 14 that is used to control the turnover of film gas between test membrane cisterna 3 and the gas flow probe 7; Gas buffer jar 2 and test also are provided with between the membrane cisterna 3 and pipeline 4 and the fluid-through tube road 11 that connects; Pipeline 4 between gas buffer jar 2 and the test membrane cisterna 3 is provided with breather valve 12; Fluid-through tube road 11 is provided with logical hydraulic control valve 13; Liquid flows out bypass 10 between the test membrane cisterna 3 and first controlled valve 14, and the endpiece that this liquid flows out bypass 10 is provided with liquid flowmeter 16 (also can adopt graduated cylinder to calculate and pass through the film fluid flow); The upper end of gas buffer jar 2 is provided with inlet, and the lower end is provided with liquid outlet, and inlet is provided with liquid inlet control valve 21, and liquid outlet is provided with out hydraulic control valve 22; This liquid flows out bypass 10 and is provided with second by-pass valve control 15 that is used to control the turnover of film liquid.
In this specific embodiment, micro-filtration membrane is tubular membrane 101 or hollow-fibre membrane 102, like Fig. 4, shown in Figure 5; Test membrane cisterna 3 comprises can fasten the last membrane cisterna 32 and following membrane cisterna 33 that forms sample chamber 31 each other, and last membrane cisterna 32 has the guide hole that is connected with following membrane cisterna 33, and wherein sample chamber 31 is cylindrical; Be communicated with exterior line 4 through guide hole 38; Be provided with the packoff that is used for sealed sample chamber 31 between last membrane cisterna 32 and the following membrane cisterna 33, the space that tubular membrane 101 or hollow-fibre membrane 102 pass between tool hole circle dull and stereotyped 18 and the tool hole circle dull and stereotyped 18 is filled with encapsulant 17, and the endpiece of tubular membrane 101 is provided with encapsulant 17; Like Fig. 6, shown in Figure 7; Tool hole circle dull and stereotyped 18 places sample chamber 31, and outward flange is pressed between membrane cisterna 32 and the following membrane cisterna 33, and wherein sample chamber 31 is cylindrical; Encapsulant 17 (all belongs to this patent protection domain so long as can play the material of sealing function like epoxy resin, polyurethane etc.; Be not limited to above-mentioned two materials), last membrane cisterna 32 periphery walls are provided with locating slot 35, and following membrane cisterna 32 is provided with the locating piece 36 that is used with locating slot 35 with last membrane cisterna 33 contacted end faces.
In this specific embodiment; Test membrane cisterna 3 also comprises upper press cover and the lower cover that is used to compress last membrane cisterna 32 of sealing and following membrane cisterna 33; Upper press cover is connected fixing with lower cover through flange (one or both modes that also can be in bolt, flange, clip and the bolt combine); Upper press cover and lower cover are provided with the clip that is used to compress upper press cover and lower cover, and upper press cover respectively has a passage and the (not shown) that links to each other into and out of pipeline with lower cover.
In this specific embodiment; The end face that last membrane cisterna 32 contacts with following membrane cisterna 33 is provided with the end face that annular groove 37 or lower cover contact with upper press cover and is provided with annular groove 37, and above-mentioned packoff is the grommet type seals (not shown) of inlay card in annular groove 37.
The automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer, as shown in Figure 3, comprise the steps:
(1) micro-filtration membrane to be tested is soaked in advance put into test membrane cisterna 3 sealing and fixing behind the infiltrate, the maximum that in the control program of computer control 8, preestablishes micro-filtration membrane is born pressure P
0With the admission pressure V that gathers way;
(2) electric flow control valve 5, breather valve 12 and first controlled valve 14 are opened, the gas in the air feed bottle gets into gas buffer jar 2 successively and tests in the membrane cisterna 3 through electric flow control valve 5;
Pressure P signal in the gas buffer jar 2 that (3) will record with pressure probe 6 collects in the data acquisition module through the gas flow Fs signal in real time of micro-filtration membrane down with the relevant pressure P that gas flow probe 7 records; Through communication module pressure P signal that collects and gas flow Fs signal are transferred in the computer control 8, form pressure P-gas flow Fs data one to one;
(4) computer control 8 is with the pressure P signal that collects and the gas flow F under the relevant pressure P
SSignal is a foundation; Aperture-flow performance parameter in conjunction with electric flow control valve 5; With the preset admission pressure V that gathers way is controlled target; Calculate in real time the aperture of electric flow control valve 5, the aperture of the electric flow control valve 5 that calculates gained is fed back on the electric flow control valve 5 in real time carry out, pilot-gas surge tank 2 internal pressures gather way and are the preset admission pressure V that gathers way;
(5) according to pressure P signal of gathering and the gas flow F under the relevant pressure P
SThe signal measuring pore diameter distribution:
A. with the pressure P substitution transmembrane pressure computing formula of measuring in the step (3)
; Obtain transmembrane pressure
; Wherein Pa is the gaseous tension that sees through the gas vent side of film; Be generally atmospheric pressure; Py is gas buffer jar and the pressure differential of measuring the film on the suction side, is instrument constant;
B. according to the Laplace law; Transmembrane pressure Δ p newly opens under the pressure reduction therewith and has following relational expression between the membrane aperture r:
; With the transmembrane pressure that obtains
substitution formula
, obtain the membrane aperture r that newly opens under this transmembrane pressure;
C. according to the gas flow Fs that measures in the step (3) under the relevant pressure P that obtains; Calculate the gas flow recruitment
(promptly being the gas flow of the through hole of r) under transmembrane pressure
and the adjacent transmembrane pressure through the aperture; Membrane aperture r is reached
substitution Hagen-Poiseuille equation:
; Obtain effective number of through-holes n of the aperture r under the relevant pressure P; Wherein σ is the surface tension of infiltrate; θ is the contact angle between infiltrate and the material; N is that the aperture is effective via count of r, and η is that gas viscosity, l are effective through hole length of film;
D. show aperture measure of spread result, i.e. effective gas flow
under hole area
, the aperture r-respective aperture under number of through-holes n, the aperture r-respective aperture under the aperture r-respective aperture;
(6) when reaching preset maximum, pressure P bears pressure P
0Or pressure P-when gas flow Fs is linear, closing electric flow control valve 5 automatically, the storing measurement result gets into step (7), otherwise, repeat above-mentioned steps (3);
Number pressure is fixed, closes breather valve door (7) and finishes to measure, and closes the breather valve 12 and first by-pass valve control 14.
In this specific embodiment; The infiltrate of micro-filtration membrane select boiling point higher not volatile, membrane material is had good wetting property but can not dissolve again simultaneously or the liquid of swelling membrane material; Like isopropyl alcohol, normal butyl alcohol equal solvent; But be not limited to above-mentioned solvent, in principle membrane material had good wetting property but can not dissolve again simultaneously or the liquid of swelling membrane material all belongs to this patent protection domain.
Full-automatic micro-filtration membrane pore diameter distribution analyzer of the present invention can be used for measuring pore diameter distribution, average pore size, gas flux and the liquid flux of micro-filtration membrane.
Three, test process of the present invention
The present invention's full-automatic micro-filtration membrane pore diameter distribution analyzer and automatic assay method thereof not only can be tested the pore diameter distribution of micro-filtration membrane with using, and can also measure the gas flux and the liquid flux of micro-filtration membrane, and concrete test process is following:
(1) full-automatic micro-filtration membrane pore diameter distribution analyzer is used to measure the process of pore diameter distribution
When measuring the micro-filtration membrane pore diameter distribution, the micro-filtration membrane to be tested of soaking into infiltrate is in advance put into test membrane cisterna 3 sealing and fixing, open electric flow control valve 5; Breather valve 12, the first controlled valves 14 are closed liquid inlet control valve 21; Logical hydraulic control valve 13; Second switch valve 15 goes out hydraulic control valve 22, and the test gas in the air feed bottle 1 (nitrogen, oxygen, helium, airborne a kind of) gets into electric flow control valve 5 behind reduction valve 9; The aperture of this electric flow control valve 5 receives the FEEDBACK CONTROL of gas surge tank 2 upward pressures probe 6 according to the setting program of measuring pore diameter distribution; Thereby guarantee that micro-filtration membrane air inlet side gaseous tension P increases according to the speed of setting, the reading of gaseous tension P collects in the computing machine through data collector, and control program gathers way according to preset admission pressure on this basis and calculates the aperture of electric flow control valve 5 in real time; And result of calculation fed back on the electric flow control valve 5 carry out; The film gas that passes through under relevant pressure P is vented in the atmosphere, and its gas flow Fs measures through gas flow probe 7, and determination data collects in the computer control 8 through data collector in real time; Form virgin pressure P-gas flow Fs data one to one with same pressure P of gathering in real time; Calculate in real time according to aforementioned bubble point flow velocity method, obtain corresponding pore size distribution data, and calculate average pore size in view of the above.
(2) full-automatic micro-filtration membrane membrane aperture distribution recognizer is used to measure the process of gas flow
When measuring under the specified pressure gas flow, the micro-filtration membrane to be tested of drying is put into corresponding test membrane cisterna 3 sealing and fixing, open electric valve flow control valve 5; Breather valve 12, the first controlled valves 14 are closed liquid inlet control valve 21; Logical hydraulic control valve 13; Go out hydraulic control valve 22, second switch valve 15, the test gas in the air feed bottle 1 (nitrogen, oxygen, helium, airborne a kind of) get into electric flow control valve 5 behind reduction valve 9; The aperture of this electric flow control valve 5 is a controlled target with the test pressure of setting; Receive the FEEDBACK CONTROL of gas surge tank upward pressure probe P, guarantee that a jar internal pressure is stabilized under the pressure of setting, the film gas flux that gas flow probe 7 is measured under the relevant pressure P.
(3) full-automatic micro-filtration membrane Membrane Pore Size Analyzer is used to measure the process of fluid flow
When measuring under the specified pressure fluid flow, close logical hydraulic control valve 13, second switch valve 15; In gas buffer jar 2, inject a certain amount of test liquid through liquid inlet control valve 21, its liquid level is lower than the position of breather valve 12, keeps gas buffer jar 2 internal upper parts that certain gas space is arranged; Close liquid inlet control valve 21; With the test membrane cisterna 3 that micro-filtration membrane to be tested drying or that the infiltrate immersion treatment is crossed is put into, open electric flow control valve 5, logical hydraulic control valve 13, second switch valve 15, close liquid inlet control valve 21, breather valve 12, go out the hydraulic control valve 22 and first controlled valve 14; Gas in the space of film air inlet side is drained fully; With the micro-filtration membrane sealing and fixing, the test gas in the air feed bottle 1 (nitrogen, oxygen, helium, airborne a kind of) gets into electric flow control valve 5 behind reduction valve 9 then, and the aperture of this electric flow control valve 5 is a controlled target with the test pressure of setting; Receive the FEEDBACK CONTROL of gas surge tank 2 upward pressures probe P; Guarantee that a jar internal pressure is stabilized under the pressure of setting, the filtrating that sees through film is flowed out bypass 10 outflows through liquid, and available graduated cylinder stopwatch method or flowmeter method are measured flow of filtrate.
The present invention controls condition determination in real time automatically and gathers measurement data through computing machine and self controlled element; Data are handled in real time; Calculate the number of through-holes under each aperture span in the micro-filtration membrane, the pore diameter range that can measure is 0.05 ~ 10 micron, can measure the gas flux and the liquid flux of film in addition; The mensuration result shows in real time, stores and print with the form of chart and pore size distribution curve, also can have access to the data of former mensuration.This instrument both can have been measured pore diameter distribution, average pore size, gas, the liquid flux of the flat sheet membrane of macromolecule or ceramic quality; Also can measure the above-mentioned performance parameter of hollow-fibre membrane, tubular membrane; Basically can satisfy evaluation requirement, for a kind of practical and convenient microporous barrier performance evaluation equipment that provides is studied and used to film to all kinds of sieve aperture property filter membrane performances.
Claims (6)
1. the automatic assay method of a full-automatic micro-filtration membrane pore diameter distribution analyzer; Described full-automatic micro-filtration membrane pore diameter distribution analyzer; Comprise air feed bottle, gas buffer jar and be used for fixing the test membrane cisterna of sealed micro filter membrane; Described air feed bottle, described gas buffer jar and described test membrane cisterna are connected through vent line successively; Be provided with electric flow control valve between described air feed bottle and the described gas buffer jar; Described gas buffer jar is provided with pressure probe, and the outlet of the micro-filtration membrane per-meate side of described test membrane cisterna is provided with gas flow probe, the signal output part of described pressure probe and described gas flow probe be used for gathering in real time pressure P signal and gas flow F
SThe data acquisition module of signal links to each other, described data acquisition module through communication module with pressure P signal that collects and gas flow F
SSignal is transferred in the computer control; The signal output part of described computer control is connected with the signal input part of described electric flow control valve and described electric flow control valve is carried out real-time FEEDBACK CONTROL; Be provided with reduction valve between described air feed bottle and the described gas buffer jar; Be provided with first controlled valve that is used to control the turnover of film gas between described test membrane cisterna and the described gas flow probe; Described vent line is in the position of section between described gas buffer jar and the described test membrane cisterna and connects and is provided with the fluid-through tube road, and the position that is in section between described gas buffer jar and the described test membrane cisterna on the described vent line is provided with breather valve, and described fluid-through tube road is provided with logical hydraulic control valve; Also be provided with liquid between the described test membrane cisterna and first controlled valve and flow out bypass; The outlet that described liquid flows out bypass is provided with liquid flowmeter, and the upper end of described gas buffer jar is provided with inlet, and the lower end is provided with liquid outlet; Described inlet is provided with liquid inlet control valve; Described liquid outlet is provided with out hydraulic control valve, and described liquid flows out bypass and is provided with the second switch valve that is used to control the turnover of film liquid, it is characterized in that automatic assay method comprises the steps:
(1) micro-filtration membrane to be tested is soaked in advance put into test membrane cisterna sealing and fixing behind the infiltrate, the maximum that in the control program of computer control, preestablishes micro-filtration membrane is born pressure P
0With the admission pressure V that gathers way;
(2) electric flow control valve, breather valve and first controlled valve are opened, the gas in the air feed bottle gets into the gas buffer jar successively and tests in the membrane cisterna through electric flow control valve;
The gas flow Fs signal in real time that the relevant pressure P that pressure P signal in the gas buffer jar that (3) will record with pressure probe and gas flow probe record sees through micro-filtration membrane down collects in the data acquisition module; Through communication module pressure P signal that collects and gas flow Fs signal are transferred in the computer control, form pressure P-gas flow Fs data one to one;
(4) computer control is with the pressure P signal that collects and the gas flow F under the relevant pressure P
SSignal is a foundation; With the preset admission pressure V that gathers way is controlled target; Calculate the aperture of electric flow control valve in real time; The aperture of the electric flow control valve that calculates gained fed back on the electric flow control valve in real time carry out, pilot-gas surge tank internal pressure gathers way and is the preset admission pressure V that gathers way;
(5) according to pressure P signal of gathering and the gas flow F under the relevant pressure P
SThe signal measuring pore diameter distribution:
A. with the pressure P substitution transmembrane pressure computing formula Δ p=P-P that measures in the step (3)
a-P
y, obtain transmembrane pressure Δ p, wherein Pa is the gaseous tension that sees through the gas vent side of film, Py is the pressure differential of gas buffer jar and micro-filtration membrane on the suction side;
B. the transmembrane pressure Δ p substitution formula
that obtains is obtained the membrane aperture r that newly opens under this transmembrane pressure;
C. according to the gas flow Fs that measures in the step (3) under the relevant pressure P that obtains, calculate the gas flow recruitment Δ F under transmembrane pressure Δ p and the adjacent transmembrane pressure
s, with membrane aperture r and Δ F
sSubstitution Hagen-Poiseuille equation:
Obtain effective number of through-holes n of the aperture r under the relevant pressure P, wherein σ is the surface tension of infiltrate, and θ is the contact angle between infiltrate and the material, and n is that the aperture is effective via count of r, and η is that gas viscosity, l are effective through hole length of film;
D. show aperture measure of spread result, i.e. effective hole area n π r under number of through-holes n, the aperture r-respective aperture under the aperture r-respective aperture
2, gas flow Δ F under the r-respective aperture of aperture
s
(6) when reaching preset maximum, pressure P bears pressure P
0Or pressure P-when flow Fs is linear, closing electric flow control valve automatically, the storing measurement result gets into step (7), otherwise, repeat above-mentioned steps (3);
(7) finish to measure, close the breather valve and first controlled valve.
2. the automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer according to claim 1 is characterized in that: described micro-filtration membrane is flat sheet membrane, hollow-fibre membrane or tubular membrane, and the material of described micro-filtration membrane is macromolecular material or inorganic material.
3. the automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer according to claim 2; It is characterized in that: described test membrane cisterna comprises can fasten the last membrane cisterna and following membrane cisterna that forms sample chamber each other; Described upward membrane cisterna and described membrane cisterna down have the guide hole that is connected; Described sample chamber is communicated with described vent line through described guide hole; Be provided with the packoff that is used to seal described sample chamber between described last membrane cisterna and the described following membrane cisterna; Described flat sheet membrane places described sample chamber, and outward flange is pressed between described last membrane cisterna and the described following membrane cisterna, and the side that sees through of described flat sheet membrane is provided with the porous gasket that is used for compensator or trimmer pressure.
4. the automatic assay method of full-automatic micro-filtration membrane pore diameter distribution analyzer according to claim 2; It is characterized in that: described test membrane cisterna comprises that mutual fastening forms the last membrane cisterna and following membrane cisterna of sample chamber; Described upward membrane cisterna and described membrane cisterna down have the guide hole that is connected; Described sample chamber is communicated with described vent line through described guide hole; Describedly go up membrane cisterna and describedly be provided with the packoff that is used to seal described sample chamber between the membrane cisterna down, it is dull and stereotyped that described hollow-fibre membrane or described tubular membrane are passed the tool hole circle, and and described tool hole circle flat board between the space be filled with encapsulant; Described tool hole circle flat board places described sample chamber, and outward flange is pressed on the described membrane cisterna and described down between the membrane cisterna of going up.
5. according to the automatic assay method of claim 3 or 4 described full-automatic micro-filtration membrane pore diameter distribution analyzers; It is characterized in that: the described membrane cisterna periphery wall of going up is provided with locating slot, and described membrane cisterna down and the described contacted end face of membrane cisterna of going up are provided with the locating piece that is used with described locating slot.
6. according to the automatic assay method of claim 3 or 4 described full-automatic micro-filtration membrane pore diameter distribution analyzers; It is characterized in that: described test membrane cisterna also comprises upper press cover and the lower cover that is used to compress described last membrane cisterna of sealing and described following membrane cisterna; It is fixing that described upper press cover and described lower cover are connected through one or both modes in screw thread, flange, clip and the bolt, and described upper press cover and described lower cover respectively have a passage to be connected with described vent line.
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| CN102954918B (en) * | 2012-11-05 | 2014-10-08 | 华北电力大学 | Measurement apparatus capable of concurrently measuring elastic modulus and airtightness of ceramic material, and method thereof |
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| CN104266952A (en) * | 2014-09-30 | 2015-01-07 | 成都易态科技有限公司 | Pore diameter detection device of porous material |
| CN104383815B (en) * | 2014-12-04 | 2016-11-02 | 南京工业大学 | A kind of method of testing of ultrafilter membrane pore-size distribution |
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| CN109900612B (en) * | 2017-12-11 | 2023-12-15 | 中国科学院大连化学物理研究所 | Porous material water permeability pressure testing device |
| CN108279200A (en) * | 2018-04-25 | 2018-07-13 | 苏州名列膜材料有限公司 | A kind of bubble point test device and bubble point test system |
| CN110531794A (en) * | 2019-08-30 | 2019-12-03 | 北京北方华创微电子装备有限公司 | Fluid pressure control device and method, cleaning solution supplying mechanism |
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