CN109665506A - Atmosphere xenon enrichment and purification method, device and the method for preparing carbon molecular sieve - Google Patents
Atmosphere xenon enrichment and purification method, device and the method for preparing carbon molecular sieve Download PDFInfo
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Abstract
The invention belongs to the monitoring system and method that atmospheric radiation environmental monitoring and nuclear facilities are safely operated, more particularly to atmosphere xenon enrichment and purification method, device and the method for preparing carbon molecular sieve, method mainly includes air pretreatment, carries out three-level concentration, isolates and purifies, sample preparation and online stable xenon detecting step, the series connection of the doughnut nitrogen-rich film component of M branch same model and/or different model and/or parallel connection are used during air pretreatment, are separated；In purification procedures using carbon molecular sieve as adsorbent, solve the problems, such as that existing atmosphere xenon enrichment and purification method and device bioaccumulation efficiency are low, amount by obtaining xenon for the system 24 hours is not less than 10mL, and xenon volume by volume concentration is not less than 30%, and stable xenon quantifies uncertainty less than 10%.
Description
Technical field
It is especially a kind of the invention belongs to the monitoring system and method that atmospheric radiation environmental monitoring and nuclear facilities are safely operated
Efficient atmosphere xenon enrichment, purification process and device.
Background technique
The volume fraction of rare gas xenon is 8.7 × 10 in air-8(V/V), wherein the content of radioactive xenon isotope is more
It is low, it is difficult to directly to analyze.The sampling of radgas xenon is the separation and concentration xenon isotope from ambient air, and reaches xenon point
Requirement of the quantitative detection sensitivity and radioactivity survey instrument of analyzer device to radioactive xenon isotope content, it is therefore necessary to from big
It will be in the volume of xenon efficient concentration a to very little in the air of amount.
The invention of 63653 army Zhou Chongyang of the Chinese People's Liberation Army et al., Patent No. CN201728039U are entitled
The patent of " a kind of separator of enriched gas xenon ", using the first order 5A molecular sieve removal of impurities column, first order active carbon adsorption column,
Second level 5A molecular sieve add active carbon removal of impurities column, second level active carbon adsorption column, third level 5A molecular sieve add active carbon removal of impurities column,
Third level active carbon adsorption column carrys out concentration and separation xenon, has used 6 adsorption columns in total, is related to the adsorption column of 2 kinds of 2 specifications, knot
Structure is complicated, and can not achieve continuous sampling.
This seminar is 2011102330695 in a number of patent application in 2012, it was recently reported that a kind of xenon in atmosphere
Normal temperature enrichment sampling method and device use hollowfibre semi-permeable membrance group as air pretreatment device, using 4 grades of adsorption columns by
Xenon in grade enrichment condensed air, wherein first order absorption cylinder uses two sets of parallel organizations, works alternatively, solving cannot connect
The problem of continuous sampling.
But the enriching and purifying of the xenon of the device is relatively inefficient, sufficiently bulky, and helium or nitrogen cylinder is needed to provide
Adsorption columns at different levels desorption transfer and regenerated carrier gas, lead to that structure is complicated, and operating cost is high；In addition the device can not judge in time
With the operating status of evaluating apparatus.For example the size of the device first order adsorption column is 60 × 3000mm of Φ；It obtains within 24 hours steady
The volume of xenon at standard conditions is determined less than 4ml, and it is 150ml that xenon sample, which measures source volume, and the volume ratio of xenon is dense in final sample
Degree is less than 3.0%.
Summary of the invention
In order to solve the problems, such as that existing atmosphere xenon enrichment and purification method and device bioaccumulation efficiency are low, the present invention provides one kind
The high atmosphere xenon enrichment and purification method of bioaccumulation efficiency, while the xenon enriching and purifying that a kind of structure simply can be realized this method being provided
Device further solves the problem of existing apparatus can not judge the operating status with evaluating apparatus in time.Pass through the system 24
The amount that hour obtains xenon is not less than 10mL, and xenon volume by volume concentration is not less than 30%, and stable xenon quantifies uncertainty less than 10%.
The technical solution of the invention is as follows provides a kind of atmosphere xenon enrichment and purification method, comprising the following steps:
1) air pretreatment:
Steam, oxygen, carbon dioxide and part nitrogen in air are removed using film drier, membrane separator, to air
In xenon carry out initial concentration；Wherein film drier removes water membrane module using doughnut, and membrane separator is by M branch same model
And/or the series connection of doughnut nitrogen-rich film component and/or parallel connection of different model, M are more than or equal to 2；
2) three-level concentration is carried out to step 1) treated gas；Concentration process includes the filling using three kinds of different models
Column successively carries out room temperature absorbing high temp three times to step 1) treated gas and desorbs, and realization is concentrated step by step；
3) gas after step 2) concentration is isolated and purified, realizes efficiently separating for xenon and radon gas；
4) sample preparation
Adsorption-desorption finally is carried out to the xenon that step 3) flows out using level V packed column, the gas after desorption is carried out
Sample preparation.
Preferably, in order to realize on-line monitoring, the operating status of device is grasped in time, further includes to preparation in step 4)
The step of gaseous sample afterwards carries out online stable xenon detection, collects filing after the completion of detection；
Above-mentioned doughnut removes water membrane module, and the UM series of model Ube UBE removes moisture film, including UMS-B10 and
UM-C10；The model of the doughnut nitrogen-rich film component of the M branch different model of membrane separator is respectively the NM system of Ube UBE
Column nitrogen-rich film, including NM-C05A, NM-B10A, NM-C07F, NM-C10F and NM-510F；Membrane separator uses NM-C05A, NM-
At least two in B10A, NM-C07F, NM-C10F and NM-510F are connected with model and/or different model film group.
The adsorbent filled in above-mentioned packed column is carbon molecular sieve, and the carbon molecular sieve is cylindrical body particle, and column diameter is
1.3~1.8mm, pillar height degree 2.5mm；The specific surface area of carbon molecular sieve is 380m2g-1, apparent density 0.6g/cm3, micropore is equal
Value aperture is 0.5nm (HK), micropore volume 0.15cm3g-1。
Preferably, in order to simplify structure and save the cost, the carrier gas of all desorption processes is the pretreated gas of step 1)
Body, without introducing external air source；In order to realize continuous sampling, in first order concentration process, using two first order carbon in parallel
Molecular sieve packed column alternating sorbent and desorption.
Preferably, when being desorbed using first order carbon molecular sieve packed column, control gas flow is 500-600mL/min, control
Barrel temperatures processed are 260 DEG C -300 DEG C；When being desorbed using second level carbon molecular sieve packed column, control gas flow is 40-50mL/
Min, control barrel temperatures are 260 DEG C -300 DEG C；When being desorbed using third level carbon molecular sieve packed column, control gas flow is
30-35mL/min, control barrel temperatures are 260 DEG C -300 DEG C；
When being desorbed using level V carbon molecular sieve packed column, control gas flow is 10-20mL/min, controls barrel temperatures
It is 180 DEG C -300 DEG C.
The present invention also provides a kind of xenon device for enriching and purifying for realizing the above method, including it is air supply system, sampling unit, pure
Change source unit and on-line measurement collector unit processed；It is characterized in that
Above-mentioned air supply system includes by the sequentially connected filter of pipeline, compressor, film drier, membrane separator, delays
Rush tank；Wherein film drier removes water membrane module using doughnut, and above-mentioned membrane separator is propped up by M with model and/or different model
Doughnut nitrogen-rich film component series connection, M be more than or equal to 2；
Above-mentioned sampling unit includes first order packed column；
Above-mentioned purifying source unit includes purification unit and sample preparation unit, above-mentioned purification unit include by pipeline and
(its main function is to realize xenon for second level packed column that valve is sequentially connected in series, third level packed column, fourth stage molecular sieve packed column
Gas and radon gas efficiently separate；The molecular sieve be 60 to 80 mesh 5A zeolite molecular sieve), level V packed column；Above-mentioned sample system
Standby unit includes the diaphragm pump being sequentially connected in series by pipeline and valve and measurement source capsule；The entrance of level V packed column and diaphragm pump
End is connected to by pipeline and valve；
Above-mentioned on-line measurement collector unit includes vacuum pump, stable xenon measurement component and filing bottle；；
The outlet of above-mentioned first order packed column is connected to by pipeline and valve with the entrance of second level packed column；
The outlet end of above-mentioned measurement source capsule is connect with the arrival end of filing bottle；
Above-mentioned vacuum pump measures component with filing bottle and stable xenon by valve and connect；
Above-mentioned first order packed column, second level packed column, third level packed column, fourth stage molecular sieve packed column, level V
Packed column is respectively connected with the exhaust valve being in communication with the outside, and when absorption, opens the exhaust valve；
It is provided with the Mass flow controllers of control gas flow on above-mentioned pipeline, measures the pressure sensing of airline pressure
Device.
Preferably, in order to improve the enrichment factor of xenon, the doughnut of film drier removes water membrane module, model Japan space
The UM series of portion UBE removes moisture film, including UMS-B10 and UM-C10；The model of the M branch doughnut nitrogen-rich film component of membrane separator
The NM series nitrogen-rich film of respectively Ube UBE, including NM-C05A, NM-B10A, NM-C07F, NM-C10F and NM-510F；
The adsorbent filled in packed column is carbon molecular sieve, and the carbon molecular sieve is cylindrical body particle, column diameter is 1.3~
1.8mm, pillar height degree 2.5mm；The specific surface area of carbon molecular sieve is 380m2g-1, apparent density 0.6g/cm3, micropore mean pore radius
For 0.5nm (HK), micropore volume 0.15cm3g-1。
Preferably, in order to realize on-line monitoring, it includes measuring device and signal acquisition and place that aforementioned stable xenon, which measures component,
Manage module；
Above-mentioned measuring device includes tube body and the temperature-sensitive element for being set to tubular body, and above-mentioned temperature-sensitive element passes through lead
It is connect with Signal acquiring and processing module；Above-mentioned Signal acquiring and processing module is for acquiring and handling real-time temperature-sensitive element electricity
Resistance value；
Tube body includes air inlet and gas outlet, and the outlet end for measuring source capsule is connect with tube body air inlet, tube body gas outlet with
File the arrival end connection of bottle, gas enters tube body by air inlet, so that temperature-sensitive element resistance value changes, signal acquisition
Resistance value information is acquired and handled with processing module, and gas enters filing bottle by gas outlet.
Preferably, the outlet of above-mentioned surge tank is filled out with first order carbon molecular sieve by pipeline with Mass flow controllers respectively
Fill column, second level carbon molecular sieve packed column, third level carbon molecular sieve packed column, fourth stage molecular sieve packed column, level V carbon point
The entrance connection of son sieve packed column；When desorption, corresponding valve is opened, does desorption carrier gas using surge tank backend gas.On
State the first order carbon molecules that sampling unit includes and alternating sorbent identical by two specifications of pipeline and valve in parallel desorption
Sieve packed column.
Preferably, in order to reduce the overall volume of device and realize modularized design, carbon molecular sieve packed column includes shell
And the absorption pole unit positioned at enclosure interior；
Above-mentioned absorption pole unit includes the N grades of adsorption columns for being serially connected and being arranged side by side；
Each absorption column outer wall winds heater strip；Be provided with air inlet and gas outlet on each adsorption column cylinder, above-mentioned air inlet and
Gas outlet is respectively positioned on one end of cylinder；In two neighboring adsorption column, gas outlet and the next stage adsorption column of upper level adsorption column
Air inlet connection；
The air inlet of first order adsorption column and the gas outlet of N grades of adsorption columns are in communication with the outside by tracheae；
It further include the socket for connecting and being set to heater strip on shell；
Above-mentioned shell includes inner housing and the outer housing for wrapping up inner housing；Heat-insulated group is equipped between inner housing and outer housing
Part；The absorption pole unit is located inside inner housing；
It further include the cooling device being arranged in outside outer enclosure interior inner housing；Cooling device is connect with socket；
It is connected with air inlet pipe on above-mentioned air inlet, above-mentioned air inlet pipe is located at the end of column body and air inlet pipe close to cylinder
Bottom, carbon molecular sieve is filled inside adsorption column.
The present invention also provides a kind of methods for preparing above-mentioned carbon molecular sieve, including prepare material, material activating, charing process
And carbon deposit, it is characterised in that: the material activating and charing process are completed by following steps, and the material of preparation is placed in furnace
300 DEG C are inside heated to, nitrogen is passed through, then is warming up to 850 °, at this temperature constant temperature 60min, material is made to carbonize and be formed
Hole recycles nitrogen to bring hydro carbons or alcohols organic compound in furnace into, and the carrier band time for controlling nitrogen is 1~2.5 hour,
Make surface of material carbon deposit plug-hole, is taken out after being cooled to room temperature.
The beneficial effects of the present invention are:
1, the sampling efficiency of xenon is greatly improved by the improvement to membrane module and adsorbent in the present invention；
Using a kind of carbon molecular sieve by performance screening as adsorbent, the bioaccumulation efficiency of xenon greatly improves the present invention；
The combined application of hollow fiber film assembly reduces membrane module sample while greatly improving xenon separation concentrated effect
The waste of product processing capacity；Air-treatment amount of the present invention is up to 1m3/min；Products obtained therefrom gas dew point is low after air supply system processing
In -45 DEG C, the volume by volume concentration of carbon dioxide is less than 50ppm, and nitrogen gas purity is producing the item that throughput is 5L/min up to 99.9%
Under part, the pre-concentration multiple of xenon is up to 40 times or more, i.e., the volume by volume concentration of xenon is greater than 3ppm；
2, device blocks degree is high, and carbon molecular sieve packed columns at different levels use modularized design thinking, using multi-stage absorption
Column is turned back series connection, integrated automatic heating and cooling component, and aviation socket is utilized to realize resistive heater, temperature sensor and drop
The integration power supply and signal acquisition and feedback of warm fan.
3, it is integrated with the on-line measurement function of stable xenon, simplifies answering using gas chromatographic technique offline inspection xenon total amount
Miscellaneous program improves the timeliness of system running state calibrating while completing atmospheric radioactivity xenon monitoring the relevant technologies process
Property；
4, the present invention greatly reduces the body of sampling unit adsorption column while xenon sampling efficiency is greatly improved
Product, reduces system energy consumption；By the improvement to carbon molecular sieve packed column, facilitates air circuit connection more neatly, be not necessarily to simultaneously
Peripheral hardware desorption purging carrier gas, does desorption carrier gas using membrane separator backend gas, so that whole equipment volume reduces, operating cost
It reduces.
Detailed description of the invention
Fig. 1 is the device of the invention structural schematic diagram；In figure: MFC0-MFC5 is Mass flow controllers, and P is pressure biography
Sensor, V are electromagnetic valve；
In figure: 51- filter, 52- compressor, 53- film drier, 54- membrane separator, 55- surge tank, 56- diaphragm pump,
57- vacuum pump, 58- measure source capsule, and 59- stable xenon measures component, and 60- files bottle, 61- pressure maintaining valve；
Fig. 2 is various gas components infiltration rate in several membrane materials；
Fig. 3 is that various gas components permeate selection coefficient in several membrane materials；
Fig. 4 is that membrane module separates concentration xenon performance test experimental apparatus flow diagram from air；
In figure: 41- air compressor, 42- gas buffer tank, 43- refrigerant type dryer, 44- tertiary filter, 45- are steady
Pressure valve, the first mass flow controller of 46-, 47- thermostatic chamber, the second mass flow controller of 48-, 49- component analysis instrument, 50-
Pressure gauge；
Under the conditions of Fig. 5 is different air-flow ratios, different single branch membrane modules separated from air the enrichment factor (θ) of xenon with
The trend chart of air-flow ratio (K is defined as the ratio between charge flow rate and production throughput)；
Fig. 6 is the 24 hourly output (V that different single branch membrane modules separates and recovers xenon from airXe) with air-flow ratio (K)
Trend chart；
Under the conditions of Fig. 7 is three kinds of productions throughputs (Q2), NM-510F and NM-C10F connect membrane module separated from air it is dense
The enrichment factor (θ) of contracting xenon is with charge flow rate and the trend chart for producing throughput；
Under the conditions of Fig. 8 is three kinds of productions throughputs (Q2), NM-510F and NM-C10F connect membrane module separated from air it is dense
24 hourly output (V of contracting xenonXe) with the trend chart of charge flow rate and production throughput；
Fig. 9 is the concentration of the separation concentration xenon from air after tri- membrane modules of NM-510F, NM-C10F and NM-B10A are connected
Coefficient (θ) is with charge flow rate and the trend chart for producing throughput；
Figure 10 is that separation is concentrated the 24 of xenon from air after tri- membrane modules of NM-510F, NM-C10F and NM-B10A are connected
Hourly output (VXe) with the trend chart of charge flow rate and production throughput；
Figure 11 a is four NM-C10F membrane modules series connection schematic diagrames；
Figure 11 b is concatenated schematic diagram again after NM-C10F membrane module is in parallel two-by-two；
Figure 11 c is the schematic diagram for being sequentially connected in series two NM-C10F membrane modules after two NM-C10F membrane modules are in parallel again；
Figure 12 is the enrichment factor (θ) that the NM-C10F membrane module of series connection different number combines the separation concentration xenon from air
With the trend chart of air inflow；
Figure 13 be different air-flow ratios under the conditions of xenon enrichment factor with concatenated NM-C10F membrane module quantity variation tendency
Figure；
Figure 14 is several adsorbent Dynamic Adsorption xenon performance curves；
Figure 15 is stable xenon measuring device structural schematic diagram of the present invention；31- tube body in figure；32- air inlet；The gas outlet 33-；
34- temperature-sensitive element；36- thermocouple lead, 37- signal output terminal, 39- measuring device.
Figure 16 is first order carbon molecular sieve packed column structural schematic diagram of the present invention；
In figure: 1- upper outer shell, 2- sunk screw, 3- electric fan, 4- first end plate, the second end plate of 5-, 6- heat insulation foam,
7- second baffle, 8- lower housing body, 9- socket, 11- internal box, 12- heater strip, 16- pan head screw, 17- adsorb pole unit,
Case lid in 18-, 19- first baffle, 21- third window.
Figure 17 is invention adsorption column cellular construction schematic diagram；
Appended drawing reference in figure are as follows: the first air inlet of 71-, the first gas outlet 72-, 73- air inlet pipe.
Specific embodiment
Below in conjunction with drawings and the specific embodiments, the present invention will be further described.
Most steam, oxygen, titanium dioxide in air are removed using film drier, membrane separator first in the present embodiment
Carbon and part nitrogen carry out initial concentration to the xenon in air；Wherein film drier removes water membrane module, film using doughnut
Separator is that M branch is connected and/or the combination of the doughnut nitrogen-rich film component of parallel connection, M are more than or equal to 2；Then to treated gas
Body carries out three-level concentration；Concentration process includes the process of room temperature absorbing high temp desorption step by step on enrichment facility, in the present embodiment
Enrichment facility is the different carbon molecular sieve packed column of three kinds of specifications, including first order carbon molecular sieve packed column, second level carbon molecules
Sieve packed column and third level carbon molecular sieve packed column；The gas after the desorption of third level carbon molecular sieve packed column is separated again
Purifying, realization xenon and radon gas efficiently separate；The xenon of outflow is concentrated again again finally, the gas after concentration is carried out
After sample preparation, then online stable xenon detection is carried out, sample filing is collected after the completion of detection；The carrier gas of all desorption processes is film
Separator treated gas.In first order concentration process, alternately inhaled using two first order carbon molecular sieve packed columns in parallel
Echo desorption.
The detailed process of room temperature absorbing high temp desorption are as follows: when desorbing using first order carbon molecular sieve packed column, control gas
Flow is 500-1000mL/min, and control first order carbon molecular sieve filling column temperature is 260 DEG C -300 DEG C；Utilize second level carbon point
When son sieve packed column desorption, control gas flow is 40-50mL/min, and control second level carbon molecular sieve filling column temperature is 260
℃-300℃；When being desorbed using third level carbon molecular sieve packed column, control gas flow is 30-35mL/min, controls the third level
Carbon molecular sieve packed column degree is 260 DEG C -300 DEG C；When being desorbed using level V carbon molecular sieve packed column, control gas flow is
10-20mL/min, control level V carbon molecular sieve filling column temperature is 180 DEG C -300 DEG C.
It will be seen from figure 1 that the present embodiment device mainly include air supply system, sampling unit, purifying source unit and
Line measurement collection unit；
Air supply system: including passing through the sequentially connected filter 51 of pipeline, compressor 52, film drier 53, membrane separator
54 and surge tank 55, the exit of surge tank 55 be provided with four-way, wherein the two of four-way outlet end respectively with absorption gas circuit with
Desorb air circuit connection.
Sampling unit (first order carbon molecular sieve packed column): a threeway, the one outlet of threeway is arranged in adsorbed gas road
Va11 is terminated, one outlet terminates Vb11；
Va11 connects the first order carbon molecules of pressure transmitter Pa1, valve Va12 and A sampling unit by two threeways respectively
Packed column Ta1 is sieved, the outlet of Ta1 passes through a threeway connecting valve Va13 and valve Va14；
Vb11 connects pressure transmitter Pb1 by two three, the first order carbon molecular sieve of valve Vb12 and B sampling unit is filled out
Column Tb1 is filled, the outlet of Tb1 passes through a threeway connecting valve Vb13 and valve Vb14；
Va14, Vb14 are connected to the two-port of the same threeway, and the third port of the threeway connects V21 and solution by threeway
The MFC2 of air-breathing road；
Pass through the MFC1 in a threeway connection parsing gas circuit between Va12 and Vb12；
Purify source unit processed: V21 is connected to second level carbon molecular sieve packed column T2, and the outlet of T2 connects V22 by threeway
And V31；
V31 connects the outlet of MFC3, pressure transmitter P3 and the third level carbon molecular sieve packed column T3, T3 by three by four
Connect valve V32 and V41, V41 by four connects MFC4, pressure transmitter P4 and molecular sieve packed column T4, and (column is helical disk
Pipe), the outlet of molecular sieve packed column T4 connects valve V42 and V51 by three, and valve V51 connects MFC5, pressure inverting by four
The outlet end of device P5 and fourth stage carbon molecular sieve packed column T5, fourth stage carbon molecular sieve packed column T5 connect valve V52 by three
And V53, V53 connection diaphragm pump 56；
The outlet connecting valve V2 of diaphragm pump 56, V2 connect pressure transmitter P6, the four-way and valve by a four-way
V3 is connected with valve V4, and valve V3 is connect with the air inlet of vacuum pump 57；The air inlet of vacuum pump 57 also passes through 1 threeway and valve
Door V7 connection；V4 is connected to by a threeway with measurement source capsule 58 and V5；
On-line measurement and collector unit: V5 stable connection xenon measures component 59.Stable xenon measures component 59 and valve V6 connects
It connects, valve V6 is connect with V7 and filing bottle 60 respectively by a threeway.
Wherein, the doughnut of film drier 53 removes water membrane module, and the UM series of model Ube UBE removes moisture film,
Including UMS-B10 and UM-C10；
The present invention is to choose in membrane separator 54 with doughnut nitrogen-rich film component with commercially available multiple gases separation
The target of hollow fiber nitrogen-rich film component quantitatively extracts hollow-fibre membrane film wire therein, according to conventional method, tests N2、O2、
CO2, tetra- kinds of pure gas of Xe permeance property, calculate separately different materials film wire to O2/N2、O2/Xe、CO2/N2And CO2The ideal of/Xe
Separation.According to the calculated result of ideal separation factor, relatively determine be applicable in from air separation the hollow of xenon is concentrated
Fiber film material.
It is chosen especially by following experiments:
1) four kinds of hollow fiber film threads of selection test
The most commonly used doughnut nitrogen-rich film component currently on the market is mainly made of three kinds of membrane materials, is poly- respectively
Acid imide (PI), polyphenylene oxide (PPO) and polysulfones (PSF).The Polyimide Hollow Fiber silk of selection includes two kinds of models, respectively
For F type and A type, i.e. PI-F and PI-A, two kinds of film wires are not uniquely both their thickness and film thickness.The physics of four kinds of film wires
Parameter is listed in table 1.
The physical parameter of 1 four kinds of hollow fiber film threads of table
2) four kinds of Hollow-fibre membranes material gas permeability experimental results
Under conditions of test temperature is fixed on 30 DEG C, N is utilized2、O2、CO2With the high-purity gas of Xe, in high side gas
Under the conditions of pressure maintains 0.3MPa, their gas permeabilities in four kinds of Hollow-fibre membranes materials are tested, as a result such as Fig. 2
It is shown.
Four kinds of Hollow-fibre membranes materials are calculated to N in the experimental results of gas permeability according to fig. 22、O2、
CO2Separating property between tetra- kinds of gases of Xe, as a result such as Fig. 3.Fig. 3 shows separation of the PI-A and PI-F film to four kinds of gas
Performance is significantly better than other two kinds of films, wherein CO2The separation of/Xe is maximum, O2The separation of/Xe takes second place；PI-A and PI-F
Two kinds of films are little to the difference between the separating property of various gases.
According to the above analysis as a result, can be determined poly- in the film of polyimides, polysulfones and polyphenylene oxide three classes different materials
Acid imide film is more suitable for the separation concentration xenon from air；Polyimide film is obvious to the separation removal effect of carbon dioxide simultaneously
Better than other two classes films.
3) it differently combines the polyimides membrane module for not having to model, research combination caudacoria component divides from air
Performance from concentration xenon.
Experimental provision is as shown in Figure 4.Air compressor 41, gas buffer tank 42, freezing type including setting gradually are dry
Device 43, tertiary filter 44, the first mass flow controller 46, thermostatic chamber 47, the second mass flow controller 48 and component point
Analyzer 49, the component analysis instrument 49 are also connect with 46 outlet end pipeline of the first mass flow controller and thermostatic chamber 47, further include
Pressure maintaining valve 45 and pressure gauge 50 in pipeline are set；Membrane module is placed in the adjustable controllable thermostatic chamber 47 of temperature, air compression
Machine 41 provides compressed air gas source, and refrigerant type dryer 43 and tertiary filter 44 pre-process compressed air, avoids sky
Mist of oil, dust in gas etc. pollute membrane module, and the first mass flow controller 46 is adjusted respectively with the second mass flow controller 48
Save membrane module front and back end gas flow.
The Polyimide Hollow Fiber component that experiment is selected includes NM-B05A, NM-B10A, NM-C07F, NM-C10F and
Five kinds of NM-510F (physical parameter is listed in table 2), be the nitrogen-rich film component of Ube Co., Ltd. (UBE).
The physical parameter of five kinds of membrane modules of table 2UBE
The separation concentration xenon from air using single branch or more Polyimide Hollow Fiber component combinations, evaluates its application
The index of effect or xenon separation concentration performance includes xenon enrichment factor (θ) and 24 hours xenon amount to obtain (VXe).Xenon enrichment factor (θ)
It is defined as the ratio between the volume by volume concentration of the volume by volume concentration of xenon and xenon in unstripped gas i.e. air in product gas；24 hours xenon amount to obtain
(VXe) it is defined as the volume of xenon at standard conditions in every 24 hours membrane module product gas.
Single branch membrane module working performance test:
Above-mentioned 5 kinds of membrane modules are respectively placed in thermostatic chamber, regulating thermostatic room temperature is 20 DEG C, compares item in different air-flows
Under part, i.e., membrane module front and back end gas flow is adjusted at random, measure the separation concentrated effect of xenon in product gas, be as a result shown in
Fig. 5 and Fig. 6.
Fig. 5 and Fig. 6 show: using the membrane module of five kinds of specifications respectively from air when separation concentration xenon, the concentration system of xenon
Number (θ) is fine with the coherence of changing trend of air-flow ratio (K is defined as charge flow rate and produces the ratio between throughput), with the increase of K
It increases rapidly, tends towards stability after reaching maximum value；Under 20 DEG C of film group operational temperature conditions, the θ value of five kinds of membrane modules is in K value
Reach its maximum value when about 40, wherein about the 4.5 of NM-B05A, other 4 kinds are each about 13.24 hourly outputs of xenon with
The variation of air-flow ratio is rendered as the trend of logarithm reduction, and wherein the rate of recovery of xenon is about 80%.The result shows that NM-B05A film
Component is since its size is smaller, and whether distance is actually answered in terms of air sample processing capacity or concentrated effect in xenon
There is larger gap between requiring；Performance difference between NM-C07F and NM-C10F is little.
Different film group tandem working performance tests:
Property of the emphasis for tri- kinds of membrane module series connection of NM-B10A, NM-C10F and NM-510F separation concentration xenon from air
It can be carried out experiment test and discuss.
The series connection of NM-C10F and NM-B10A film group is placed in thermostatic chamber, providing maximum pressure in air supply system is about 8
Under a atmospheric pressure, controls two series connection film group rear ends production throughputs and be not more than 2L/min, then two film group front ends of connecting
Maximum steady state charge flow rate is about 100L/min.Table 3 is the concentration and separation effect of xenon under two kinds of application conditions.
Xenon performance test and calculated result is concentrated in table 3NM-C10F and NM-B10A separation
By table 3 it follows that NM-C10F and NM-B10A tandem working separates the property of concentration xenon from air
Can the performance of more single film group be substantially improved；The xenon enrichment factor of two film group tandem workings does not work close to single branch membrane component
The product of xenon enrichment factor under the conditions of same airflow ratio.But single branch film group of two film groups the series connection applications and larger size
Using comparing, fail the treating capacity for improving air sample.
NM-510F and NM-C10F series connection is placed in thermostatic chamber, providing maximum pressure in air supply system is about 8 big
Under air pressure conditions, the charge flow rate (Q of two series connection film group front end maximum steady states1) it is about 550L/min.Three kinds of production throughputs
(Q2) under the conditions of, which separates the effect of concentration xenon with charge flow rate from air and produces the variation tendency of throughput such as
Shown in Fig. 7 and Fig. 8.
By Fig. 7 and Fig. 8 it is found that the more single film group of performance of NM-510F and NM-C10F series connection separation concentration xenon from air
Performance be substantially improved.
NM-510F, NM-C10F and NM-B10A tri- different membrane module sequential series are placed in thermostatic chamber, in gas source
It is about the charge flow rate (Q of three series connection film group front end maximum steady states under 8 atmospheric pressures that system, which provides maximum pressure,1) about
For 600L/min.The series connection film group is to the concentration and separation effect of xenon with charge flow rate (Q1) and production throughput (Q2) variation tendency
As shown in Figure 9 and Figure 10.
By Fig. 9 and Figure 10 it is found that tri- membrane module sequential series of NM-510F, NM-C10F and NM-B10A divide from air
Whether the enrichment factor of xenon or the output of xenon are substantially improved effect from concentration xenon.
Same film group cascade operation performance test:
Carry out experimental study using four NM-C10F membrane modules, four membrane modules are respectively according to such as Figure 11 a to Figure 11 c three
Kind mode is combined cascade.
4 concatenated NM-C10F film groups are placed in thermostatic chamber first, the air inlet of 4 series connection film group front end maximum steady states
Flow (Q1) it is about 400L/min.Producing throughput (Q2) be set as under the conditions of 5L/min, which separates dense from air
The effect of contracting xenon is as shown in table 4.
Secondly according to cascade connection shown in Figure 11 b, it will connect again after NM-C10F membrane module is in parallel two-by-two and be placed in thermostatic chamber
It is interior, the charge flow rate (Q of front end maximum steady state1) it is about 400L/min.Producing throughput (Q2) be set as under the conditions of 5L/min, it should
The effect of film group of connecting combination separation concentration xenon from air is as shown in table 4.
Finally according to cascade connection shown in Figure 11 c, two will be sequentially connected in series again after two NM-C10F membrane modules parallel connections
NM-C10F membrane module, the charge flow rate (Q of front end maximum steady state1) it is about 400L/min.Producing throughput (Q2) it is set as 5L/
Under the conditions of min, the effect of series connection film group combination separation concentration xenon from air is as shown in table 4.
4 four NM-C10F membrane modules of table are concentrated and separated the performance of xenon under various combination mode from air
From table 4, it can be seen that the property of the membrane module of identical quantity separation concentration xenon from air under various combination mode
Energy difference is very big.By taking 4 NM-C10F membrane modules as an example, 2 parallel connections operating mode of continuous series and 4 continuous series again
Operating mode, performance difference between the two is smaller, but more other two kinds of the differences of performance of 2-2 parallel connection concatenated operating mode again
Away from very big.
Using 1 to 7 NM-C10F membrane module series connection application separation concentration xenon from air, provided in air supply system maximum
Pressure is about under 8 atmospheric pressures, and experiment test shows: 7 film group series connection and 6 membrane module tandem working inlet ends are maximum
Current stabilization charge flow rate respectively may be about 610L/min and 595L/min.
Regulating thermostatic room temperature and production throughput are respectively 20 DEG C and 5L/min, in different inlet air conditions (inlet air flows
Amount and admission pressure) under, the xenon enrichment factor in every kind of film group system production gas is measured, the enrichment factor is with film group system inlet air flow
Amount and the variation tendency of air-flow ratio are as shown in Figure 12 and Figure 13.
By Figure 11 and Figure 12 it can be seen that separating answering for concentration xenon from air using concatenated NM-C10F membrane module
In, temperature and production throughput are respectively 20 DEG C under the conditions of 5L/min, are connected for the film group of 3 to 7 grades of different numbers, if being
Charge flow rate of uniting is identical (between 200~500L/min), then the enrichment factor that film group system produces xenon in gas changes less, opposite
Standard deviation is about 8%；Various film group systems separate the xenon enrichment factor of concentration xenon with charge flow rate (air-flow from air
Than) increase approximately linear increase.
By above-mentioned experiment it follows that
(1) hollow fiber film thread of different materials is to N2、O2、CO2, the separating property difference between tetra- kinds of gases of Xe it is very big；
Common PI film is significantly better than PSF and PPO film to the separating property between four kinds of gases currently on the market.
(2) when the separation concentration xenon from air is used alone in different dimension hollow fiber film components, the enrichment factor of xenon is most
About 13；24 hourly outputs of xenon increase with the increase of film packet size.
(3) the effect mode in combination of identical size membrane module combined application is closely related, with 4 NM-C10F film groups
For part, the operating mode of 2 parallel connections continuous series again is compared with the operating mode of 4 continuous series, performance between the two
Difference is smaller, but 2-2 parallel connection more other two kinds of performance of concatenated operating mode has a long way to go again.
(4) identical size membrane module series connection application need to select the membrane module string of most suitable quantity according to practical application condition
Connection.
(5) effect of different size membrane module series connection applications is substantially better than the application effect of single branch membrane module.With 5L/min
For producing throughput, the application effect of tri- membrane module sequential series of NM-510F, NM-C10F and NM-B10A, hence it is evident that be better than NM-
510F and NM-C10F two series connection or the concatenated application effect of 6 to 7 NM-C10F.
Therefore, doughnut nitrogen-rich film chooses the NM series of Ube UBE in membrane separator 54 in the present embodiment, specifically
At least three kinds of membrane modules that can be chosen in NM-C05A, NM-B10A, NM-C07F, NM-C10F, NM-510F are serially connected.
The present invention is prepared and is filtered out the carbon molecular sieve of absorption xenon best performance by experiment, passes through the working condition system of control
For CMS-1 out to CMS-7 carbon molecular sieve.CMS-1 to CMS-5 is phenolic resin based carbon molecular sieve, the difference between them
Include whether the length of time that the processing of Carbon deposition tune hole and Carbon deposition are carried out using chemical deposition (CVD)；CMS-6 and CMS-
7 be coconut husk based carbon molecular sieve, and CMS-6 does not carry out the processing of CVD tune hole；CMS-7 has carried out the processing of tune hole.CMS-1 to CMS-4 is adopted
It is respectively 1.5h, 2.0h, 2.5h and 3.5h with the time that CVD carries out Carbon deposition；CMS-5 progress Carbon deposition processing useless.
Select molecular sieve, active carbon, the above-mentioned preparation of active carbon fibre peacekeeping 31 kinds of carbon molecular sieve etc. of sorbent material into
Row xenon adsorbs comparative experiments.Experiment test is carried out using xenon Dynamic Adsorption through transmission technique.Specific experiment process and method are as follows:
(1) sorbent material is filled in 70cm long, in 1/2 inch of stainless steel tube packed column, packed column both ends 1cm is by interior
Installation absorbent cotton and Vented metal pad outward, stainless steel tube outer wall package power be greater than 200W, 4m long heating tape and install temperature additional
Control device.
(2) packed column filled is de-gassed, treatment conditions are 200 DEG C, blow under 50mL/min condition of nitrogen gas
It sweeps 30 minutes.
(3) controlling column flow on gas source is 1200mL/min, and xenon in adsorption column tail gas is measured under the conditions of 25 DEG C of room temperature
Volume by volume concentration with time of break-through variation relation, with half time of break-through (t of xenon0.5, i.e. C/C0Corresponding air-flow stream when=0.5
Spend the time) length evaluates the xenon absorption property of packing material.
(4) using the volume by volume concentration of gas chromatography-mass spectrography measurement xenon；
It is macroscopically non-adsorbable to xenon to have 8 kinds in 31 kinds of adsorbents being related to of experiment, including CMS-1, CMS-6 and
CMS-7；Absorption property has 3 kinds significantly better than certain active carbon CF1450's, is CMS-2, CMS-3 and CMS-4 respectively；Absorption property
With CF1450 is comparable 7 kinds, including CMS-5.
For benefit of the invention is further intuitively presented, that is, the xenon absorption property of adsorbent greatly improved, experiment is chosen
Three kinds of materials of carbon molecular sieve TianJin, CMS-2 carbon molecular sieve and CF1450 active carbon of certain better performances, have carried out the suction of xenon
Attached breakthrough experiment.Specific experiment process is as follows: 3 kinds of adsorbents being loaded in Ф 12 × 1000mm stainless-steel tubing pillar, by de-
After gas disposal, under the conditions of absorption column temperature is 25 DEG C, gas source and flow amount is 400mL/min, measurement xenon is inhaled in the above a variety of materials
Xenon Dynamic Adsorption in attached column penetrates behavior, and unstripped gas is the gaseous mixture of xenon and nitrogen, and wherein the volume by volume concentration of xenon is
0.14ppm (V/V), upper prop gas pressure are 3.2 atmospheric pressure.Test result such as Figure 14.Abscissa is adsorption time in figure
(min), ordinate is the penetrance of xenon, i.e., the ratio between the volume by volume concentration of xenon in tail gas and unstripped gas.The result shows that CMS-2 carbon point
The performance of son sieve Dynamic Adsorption xenon is much better than two kinds of materials of TianJin and CF1450.
CMS-2 is prepared by following methods: including preparing material, material activating, charing process and carbon deposit process,
It prepares material and carbon deposit is that conventional preparation method, material activating and charing process are completed by following steps, by preparation
Material, which is placed in furnace, is heated to 300 DEG C, is passed through nitrogen, then be warming up to 850 °, constant temperature 60min, makes material at this temperature
Hole is carbonized and formed, nitrogen is recycled to bring hydro carbons or alcohols organic compound in furnace into, the carrier band time for controlling nitrogen is 1
To 2.5 hours, makes surface of material carbon deposit plug-hole, taken out after being cooled to room temperature.
After CMS-2 carbon molecular sieve characterization, show that its specific surface area is 380m2g-1, apparent density 0.6g/cm3, micropore
Mean pore radius is 0.5nm (HK), micropore volume 0.15cm3g-1。
As can be seen from Figure 16, in order to realize the overall volume of desorption under high temperature and reduction device and realize modularized design,
Carbon molecular sieve packed column includes outer housing, inner housing and absorption pole unit 17 in the present embodiment, and outer housing includes upper outer shell 1
And the lower housing body 8 mutually fastened with upper outer shell 1, the two are fastened after fastening with sunk screw 2.Inner housing includes interior case
Body 11 and interior case lid 18, interior case lid 18 are fastened on internal box 11, and are fastened by pan head screw 16.Inner housing is set to shell
Internal portion, and heat insulation foam 6 is provided therebetween.
Adsorbing pole unit 17 includes the N grades of adsorption columns being serially connected, and the N grades of adsorption columns being serially connected are arranged side by side in interior case
In body 11, the same end of each adsorption column is provided with the first air inlet 71 and the first gas outlet 72, connects on the first air inlet 71
It is connected to air inlet pipe 73, air inlet pipe 73 is located at the end of column body and air inlet pipe close to the bottom of cylinder, two neighboring adsorption column
First gas outlet 72 of middle upper level adsorption column is connected to the first air inlet 71 of next stage adsorption column；The of first order adsorption column
First gas outlet 72 of one air inlet 71 and N grades of adsorption columns is in communication with the outside by tracheae.
Each absorption column outer wall winds heater strip 12, and (socket 9 is simultaneously equipped with the socket 9 connecting with heater strip for outer housing
It is connect with following electric fans)；Simultaneously in order to accelerate to radiate, the second end plate is set in one end along outer housing inner length direction
5 and first end plate 4, electric fan 3 is installed between the second end plate 5 and first end plate 4, the second end plate 5 is close to internal box 11, and the
It is provided with air outlet on two end plates 5, internal box 11 is relative to being provided with first window at the position of air outlet, when cooling, open electric wind
Fan, cooling air-flow enter internal box 11 by first window, cool down to cylinder.Second baffle can also be installed on first window
7, when cooling, cooling air-flow starts second baffle 7, and when closing electric fan, second baffle 7 is automatically fallen off, close to first window
Envelope.It is provided with the second window on interior case lid 18, the first baffle 19 that can be opened and closed, upper outer shell are installed on second window
The third window 21 communicated with the second window is provided on 1, electric fan is opened, and hot-air disturbance can start interior 18 second window of case lid
First baffle 19 on mouth, hot-air shed and are discharged from third window 21；When electric fan does not start, first baffle 19 is automatic close
Seal the second window.
In order to which xenon is concentrated step by step on packed column, above-mentioned first order carbon molecular sieve packed column, second level carbon molecular sieve are filled out
Fill column, third level carbon molecular sieve packed column, fourth stage molecular sieve packed column, level V carbon molecular sieve packed column size be followed successively by
3×Φ45×340mm、Φ20×450mm、Φ12×380mm、Φ6×6000mm、Φ6×300mm。
It can be seen from fig. 15 that stable xenon measurement component includes measuring device 39 and Signal acquiring and processing in the present embodiment
Module；Measuring device 39 passes through lead including tube body 31 and the temperature-sensitive element 34 being set to inside tube body 31, temperature-sensitive element 34
It is connect with Signal acquiring and processing module；Tube body includes air inlet 32 and gas outlet 33, and gas enters tube body by air inlet, is made
It obtains temperature-sensitive element resistance value to change, Signal acquiring and processing module acquires and handles resistance value information, and gas passes through outlet
Mouth enters filing bottle.
Its middle tube body 31 can be a Stainless steel tee, and two transverse ports of threeway are respectively as air inlet and outlet
Mouthful, temperature-sensitive element is placed in the another port of the threeway, one end of temperature-sensitive element, which is located in the lateral pipeline section of threeway, is located at gas
Lu Zhong, the other end of temperature-sensitive element are connect with by thermocouple lead 36 with the signal input part of signal output terminal 37, signal
The signal output end of output terminal 37 is connect with Signal acquiring and processing module.The tube body of Stainless steel tee is in the present embodiment
Length is 20~40mm, and internal diameter is 3~6mm；Temperature-sensitive element is E type thermocouple.
The principle of the invention:
Air removes water membrane module and hollow fiber film assembly combination pretreatment through doughnut, and warp first is empty except moisture film removes
Most steam in gas, using more efficient steam, the oxygen, titanium dioxide removed in air of doughnut nitrogen-rich film component
Carbon and part nitrogen；The basic principle of gas membrane Seperation Technology is the infiltration that each component penetrates film under pressure promotion in mixed gas
Saturating rate difference is to realize the separation between each component.Gas separation membrane module separates the performance of concentration xenon not only from air
It is related with the characteristic of membrane module itself, it is also closely related with the Engineering operation parameter in application process.The present invention is ground by experiment
Study carefully, finds same membrane module under the conditions of different operation air-flow ratios, the concentration performance difference of xenon is very big；The film group of same model
For part under the conditions of different combined applications, the concentration performance of xenon also has very big difference；The membrane module combined application of different model
Benefit is evident greater than single branch or the benefit of same model membrane module combined application.
Pretreated gas is adsorbed xenon therein by carbon molecular sieve at room temperature, is adsorbed on the xenon on carbon molecular sieve in height
It is desorbed under warm (180 DEG C -300 DEG C), the xenon of desorption is adsorbed again on secondary carbon molecular sieve column at room temperature, is used in total
4 grades of carbon molecular sieve adsorption columns adsorption-desorption step by step；When desorption, by controlling gas circuit, it will be handled through film drier and membrane separator
Gas afterwards is as purging carrier gas；Using two sets of first order adsorption column alternate samples in parallel, switch Tb1 after Ta1 adsorption saturation
Absorption, while Ta1 desorption and regeneration switch Ta1 absorption, while Tb1 desorption and regeneration, are repeated, protect after Tb1 adsorption saturation
It is continuous to demonstrate,prove adsorption process；
After the completion of sample preparation, online stable xenon detection is carried out using stable xenon measurement component, because gas with various is in phase
Thermal coefficient under synthermal has differences, and for the mixed gas of binary composition, apparent thermal conductivity is with binary composition
The variation of volume by volume concentration and change.So when binary mixture (being nitrogen and xenon in the present invention) passes through temperature-sensitive element,
It can cause the variation of temperature-sensitive element resistance value.It, can be by the volume ratio of xenon in binary composition using signal acquisition and output module
Concentration (C/%, Xe+N2) connected with resistance variations amplitude, to achieve the purpose that detect binary composition composition.Resistance becomes
Change amplitude to acquire and convert by data, is presented in the form of pulse peak height (h), following formula is met with the variation relation of C
(under specified conditions):
H=1531-9.22 × C
The course of work of the present invention are as follows:
To the air come out from compressor by doughnut except moisture film is dried, then it is rich by nitrogen-rich film progress xenon
Collection, then gas enters surge tank, valve Va11 and Va13 is first turned on, so that gas enters first order carbon molecular sieve packed column
Ta1 is adsorbed, and adsorption time and gas flow are controlled, rear to close valve Va11 and Va13, open MFC1, Va12, Va14,
V21 and V22, while first order carbon molecular sieve packed column Ta1 is heated, so that gas is solved from first order carbon molecular sieve packed column Ta1
It inhales, second level carbon molecular sieve packed column T2 adsorbs gas, controls gas flow and adsorption took time, rear to close
MFC1, Va12, Va14 and V22, open MFC2, V31, V32, and heating second level carbon molecular sieve packed column T2 is desorbed, controlled
Flow so that gas enters third level carbon molecular sieve packed column T3, lasting absorption after a certain period of time, close MFC2, V31, V32,
MFC3, V41, V42 are opened, third level carbon molecular sieve packed column T3 is heated, control flow makes gas enter molecular sieve packed column
T4 is purified, and after removing interfering component such as radon gas, is closed V42, is opened V51 and V52, and xenon introducing fourth stage carbon molecular sieve is filled out
It fills column T5 to be adsorbed, absorption after a certain period of time, closes MFC3, V51 and V52；T5 is heated, diaphragm pump, V53, V2 and V4 are opened,
Pulsed opens MFC5, will be transferred in measurement source capsule 58 from the pressurization of the gaseous mixture for the xenon and nitrogen that T5 is desorbed.Xenon from
Measure source capsule 58 to filing bottle 60 spread during, by stable xenon measure component 59 whether worked normally come monitoring system and
Quantitative measurment is carried out to gas composition, if the volume by volume concentration of xenon deviates normal value ± 20%, i.e. decision-making system is operating abnormally.
Sampling when can also two sampling processes carry out simultaneously, i.e., the first order carbon molecular sieve in A sampling unit is filled out
When filling column Ta1 parsing, the Vb11 and Vb13 of B sampling unit are opened, so that the first order carbon molecular sieve packed column of B sampling unit
Tb1 absorption.A, two sampling units of B and purifying source unit, have independent electric-control system respectively, can independently transport
Row；
Whole system has manually and automatically two kinds of operational modes, under automated system operation mode, has two kinds of operations
Mode, first is that 1 sample of acquisition in every 12 hours, second is that 1 sample of acquisition in every 24 hours, can be selected before system operation with menu mode
Setting；
It is provided with the touch screen for carrying out human-computer interaction on purifying source module panel processed, people can be carried out by the touch screen
Machine interactive controlling can also realize human-computer interactive control by host computer, can also be configured with remote communication module in system, can
To realize that the remote interaction to system controls.
Claims (10)
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| CN111874881A (en) * | 2019-06-27 | 2020-11-03 | 南京工业大学 | Method for purifying xenon by using DD3R molecular sieve membrane |
| CN112557158A (en) * | 2021-02-28 | 2021-03-26 | 中国工程物理研究院核物理与化学研究所 | Separation, purification and collection device for xenon in air sample |
| CN115979779A (en) * | 2023-01-10 | 2023-04-18 | 浙江恒达仪器仪表股份有限公司 | Control method of xenon background multi-mode enrichment analysis device |
| CN116594053A (en) * | 2023-07-18 | 2023-08-15 | 清华大学 | Group separation system and device for transuranic alpha nuclides, 90Sr and 137Cs in radioactive solution |
| CN117531333A (en) * | 2024-01-08 | 2024-02-09 | 西安瑞恒测控设备有限公司 | Filtering system of gas chromatograph in krypton-xenon detection |
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| CN116594053A (en) * | 2023-07-18 | 2023-08-15 | 清华大学 | Group separation system and device for transuranic alpha nuclides, 90Sr and 137Cs in radioactive solution |
| CN116594053B (en) * | 2023-07-18 | 2024-01-19 | 清华大学 | The radioactive solution contains transuranic alpha nuclide, 90 Sr and 137 cs separation system and device |
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