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 PDF

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CN109665506A
CN109665506A CN201811572636.8A CN201811572636A CN109665506A CN 109665506 A CN109665506 A CN 109665506A CN 201811572636 A CN201811572636 A CN 201811572636A CN 109665506 A CN109665506 A CN 109665506A
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xenon
packed column
molecular sieve
gas
level
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CN109665506B (en
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陈占营
刘蜀疆
黑东炜
常印忠
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BEIJING RADIONUCLIDE LOBOROTARY
Northwest Institute of Nuclear Technology
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BEIJING RADIONUCLIDE LOBOROTARY
Northwest Institute of Nuclear Technology
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • C01B23/001—Purification or separation processes of noble gases
    • C01B23/0036—Physical processing only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/306—Active carbon with molecular sieve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/001—Physical processing by making use of membranes
    • C01B2210/0012—Physical processing by making use of membranes characterised by the membrane
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    • C01B2210/0017—Carbon-based materials
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    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0029—Obtaining noble gases
    • C01B2210/0037—Xenon
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
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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

Atmosphere xenon enrichment and purification method, device and the method for preparing carbon molecular sieve
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)

1. a kind of atmosphere xenon enrichment and purification method, which comprises the following steps:
1) air pretreatment:
Steam, oxygen, carbon dioxide and part nitrogen in air are removed using film drier, membrane separator, in air Xenon carries out initial concentration；Wherein film drier using doughnut remove water membrane module, membrane separator 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 include using three kinds of different models packed column according to Secondary to carry out the desorption of three-level room temperature absorbing high temp to step 1) treated gas, 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, sample is carried out to the gas after desorption Preparation；
5) online stable xenon detection
Online stable xenon detection is carried out to the gas after preparation, sample collection is filed after the completion of detection.
2. atmosphere xenon enrichment and purification method according to claim 1, it is characterised in that:
The doughnut removes water membrane module, and the UM series of model Ube UBE removes moisture film, including UMS-B10 and UM- C10；
The doughnut nitrogen-rich film component is NM-C05A, NM-B10A, NM-C07F, NM-C10F or NM-510F.
3. atmosphere xenon enrichment and purification method according to claim 2, it is characterised in that:
The carrier gas of all desorption processes is the pretreated gas of step 1)；It is in parallel using two in first order concentration process First order packed column alternating sorbent and desorption；
Membrane separator is sequentially connected in series using NM-510F, NM-C10F and NM-B10A；
The adsorbent filled in the 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。
4. atmosphere xenon enrichment and purification method according to claim 2, it is characterised in that: desorbed using first order packed column When, control gas flow is 500-600mL/min, and control first order carbon molecular sieve temperature is 260 DEG C -300 DEG C；Utilize the second level When packed column desorbs, control gas flow is 40-50mL/min, and control second level carbon molecular sieve temperature is 260 DEG C -300 DEG C；Benefit With third level packed column desorb when, control gas flow be 30-35mL/min, control third level carbon molecular sieve temperature for 260 DEG C- 300℃；
When being desorbed using level V packed column, control gas flow is 10-20mL/min, and control level V carbon molecular sieve temperature is 180℃-300℃。
5. a kind of xenon device for enriching and purifying for realizing any atmosphere xenon enrichment and purification method of claim 1-4, including according to Air supply system, sampling unit, purifying source unit and the on-line measurement collector unit of secondary connection；
It is characterized by: the air supply system includes by the sequentially connected filter of pipeline, compressor, film drier, film point From device, surge tank；Wherein film drier removes water membrane module using doughnut, the membrane separator by M branch same model and/or The doughnut nitrogen-rich film component of different model is connected and/or parallel connection, and M is more than or equal to 2；
The sampling unit includes first order packed column；
The purifying source unit processed includes purification unit and sample preparation unit, and the purification unit includes passing through pipeline and valve Second level packed column, third level packed column, fourth stage molecular sieve packed column, the level V packed column being sequentially connected in series；The sample Preparation unit includes the diaphragm pump being sequentially connected in series by pipeline and valve and measurement source capsule；Level V packed column and diaphragm pump enter Mouth end is connected to by pipeline and valve；
The on-line measurement collector unit includes vacuum pump, stable xenon measurement component and filing bottle；
The outlet of the first order packed column is connected to by pipeline and valve with the entrance of second level packed column；
The outlet end of the measurement source capsule is connect with the sample inlet end of stable xenon measurement component；
The outlet end of the filing bottle is connect with the sample export end of stable xenon measurement component；
The vacuum pump measures component with filing bottle and stable xenon by valve and connect；
The first order packed column, second level packed column, third level packed column, fourth stage molecular sieve packed column, level V filling Column is respectively connected with the exhaust valve being in communication with the outside；
It is provided with the Mass flow controllers of control gas flow on the pipeline, measures the pressure sensor of airline pressure.
6. xenon device for enriching and purifying according to claim 5, it is characterised in that: the doughnut of film drier removes moisture film group The UM series of part, model Ube UBE removes moisture film, including UMS-B10 and UM-C10；
The doughnut nitrogen-rich film component is NM-C05A, NM-B10A, NM-C07F, NM-C10F or NM-510F.
7. xenon device for enriching and purifying according to claim 6, it is characterised in that: the stable xenon measurement component includes measurement Device and Signal acquiring and processing module；
The measuring device includes tube body and the temperature-sensitive element for being set to tubular body, and the temperature-sensitive element passes through lead and letter Number acquisition is connect with processing module；The Signal acquiring and processing module is for acquiring and handling real-time temperature-sensitive element 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 and filing The arrival end connection of bottle, gas enters tube body by air inlet, so that temperature-sensitive element resistance value changes, signal acquisition and place Reason module acquires and handles resistance value information, and gas enters filing bottle by gas outlet；
Carbon molecular sieve is filled in packed column, 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 mean pore radius be 0.5nm (HK), Micropore volume is 0.15cm3g-1。
8. xenon device for enriching and purifying according to claim 7, it is characterised in that: the outlet of the surge tank by pipeline and Mass flow controllers are molecular sieve filled with first order packed column, second level packed column, third level packed column, the fourth stage respectively The entrance connection of column, level V packed column；The sampling unit includes identical by two specifications of pipeline and valve in parallel And the first order packed column of alternating sorbent desorption.
9. according to any xenon device for enriching and purifying of claim 5-8, it is characterised in that: packed column includes shell and is located at The absorption pole unit of enclosure interior；
The 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；Air inlet and gas outlet, the air inlet and outlet are provided on each adsorption column cylinder Mouth is respectively positioned on one end of cylinder；In two neighboring adsorption column, the gas outlet of upper level adsorption column and the air inlet of next stage adsorption column Mouth 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；
The shell includes inner housing and the outer housing for wrapping up inner housing；Insulating assembly is equipped between inner housing and outer housing；Institute Absorption pole unit is stated to be 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.
10. a kind of method for preparing carbon molecular sieve in claim 4 or 7, 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 heated to, nitrogen is passed through, then is warming up to 850 °, at this temperature constant temperature 60min, material is carbonized and forms hole Gap 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, makes Surface of material carbon deposit plug-hole, takes out after being cooled to room temperature.
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