CN106693704A - Enrichment separation method of hydrogen isotopes through displacement chromatography - Google Patents
Enrichment separation method of hydrogen isotopes through displacement chromatography Download PDFInfo
- Publication number
- CN106693704A CN106693704A CN201710081992.9A CN201710081992A CN106693704A CN 106693704 A CN106693704 A CN 106693704A CN 201710081992 A CN201710081992 A CN 201710081992A CN 106693704 A CN106693704 A CN 106693704A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hydrogen
- separation
- sieve column
- column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/28—Separation by chemical exchange
-
- 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
Abstract
The invention discloses an enrichment separation method of hydrogen isotopes through displacement chromatography. The enrichment separation method comprises the following steps: (1) reducing the temperature: making a molecular sieve column into a spiral coil, loading a container with liquid nitrogen, wholly immersing the molecular sieve column into the liquid nitrogen, and enabling the temperature of a molecular sieve to be maintained to be the temperature of the liquid nitrogen; (2) performing adsorption: enabling hydrogen to be introduced into the molecular sieve column, measuring the quantity of the hydrogen introduced into the molecular sieve, and after the gas pressure in the molecular sieve reaches to a definite pressure, stopping introducing the hydrogen; (3) performing warming for separation: upwards lifting the spiral molecular sieve column, so that the molecular sieve column is separated from the liquid surface of the liquid nitrogen, heating the molecular sieve column with air, and controlling the speed of the molecular sieve column being lifted out of the liquid surface of the liquid nitrogen to be 0.5-5 cm/min; and (4) performing detection and collection: oxidizing hydrogen into liquid water through an oxyhydrogen compositor at a rear end for the hydrogen discharged from the molecular sieve column, and then detecting the deuterium abundance in the liquid water through a magnetic mass spectrometer. According to the enrichment separation method of tritium through displacement chromatography disclosed by the invention, changes in the controlled process of reducing the temperature and raising the temperature have continuity, the hydrogen isotope separation efficiency is extremely high, and the separation effects are good.
Description
Technical field
The invention belongs to separation purifying technique field, it is related to a kind of isotope separation method, more particularly to a kind of same position of hydrogen
Plain separation method.
Background technology
The fusion reactor of superconducting Tokamak is considered as the fusion reactor of most practical application potentiality, can be with
The green nuclear energy technology of extremely low radiation pollution is realized, global every country has all put into substantial amounts of manpower and materials and answered
With research.As the hydrogen isotope of fusion reactor fuel --- the demand of deuterium and tritium in application is studied is very big, and
The yield of the application once thermonuclear fusion reactor formally puts into production, existing deuterium and tritium will turn into limitation thermonuclear reactor should
Key factor.
Hydrogen isotope deuterium and tritium are typically all to be uniformly dispersed in natural hydrogeneous raw material, are also contained in common hydrogen
Micro tritium.And common hydrogen is with its distinctive high-purity feature, the deuterium required for being directly isolated to obtain fusion reaction
And tritium, existing part research shows that dodging separation method by liquid can obtain the deuterium and tritium of higher degree, but specifically separates
The method also scheme without definite industrialized implementation.
Again with the efficiency highest of cryogenic rectification hydrogen isotope separation method in concentration and separation technology, not only with treating capacity
Greatly, the larger advantage of facility compact separation factor, and the cost produced in separation process is relatively low, and application potential is big.It is existing
In concentration and separation technology, the part mainly including application response device, electromagnetic heater etc., in course of reaction the need for separation unit
Part is heated and regenerated, wherein the matching relationship between the heating part applied and reactor is mainly directly heat comprehensively.
Programming rate during directly heating for system is very fast, but is comprehensive total event heating when heating,
Cause to lack the controllable effect of continuity for the rate of departure of the hydrogen isotope of system when separating.In separation process, for items
The Adjustment precision of released state parameter is relatively low, only from it is big analyze cryogenic rectification separation process in theory in separation effect
Really, comprehensive accurate research when separation for cryogenic rectification, carries for the efficiency in later actual popularization and application
Rise research and help limited, in other words, it is impossible to preferably play the separative efficiency that cryogenic rectification separates hydrogen isotope.
The content of the invention
Lack feasible efficient hydrogen isotope separation technology in the prior art it is an object of the invention to overcome, there is provided a kind of
Displacement chromatography hydrogen isotope enrichment and separation method.The method of the present invention can be efficiently quickly isolated from natural pure hydrogen
The isotope of hydrogen --- deuterium and tritium, with implement it is simple and convenient efficient the characteristics of, can effectively improve deuterium tritium separation and concentration be stranded
Difficult problem, the reactive fuel of abundance is provided for thermonuclear fusion reactor.
In order to realize foregoing invention purpose, the invention provides following technical scheme：
A kind of method of displacement chromatography hydrogen isotope concentration and separation, comprises the following steps：
(1) lower the temperature：Molecular sieve column is fabricated to helical coiled tube, liquid nitrogen is contained in a container, molecular sieve column all soaks
Enter in liquid nitrogen, allow molecular sieve temperature to be maintained at liquid nitrogen temperature；
(2) adsorb：To hydrogen is passed through in molecular sieve column, metering is passed through the amounts of hydrogen of molecular sieve, when the air pressure in molecular sieve
Reach after certain pressure, stopping is passed through hydrogen.Wherein, air pressure is preferably controlled to an atmospheric pressure, for the requirement of equipment
It is lower, it is more easy to implement, and separating effect is preferable.The hydrogen contains the deuterium/tritium of natural abundance.
(3) heat up and separate：Spiral helicine molecular sieve column is lifted upwards, molecular sieve column is departed from liquid nitrogen liquid level, using sky
Gas is heated to molecular sieve column.Preferably slow lifting molecular sieve column, makes the temperature of molecular sieve column slowly raise.In lifting
During, spiral helicine molecular sieve column realizes thermal release by air heating, especially can be achieved on heat stepwise so that point
The temperature section of son sieve post gradually rises.Control molecular sieve column to propose that the speed of liquid nitrogen liquid level is 0.5-5cm/min, preferably lift
Speed is 1-2.5cm/min, the slow heating process for completing molecular sieve column.
(4) detect and collect：For the hydrogen that molecular sieve column is discharged, it is by oxidation of hydrogen using hydrogen oxygen recombination device in rear end
Aqueous water, then uses magnetic Mass Spectrometer Method D abundance therein.Detection splitter (molecular sieve column) of the hydrogen by varying number
The concentration of deuterium afterwards, the efficiency that every one-level pillar to hydrogen deuterium separate is determined with this.Clearly separate column length, filler etc. because
Element to splitter for can just optimize design after the influence of segregation ratio, it is ensured that required for being obtained when carrying out deuterium enriched
The product of concentration.
Displcement chromatography deuterium/tritium enrichment and separation method of the invention, has been arranged to helical coiled tube structure, outward by molecular sieve column
Shape controls the temperature of molecular sieve column in extremely low level, then by lifting similar to spring first with low temperature liquid nitrogen cooling
Mode cause that molecular sieve column slowly leaves liquid nitrogen liquid level, using air heat complete for molecular sieve column heating separate, lead to
The temperature change for changing molecular sieve pillar is crossed, the centrifugation for the isotope in hydrogen is realized.The hydrogen being wherein passed through is
The abundance of the hydrogen of deuterium, tritium containing natural abundance, or the deuterium by certain enrichment treatment and/or tritium is more than general
Natural hydrogen Artificial gas' (manually pre-processing hydrogen), or nuclear reactor accessory substance containing deuterium, gas containing hydrogen tritide.Because,
The temperature of molecular sieve is controlled by liquid nitrogen and air during separation, and the external condition of control is relatively simple, while control
Cooling and temperature-rise period in change there is continuity, it is possible to achieve temperature consecutive variations ensure that the efficiency of separation so that
Separate is better.Wherein, the molecular sieve column is filled with the tubular posts of molecular sieve.The section shape of molecular sieve column pipe
Shape can be the shapes such as circle, ellipse, rectangle, preferably circular, and the amount for filling molecular sieve is maximum, and structure is stablized the most.
Further, in step (1), the molecular sieve column is prepared from molecular sieve filled in stainless steel tube.Will
Molecular sieve is bonded compressing post package in column, the helical pipe of strip, and the continuous molecular sieve column of composition is to realize
The key factor of hydrogen isotope separation, control molecular sieve column have continuous long pipeline can realize continuous multi-stage separate tower structure
The concentration and separation for extremely low concentration deuterium is completed, and can realize that the deuterium of high concentration is further purified enrichment.Preferably may be used
The molecular sieve material that filling molecular sieve is formed by bonding is carried out with using helix tube, mixing packed density more preferably, can more fill
The natural hydrogen of absorption for dividing, completes for deuterium and/or the separation and concentration of tritium.
Further, in step (1), the molecular sieve of described molecular sieve column filling be one kind in A, X or Y type molecular sieve or
Several mixtures.Preferably, the molecular sieve is the molecular sieve of A and/or X-type, is more suitable for gas and dries, separates, purifies
Work.Molecular sieve is artificial synthesized zeolite, the crystal of silicate, and into white powder, granularity is 0.5 micron to 10 microns, point
Son sieve forms many holes after heating loses the crystallization water in crystal, and the size in its aperture is close with molecular diameter and non-
It is often uniform.During molecular sieve is all kinds of adsorbents, the class adsorbent that pore-size distribution is most concentrated.It can inhale the molecule less than aperture
Enter in hole, the molecule more than aperture is kept off outside hole, therefore with very strong adsorption selectivity.Due to the original of hydrogen isotope
Protonatomic mass is different, and its suction-operated in molecular sieve has small difference, using a large amount of continuous molecular sieve columns to natural
Hydrogen carries out the separating treatment of continuous several times, and this small difference is amplified, and can cause the hydrogen isotope in molecular sieve column
Quickly separate.
Further, in step (2), the hydrogen is natural hydrogen, wherein the deuterium/tritium containing natural abundance, if
The purpose of enrichment can also be realized as raw material using the hydrogen rich in deuterium/tritium, and is enriched with the deuterium in the rich deuterium hydrogen for obtaining
Content ratio it is higher.Deuterium containing 150ppm in general natural hydrogen, higher degree can be obtained by enrichment treatment
Rich deuterium hydrogen, or even pure deuterium.
Adsorption technology is widely used in fusion reactor deuterium, tritium and fuel recycle, such as doughnut plasma discharge gas
Pumping, plasma discharge gas in tritium cleaning, containing tritium impurity go tritiated treatment, chromatography of gases hydrogen isotope separation and
First analysis and the extraction of high-purity gas etc..The cryogenic absorption thermoisopleth of adsorbent is critically important design parameter, with absorption etc.
Warm line can very easily estimate the adsorption capacity of adsorbent bed, adsorption equilibrium pressure etc..
Further, it is preferred that in step (2), during being passed through hydrogen, first to hydrogen is passed through in constant volume container, then
Hydrogen is passed into molecular sieve column from constant volume container again, to realize that accurate quantification is passed through the purpose of hydrogen.Preferably, using point
The method for walking ventilation, to hydrogen is passed through in molecular sieve, control air pressure is not so high, it is to avoid hydrogen penetrates container.Because it is fixed to be passed through
Hold in container, realize the hydrogen injection of intermediary's formula, be segmented into multipass constant volume container injection hydrogen, hydrogen was passed through
Control the gas pulsation of constant volume container smaller in journey, prevent hydrogen from being compressed so that the total amount meter of the hydrogen of injection molecular sieve column
Calculate more accurate, it also avoid the problem of high pressure hydrogen infiltration.
Specific operating process is as follows：The amounts of hydrogen of molecular sieve is passed through to accurately measure, one constant volume is set in front end
Container.Hydrogen is first passed through constant volume container, pressure value now is recorded, then again by constant volume container to being passed through in molecular sieve
Hydrogen.In order to guarantee normally to be passed through hydrogen and external hydrogen pressure is not so high, using the method for substep ventilation.Ensure fixed
The pressure held in container is consistently higher than an atmospheric pressure, when the pressure drops, toward the inflation of constant volume container.Record supplement gas every time
Pressure difference value that is front and rear and being ventilated to molecular sieve.Due to environmental temperature fluctuation very little, it is possible to be considered in isoperibol.Institute
It refers to during being passed through hydrogen, to be passed through hydrogen to molecular sieve column by constant volume container several times to state substep ventilation, and statistics is multiple
Constant volume container gas pressure change numerical value, with reference to the volume of constant volume container, calculating is passed through the total amount of gas.
When the pressure in detecting molecular sieve column is more than an atmospheric pressure, it is believed that now uptake through saturation.Record
Under all pressure drop Δ P now, the amounts of hydrogen of absorption can be calculated.The volume of constant volume container is multiplied by by calculating pressure drop Δ P,
The amounts of hydrogen of absorption can be quickly calculated, control gas pressure is relatively low, no more than an atmospheric pressure, it is ensured that measurement result
Accurate reliability.
Further, described molecular sieve column includes many-level molecule sieve post, and continuous point is set between many-level molecule sieve post
Son sieve post.End to end structure can be arranged between many-level molecule sieve post, when first order molecular sieve post completes adsorbing separation
After, gas proceeds separating treatment into rear stage molecular sieve column.Being so designed that can be according to separate situation, separation
The different molecular sieve column combining structure of purpose adjusted design, reaches the adjustment control of the overall continuous length for molecular sieve column.
Separative efficiency higher can be realized by increasing many-level molecule sieve rod structure.Preferably, flexible pipe is used between many-level molecule sieve post
Couple together, it is possible to achieve stepped heating separating treatment.
Further, step (3) heats up and separates：
Intensification separation process is as follows：
Heated using the mode of lifting (lifting), molecular sieve column is slowly departed from liquid nitrogen, temperature is gradually risen.Molecule
The hydrogen adsorbed in sieve starts release after molecular sieve column departs from liquid nitrogen temperature rising.One end valve is closed, after desorbing gas
Pressure difference, the past end molecule sieve post starts to lift successively, and Q2 successively the past end molecule is sieved into post toward driveing in the pillar of rear end.Plus
Radiation heat transfer can be completed thermal process at room temperature, and energy consumption is low.
Different pull rate can obtain different separative efficiencies.Optimal work parameter is obtained by Test Summary.Experiment card
It is bright, because molecular sieve adsorption temperature is very low, even if so in winter, room temperature is still present the very big temperature difference with the temperature of 20K, divides
Separation process is capable of achieving after liquid nitrogen is departed from from post.
Molecular sieve is being saturated with and is being heated to more than liquid nitrogen temperature afterwards, protium is preferentially discharged, next to that deuterium, is finally only tritium.
For 5A molecular sieves, the separation temperature of molecular sieve is -100 DEG C, and heating system only needs to be arrived by lifting splitter
On liquid nitrogen liquid level, splitter heat stepwise is capable of achieving by air heating.The ascending suit in layer of splitter.Examination
Test initial, original gas are filled with the splitter of most inner side.It is then lifted out splitter.Respectively according to 1cm/min, the speed of 2cm/min
Degree is lifted, and molecular sieve column departs from liquid nitrogen in lifting process, is heated by upper air, is heated up naturally.Until all of post
Body (molecular sieve column) leaves liquid nitrogen surface.The hydrogen of first pillar (molecular sieve column) is completed and separated for the first time.And can be by
Second pillar (molecular sieve column) absorbs.
Further, the molecular sieve column has multiple, and multiple molecular sieve columns are interconnected, isolated from previous molecular sieve column
Hydrogen can reach the effect for being continuously separated enrichment into next molecular sieve column.
A pillar, the separating effect of two pillars and three pillars to isotope are tested respectively.Experiment shows, single post
Sub (molecular sieve column), the deuterium of the natural abundance of 150ppm is by after separation, enrichment end has reached 650ppm, two pillars in hydrogen
When reached 1000ppm, reached 2300ppm during three pillars.
Can continue Optimum Experiment process by changing lifting speed, finally give optimal intensification sequence (speed).Examination
Testing can continue checking separation column length, mode of heating, influence of the firing rate to separating property.
Further, molecular sieve column has been designed to helical disk tubulose, and the molecular sieve column of helical disk tubulose has longer length
Degree, while volume is maintained at less level, easier can be put into liquid nitrogen tank, and cooling treatment is carried out using liquid nitrogen.And
And, spiral helicine molecular sieve column can also carry out non-contact thermal by intermediate frequency coil, and spiral helicine structure causes molecular sieve
The heating-up temperature of each end position of post is consistent substantially, overcomes the temperature difference to influence, and separating effect is more preferably.
Test objective is the separating effect in order to verify molecular sieve heat stepwise method to hydrogen isotope.The absorption of molecular sieve
Amount has been described in the literature, but according to different particle diameter and type of feed, actual uptake still allow it needs to be determined that.First
It needs to be determined that the Q2 amounts of sum are saturated with actual experiment in molecular sieve.Q2 represents the hydrogen isotope gaseous mixture scale of construction, is conventional expression shape
Formula.Can be estimated by the data in document, other test parameters are determined with this.
Further, the body material of manufacture molecular sieve column is stainless steel material, preferably 316 stainless steels.Corrosion resistance is excellent
It is good, while having preferable high-temperature behavior, disclosure satisfy that the temperature change Stress Control in molecular sieve column heating process so that point
Performance of the son sieve post when temperature programming is separate significantly improves.316 stainless steels can better meet molecular sieve column and separate
Cheng Zhong, the tolerance of variation of ambient temperature when separation for liquid nitrogen frozen and heating, being capable of more preferable holding meanss structure
Resistance to overturning, for improving separating effect and follow-up adjustment improves that to separate heating schedule/scheme more favourable.
Further, in step (4), during the hydrogen of test molecule sieve post discharge, the analyzing detecting method of use is indirect
Detection.Specifically, detection method is the hydrogen for first discharging molecular sieve column passes through hydrogen oxygen recombination device, by oxidation of hydrogen into liquid
Water, is then detected by nucleus n-ness spectrum.Using the method for indirect detection, can be by the precision of the detection and analysis of deuterium content in hydrogen
Bring up to the left and right of 5ppm.Accordingly, the mode sampled preferably during indirect detection is interval sampling, preferably fixed time interval
Sampling analysis.
After gas is separated, it is an important problem that accurate measurement how is carried out to the gas after separation.Due to
Under natural abundance, the concentration of deuterium is very low, unworkable by the way of gas-chromatography on-line checking after isolation.The above method,
During experiment, by hydrogen oxygen recombination device, by oxidation of hydrogen into aqueous water, then by magnetic Mass Spectrometer Method, it is right for separate to realize
The accurate detection analysis of the low concentration of elephant, the precision of detection and analysis can bring up to 5ppm.
Preferably, sampled using fixed time interval during sampling, then unification is detected water sample using nucleus n-ness spectrum.As a result
Show, by 2-3 separation, 2 kinds of splitters may be such that natural abundance is concentrated to more than 2000ppm.
Compared with prior art, beneficial effects of the present invention：
1. displcement chromatography tritium enrichment and separation method of the invention, is controlled, the external condition of control by liquid nitrogen and air
It is relatively simple, while the cooling of control has continuity with the change in temperature-rise period, it is possible to achieve temperature consecutive variations ensure
The ultrahigh in efficiency of cryogenic separation hydrogen isotope, it is ensured that separating effect is more preferably.
2. the molecular screen material selection application applied in displcement chromatography tritium enrichment and separation method of the invention is high-quality
Molecular screen material, for the good separating effect of hydrogen, can live again recycling, be capable of low cost realize hydrogen isotope point
From enrichment, the potentiality with high industrial applications.
Brief description of the drawings：
Fig. 1 is the schematic diagram of low-temperature displacement chromatography tritium concentration and separation technological system of the invention.
Marked in figure：1- constant volume containers, 2- molecular sieve column separators, 3- hydrogen oxygen recombination devices, 4- mass spectrographs, 5- vacuum
Pump.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
For the scope of above-mentioned theme of the invention is only limitted to following embodiment, all technologies realized based on present invention belong to this
The scope of invention.
Embodiment 1
Prepare molecular sieve column：
Prepare molecular sieve column when, from internal diameter for 12mm stainless steel tube as molecular sieve column agent structure.Make
After being well mixed with adhesive and 5A molecular sieves, it is filled into above-mentioned stainless steel tube, fills out after being filled with, will using bend pipe machine
Stainless steel tube bends to spiral coil structure, and the diameter of spiral coil is the size that can be put into liquid nitrogen tank, must both be tested
Required molecular sieve column.
Compared with general molecular sieve column filling mode, spiral coil structure of the invention has significantly saved molecular sieve column
Volume, it can be cooled down using liquid nitrogen more easily.
Displcement chromatography tritium concentration and separation：
Molecular sieve column is all immersed in the middle of liquid nitrogen, the temperature of molecular sieve column is reduced to the temperature of liquid nitrogen.To constant volume
Natural hydrogen (deuterium containing natural abundance) is injected in container, after constant volume container pressure stabilization, injection valve is closed, then opened
Valve between constant volume container and molecular sieve column, makes natural hydrogen be passed into molecular sieve column, after after stable gas pressure, shutoff valve
Door.Separation is started to warm up, and intensification separation process is that molecular sieve column is gradually proposed on liquid nitrogen liquid level, using liquid nitrogen ullage
Air heating molecular sieve column, realize the heating of splitter, lifting speed control is 1cm/min, slowly completes molecular sieve column
Heating process, what is first separated from molecular sieve column is protium, followed by deuterium and tritium, will be enriched with the isotope for obtaining and separately receive
Collect and detect isotope abundance therein.
It is dipped into the middle of liquid nitrogen by by molecular sieve column, liquid nitrogen is quickly cooled down to molecular sieve column, cooling speed
Degree is exceedingly fast, because the spiral coil structure of molecular sieve column makes its contact surface with liquid nitrogen big, good cooling results and it is fast.Spiral coil
During the molecular sieve column of structure is cooled down in liquid nitrogen, there is Quick-gasifying, the gas of formation in liquid nitrogen on the surface of molecular sieve column
Bubble can produce good stirring action to liquid nitrogen solution, promote the excellent that cools of liquid nitrogen.
Embodiment 2
X molecular sieve material, influence of the difference lifting speed for the separation of hydrogen isotope
Prepare the molecular sieve of X-type, extruded into strips after adding adhesive, be filled in the middle of molecular sieve column.By this molecular sieve
Post is all immersed in the middle of liquid nitrogen, and be totally submerged for molecular sieve column by liquid nitrogen, the temperature of molecular sieve column is reduced to the temperature of liquid nitrogen.
To natural hydrogen (deuterium containing natural abundance) is injected in constant volume container, constant volume container pressure reaches an atmospheric pressure and stabilization
Afterwards, injection valve is closed, the valve between constant volume container and molecular sieve column is then opened, natural hydrogen is passed into molecular sieve column
In, after after stable gas pressure, valve is closed, its hydrogen is sufficiently adsorbed on adsorption column.
Implement the separation and concentration of hydrogen isotope on separation equipment as shown in Figure 1, hydrogen is passed into constant volume first holds
In device 1, the Hydrogen Vapor Pressure in control constant volume container 1 is in an atm higher, the convenient exact value for calculating hydrogen usage.Open
Vavuum pump 5 is opened, by the evacuating air discharge in molecular sieve column in molecular sieve column separation equipment 2.Molecular sieve column is immersed into liquid nitrogen
In the middle of solution, molecular sieve column is cooled down using liquid nitrogen solution, until both temperature are equal.Using constant volume container 1
Hydrogen is passed into molecular sieve column several times, the pressure reduction numerical value of constant volume container 1 when record is passed through hydrogen each time.Until
Hydrogen Vapor Pressure in molecular sieve column reaches 1bar, calculates the overall presure drop numerical value of constant volume container 1, is multiplied by the volume of constant volume container 1, obtains
Go out to inject the total amount Q2 of hydrogen.Slowly lift molecular sieve column, it is partially disengaged liquid nitrogen solution, it is heated using air
Treatment, the gas for separating discharge from molecular sieve column is entered into hydrogen oxygen recombination device 3 from pipeline, and oxidation is converted into the aqueous solution, is utilized
Mass spectrograph 4 carries out mass spectral analysis, the deuterium content in the quick hydrogen for determining discharge, deuterium content component higher is collected, it is determined that most
Excellent separation and Extraction parameter.
Specific intensification separable programming is as follows：Intensification separation process is gradually to propose on liquid nitrogen liquid level molecular sieve column,
Molecular sieve column is heated using the air of liquid nitrogen ullage, the heating of splitter is realized, lifting speed control is 2cm/min, is delayed
The heating process of slow completion molecular sieve column.During separation, the hydrogen intermittent sampling that molecular sieve column is discharged, by hydrogen-oxygen
Recombiner, then sampling oxidation of hydrogen into aqueous water is detected by nucleus n-ness spectrum.As the change of disengaging time is (during heating
Between change), the isotope ratio in the gas of discharge changes, because first separated from molecular sieve column is protium, so
After be deuterium and tritium.Using the method for indirect detection, the precision that can will discharge the content detection analysis of deuterium and/tritium in hydrogen is improved
To the left and right of 5ppm, for the efficiency that research is separate, optimize separate method significant.
During lifting, when the molecular sieve column of helical disk tubulose leaves liquid nitrogen liquid level, lifting speed without too fast,
It is a-circle-by-a-circle continuously to leave when actually spiral coil leaves liquid nitrogen, although lifting speed is unhappy, but it is actual
The part of spiral coil heating is simultaneously many, and the speed for also allowing for heating is faster.Simultaneously because spiral coil has continuously
Structure, the low temperature of hydrogen isotope in molecular sieve column during lifting in the high temperature and liquid nitrogen of air heating part
Part quickly continuous flowing transfer, acts on so that actually wrapped in single molecular sieve column by a series of alternate analysis
Substantial amounts of centrifugation is repeatedly contained, can quickly reach and its prominent separative efficiency.
Contrast influence of various different pull rate for the separative efficiency of hydrogen isotope in molecular sieve column, period control
The pull rate of molecular sieve column is respectively 1cm/min, 2cm/min, 2.5cm/min, 4cm/min, 5cm/min, 8cm/min.Knot
Fruit finds that different pull rate have significant impact for the separation of the hydrogen isotope in molecular sieve column.According to lifting speed
Control situation, the improvement result of different separative efficiencies can also be realized because when lifting speed control when relatively low, in liquid
The separating effect of nitrogen interface is more prominent, and separating effect is better.Be have studied in embodiments of the invention specific different
As a result lifting speed is found when speed control is lifted in 2cm/min, single molecular sieve column for the influence of separating effect
Separative efficiency can reach the enrichment of 2364ppm.If lifting speed increases to 8cm/min, because molecular sieve column is in sky
The alternate analysis effect of gas and liquid nitrogen interface dies down, and actual separation factor deterioration, separative efficiency is deteriorated.
As shown in figure 1, being provided with a hydrogen oxygen recombination device (oxidation unit) before detecting instrument, deuterium body is oxidized to deuterated
Water, in order to measure amount containing deuterium therein with nucleus n-ness spectrum, so as to measure isotopic separation efficiency.
Embodiment 3
Analyze the influence of the internal diameter size for separative efficiency of different size of stainless-steel pipe
Prepare the molecular sieve of A types, be filled in 316 stainless-steel pipes of internal diameter 12mm and be made molecular sieve column.By this molecule
Sieve post is all immersed in the middle of liquid nitrogen, the temperature of molecular sieve column is reduced to the temperature of liquid nitrogen.Emptying molecular sieve is replaced with hydrogen
In gas, then treat in molecular sieve column, then vacuumize process, makes to keep vacuum in molecular sieve column.To in constant volume container
Natural hydrogen (deuterium containing natural abundance) is injected, after constant volume container pressure reaches an atmospheric pressure and stabilization, injection is closed
Valve, then opens the valve between constant volume container and molecular sieve column, natural hydrogen is passed into molecular sieve column, treats that air pressure is steady
After fixed, valve is closed.Start to warm up separation：Intensification separation process is gradually to propose on liquid nitrogen liquid level molecular sieve column, is utilized
The air heating molecular sieve column of liquid nitrogen ullage, realizes the heating of splitter, and lifting speed control is 5cm/min, slowly
Complete the heating process of molecular sieve column.During separation, the hydrogen that molecular sieve column is discharged passes through hydrogen oxygen recombination device, by hydrogen
Aqueous water is oxidized to, is then detected by nucleus n-ness spectrum, the same position of the hydrogen of molecular sieve column separation and concentration is determined by the result for detecting
The collection opportunity of element.
316 stainless-steel pipes of 6mm, 10mm, 14mm, 18mm are respectively from internal diameter, using same method filling point
Son sieve filler processing prepares pipe diameter molecular sieve column of different sizes, bends to the later molecular sieve column of coil shape
Coil radius are identical, and the length of each molecular sieve column is 45m.During experiment, whole molecular sieve columns are cold using liquid nitrogen
Freeze 20 minutes, the natural hydrogen (deuterium content 150ppm) of 1bar is passed through by constant volume vessel buffers, after adsorbing 10 minutes, according to
The speed of 2cm/min is lifted, and the deuterium content in the hydrogen of discharge is tested and analyzed during lifting.
Result shows that the molecular sieve column that the stainless-steel pipe of the caliber for employing different is prepared into is obtained for separation and concentration
The abundance of hydrogen isotope there is certain difference, the size of caliber is not significantly to correspond to separative efficiency, works as caliber
When excessive, the efficiency of separation is not good on the contrary, can improve the effect of separation if same control pipe with small pipe diameter within the specific limits
Rate, but more than certain scope after, separative efficiency begins to significantly reduce.So finally be control displcement chromatography in
The stainless-steel pipe internal diameter of the molecular sieve column of application is between 10-14mm, separating effect is preferable, and single is filled with Hydrogen Separation
Total amount is larger.
Further, wherein the heating hydrogen that obtains of separation initial stage separately collects the ground that purified hydrogen is needed to use as other
Side, it is to avoid emptying is wasted.
Embodiment 4
Displcement chromatography tritium concentration and separation, influence of the different size of molecular sieve filling for separative efficiency
First, using 2-5 microns of mixed molecular sieve as filler, it is filled in the stainless-steel pipe of internal diameter 12mm and is made
Molecular sieve column 45m long.Then this molecular sieve column is totally immersed into liquid nitrogen, allows molecular sieve temperature to be maintained at liquid nitrogen temperature.
Then, to the hydrogen containing natural abundance deuterium is passed through in molecular sieve column, the air pressure of molecular sieve column is controlled to reach 1bar, and keep permanent
Fixed 3 minutes, metering is passed through the amounts of hydrogen of molecular sieve, and after the air pressure in molecular sieve reaches an atmospheric pressure, stopping is passed through hydrogen
Gas.Then separation is started to warm up：Slow-paced according to 2cm/min proposes on liquid nitrogen liquid level molecular sieve column so that
The temperature of molecular sieve column raises (note：24 DEG C of room temperature).For the hydrogen that molecular sieve column is discharged, examined with analysis and detecting instrument in rear end
Survey the change of deuterium content ratio therein, detect molecular sieve column discharge hydrogen in deuterium content it is higher when, for example
More than 650ppm, corresponding rich deuterium hydrogen is collected.The separation for hydrogen isotope of the different Molecular sieve raw material of comparative analysis is imitated
The influence of rate.
Result shows when the Molecular sieve raw material of different-grain diameter is used, there is one for the separative efficiency of hydrogen isotope
Fixed influence, when particle diameter is less than 5 μm, the influence of separative efficiency is minimum, only when molecular sieve particle diameter is more than 15 μm
Time just occurs the decay of separative efficiency, and this is relevant with molecular sieve specific surface area reduction, simultaneously because being needed during preparing
Using to a certain amount of bonding agent, glued dose of the part surface of molecular sieve is destroyed when bonding, so particle diameter reduction is right
It is not notable in the castering action performance of specific surface area, preferably control the scope of particle diameter that preferably separation is can obtain at 3-8 μm
Efficiency, integrated cost more preferably 5-8 μm of molecular sieve.
Embodiment 5
Situation of realizing based on above-described embodiment 1-4, the optimal hydrogen isotope separation control method of research and design one
Prepare molecular sieve column：
From X-type molecular sieve raw material, the raw material of 2-3 μm of particle diameter is screened, add appropriate adhesive, be well mixed, then
It is filled in 316 stainless-steel pipes of internal diameter 12mm.By populated stainless-steel pipe bending machine, the radius of spin is processed into
1.5 meters of spiral bending tube (structure is similar to spring), 45 meters of stainless steel tube total length.
Hydrogen isotope separation：
(1) lower the temperature：Above-mentioned molecular sieve column is dipped into the container for containing liquid nitrogen, liquid nitrogen is flooded molecular sieve column, kept
Molecular sieve temperature is allowed within more than 10 minutes to be reduced to liquid nitrogen temperature.
(2) adsorb：Using a constant volume container for fixed volume, contain natural abundance deuterium to being passed through in molecular sieve column indirectly
Hydrogen.After the air pressure in molecular sieve reaches 1bar, stopping is passed through hydrogen, and metering is passed through the amounts of hydrogen of molecular sieve.
(3) heat up and separate：Spiral helicine molecular sieve column is lifted upwards, molecular sieve column is departed from liquid nitrogen liquid level, using sky
Gas is heated to molecular sieve column.Control molecular sieve column to propose that the speed of liquid nitrogen liquid level is 2.5cm/min, slowly complete molecule
The heating process of post is sieved, realizes that heat stepwise is separated by air heating.Hydrogen is heated in molecular sieve column and drives, isotope
, because the separation factor in molecular sieve is different from protium, both separative efficiencies in place of air heating are different, and hydrogen is dividing for deuterium
Continuously moved in son sieve post, form different separation factor control intensity.
(4) detect and collect：For the hydrogen that molecular sieve column is discharged, it is by oxidation of hydrogen using hydrogen oxygen recombination device in rear end
Aqueous water, then uses magnetic Mass Spectrometer Method D abundance therein.Determine the efficiency that first order molecular sieve post to hydrogen deuterium separate, calculate
Go out separation factor, the separative efficiency of molecular sieve filling for hydrogen isotope etc..
Final testing result shows, using the later natural hydrogen of above-mentioned hydrogen isotope separation method treatment, by 1 time
Separation can reach the deuterium concentration of 700ppm, and the deuterium concentration that can reach 1050ppm is separated by 2 times, after 3 times separate
The deuterium concentration of 2400ppm can be reached.
Claims (10)
1. a kind of method of displacement chromatography hydrogen isotope concentration and separation, comprises the following steps：
（1）Cooling：Molecular sieve column is fabricated to helical coiled tube, liquid nitrogen is contained in a container, molecular sieve column is totally immersed into
In liquid nitrogen, molecular sieve temperature is allowed to be maintained at liquid nitrogen temperature；
（2）Absorption：To hydrogen is passed through in molecular sieve column, metering is passed through the amounts of hydrogen of molecular sieve, when the air pressure in molecular sieve reaches
After certain pressure, stopping is passed through hydrogen；
（3）Heat up and separate：Spiral helicine molecular sieve column is lifted upwards, molecular sieve column is departed from liquid nitrogen liquid level, using air pair
Molecular sieve column is heated；Molecular sieve column is controlled to propose that the speed of liquid nitrogen liquid level is 0.5-5cm/min；
（4）Detection and collection：For the hydrogen that molecular sieve column is discharged, it is liquid by oxidation of hydrogen to use hydrogen oxygen recombination device in rear end
Water, then uses magnetic Mass Spectrometer Method D abundance therein.
2. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that step（1）In, the molecular sieve
Be filled in molecular sieve filling in stainless steel tube and be prepared from by post.
3. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that step（1）In, described molecule
The molecular sieve of sieve post filling is the mixture of one or more in A, X or Y type molecular sieve.
4. the method for displcement chromatography tritium concentration and separation as claimed in claim 3, it is characterised in that step（1）In, the molecular sieve
It is the molecular sieve of A and/or X-type.
5. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that step（2）In, it is passed through hydrogen：
First to hydrogen is passed through in constant volume container, then hydrogen is passed into molecular sieve from constant volume container again.
6. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that step（2）In, control is passed through hydrogen
Atmospheric pressure is an atmospheric pressure.
7. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that the body material of manufacture molecular sieve column
Material is stainless steel material.
8. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that in step（4）In, test molecule
During the hydrogen of sieve post discharge, the analyzing detecting method of use is indirect detection.
9. the method for displcement chromatography tritium concentration and separation as claimed in claim 8, it is characterised in that in step（4）In, detection method
It is that the hydrogen for first discharging molecular sieve column passes through hydrogen oxygen recombination device, then oxidation of hydrogen into aqueous water is examined by nucleus n-ness spectrum
Survey.
10. the method for displcement chromatography tritium concentration and separation as claimed in claim 1, it is characterised in that separated using timing during sampling
Sampling, then unifies to compose water sample using magnetic substance to be detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710081992.9A CN106693704B (en) | 2017-02-15 | 2017-02-15 | A kind of displacement chromatography hydrogen isotope enrichment and separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710081992.9A CN106693704B (en) | 2017-02-15 | 2017-02-15 | A kind of displacement chromatography hydrogen isotope enrichment and separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106693704A true CN106693704A (en) | 2017-05-24 |
| CN106693704B CN106693704B (en) | 2019-06-04 |
Family
ID=58909181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710081992.9A Active CN106693704B (en) | 2017-02-15 | 2017-02-15 | A kind of displacement chromatography hydrogen isotope enrichment and separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106693704B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289526A (en) * | 2018-09-20 | 2019-02-01 | 中国工程物理研究院材料研究所 | A kind of rotary low temperature hydrogen isotope separation system and separation method |
| CN109663456A (en) * | 2019-01-09 | 2019-04-23 | 中国工程物理研究院材料研究所 | A kind of hydrogen displacement sorption method is enriched with the method and system of trace heavy nucleus hydrogen isotope in hydrogen isotope |
| CN110354636A (en) * | 2019-07-05 | 2019-10-22 | 四川远方高新装备零部件股份有限公司 | A kind of pressure-variable adsorption splitter and its electric-control system |
| CN111307921A (en) * | 2019-11-26 | 2020-06-19 | 中国工程物理研究院材料研究所 | Absolute measurement quadrupole mass spectrum hydrogen isotope gas abundance analysis method and device |
| CN111569657A (en) * | 2020-04-22 | 2020-08-25 | 中国工程物理研究院材料研究所 | Method for manufacturing spiral separation column and equipment for realizing method |
| CN112892212A (en) * | 2021-01-26 | 2021-06-04 | 中国工程物理研究院核物理与化学研究所 | Fusion reactor low tritium retained hydrogen isotope separation device |
| CN113491947A (en) * | 2020-03-19 | 2021-10-12 | 中国科学院福建物质结构研究所 | Stable isotope gas separation method and apparatus |
| CN115325439A (en) * | 2022-08-23 | 2022-11-11 | 中国原子能科学研究院 | Hydrogen isotope gas drawing and storing device and method for processing gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276060A (en) * | 1979-05-22 | 1981-06-30 | The United States Of America As Represented By The United States Department Of Energy | Chromatographic hydrogen isotope separation |
| US4780116A (en) * | 1987-11-20 | 1988-10-25 | Cheh Christopher H | Low temperature preparative gas chromatography apparatus |
| JPH0412167B2 (en) * | 1986-05-08 | 1992-03-03 | Fukuushi Chee Kurisutofuaa | |
| US5904749A (en) * | 1992-12-14 | 1999-05-18 | Chen; Christopher Huk-Shi | Gas chromatographic method |
| CN101850215A (en) * | 2010-05-24 | 2010-10-06 | 四川材料与工艺研究所 | Low-temperature displacement chromatography hydrogen isotope separation device and method |
-
2017
- 2017-02-15 CN CN201710081992.9A patent/CN106693704B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276060A (en) * | 1979-05-22 | 1981-06-30 | The United States Of America As Represented By The United States Department Of Energy | Chromatographic hydrogen isotope separation |
| JPH0412167B2 (en) * | 1986-05-08 | 1992-03-03 | Fukuushi Chee Kurisutofuaa | |
| US4780116A (en) * | 1987-11-20 | 1988-10-25 | Cheh Christopher H | Low temperature preparative gas chromatography apparatus |
| US5904749A (en) * | 1992-12-14 | 1999-05-18 | Chen; Christopher Huk-Shi | Gas chromatographic method |
| CN101850215A (en) * | 2010-05-24 | 2010-10-06 | 四川材料与工艺研究所 | Low-temperature displacement chromatography hydrogen isotope separation device and method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289526A (en) * | 2018-09-20 | 2019-02-01 | 中国工程物理研究院材料研究所 | A kind of rotary low temperature hydrogen isotope separation system and separation method |
| CN109289526B (en) * | 2018-09-20 | 2021-10-22 | 中国工程物理研究院材料研究所 | Rotary low-temperature hydrogen isotope separation system and separation method |
| CN109663456A (en) * | 2019-01-09 | 2019-04-23 | 中国工程物理研究院材料研究所 | A kind of hydrogen displacement sorption method is enriched with the method and system of trace heavy nucleus hydrogen isotope in hydrogen isotope |
| CN109663456B (en) * | 2019-01-09 | 2021-07-13 | 中国工程物理研究院材料研究所 | Method and system for enriching trace heavy nuclear hydrogen isotopes in hydrogen isotopes by hydrogen replacement adsorption method |
| CN110354636A (en) * | 2019-07-05 | 2019-10-22 | 四川远方高新装备零部件股份有限公司 | A kind of pressure-variable adsorption splitter and its electric-control system |
| CN111307921A (en) * | 2019-11-26 | 2020-06-19 | 中国工程物理研究院材料研究所 | Absolute measurement quadrupole mass spectrum hydrogen isotope gas abundance analysis method and device |
| CN111307921B (en) * | 2019-11-26 | 2022-11-25 | 中国工程物理研究院材料研究所 | Absolute measurement quadrupole mass spectrum hydrogen isotope gas abundance analysis method and device |
| CN113491947A (en) * | 2020-03-19 | 2021-10-12 | 中国科学院福建物质结构研究所 | Stable isotope gas separation method and apparatus |
| CN111569657A (en) * | 2020-04-22 | 2020-08-25 | 中国工程物理研究院材料研究所 | Method for manufacturing spiral separation column and equipment for realizing method |
| CN112892212A (en) * | 2021-01-26 | 2021-06-04 | 中国工程物理研究院核物理与化学研究所 | Fusion reactor low tritium retained hydrogen isotope separation device |
| CN115325439A (en) * | 2022-08-23 | 2022-11-11 | 中国原子能科学研究院 | Hydrogen isotope gas drawing and storing device and method for processing gas |
| CN115325439B (en) * | 2022-08-23 | 2023-10-27 | 中国原子能科学研究院 | Hydrogen isotope gas drawing and storing device and method for treating gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106693704B (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106693704B (en) | A kind of displacement chromatography hydrogen isotope enrichment and separation method | |
| CN101850215B (en) | Low-temperature displacement chromatography hydrogen isotope separation device and method | |
| CN107051205B (en) | A kind of low temperature palladium displacement separation method | |
| EP2415512A1 (en) | Pressure variation adsorption method for gas separation of gas and apparatus therefor | |
| CN103323366B (en) | Shale gas growing amount and burst size on-line determination device | |
| CN104912525B (en) | Oil displacement experiment device and method for low permeability sandstone reservoir | |
| CN109313167A (en) | Multi-capillary column preconcentration technique for enhancing sensibility in gas-chromatography (GC) and gas chromatography-mass spectrum (GCMS) | |
| CN107796894A (en) | Sample preparation device and method for the improvement of elementary analysis spectrometer | |
| CN106693703B (en) | A kind of displacement chromatography hydrogen isotope separation device | |
| CN110873688B (en) | Method and system for measuring pore structure of tight sandstone | |
| CN110261280A (en) | A kind of reverse imbibition on-line monitoring experimental provision of high temperature and pressure rock core and experimental method | |
| CN110146640A (en) | The analysis system and method for micro nitrogen isotope | |
| CN205333462U (en) | A servo measurement testing system for testing coal sample gas absorption desorption rule | |
| JP2008296089A (en) | Method for isolating and enriching hydrogen isotope | |
| CN109663456A (en) | A kind of hydrogen displacement sorption method is enriched with the method and system of trace heavy nucleus hydrogen isotope in hydrogen isotope | |
| CN107894472B (en) | Method for measuring hydrogen isotope mixed gas separation factor of separation material | |
| Shin et al. | Design and experimental study of adsorption bed for the helium coolant purification system | |
| US9851335B2 (en) | Method and system for analyzing a gaseous fluid comprising at least one rare gas by means of a getterizing substrate | |
| CN111351884A (en) | Device for enriching and measuring nitrogen stable isotope and method for measuring nitrogen stable isotope in seawater | |
| Aoki et al. | The concentration of krypton in the atmosphere—its revision after half a century— | |
| CN112892211A (en) | Column type hydrogen-helium separation and concentration coupling device and method | |
| Aldridge | Gas chromatographic separation of hydrogen isotopes using metal hydrides | |
| Michel et al. | Adsorption of oxygen on the (110) plane of tungsten at low temperatures | |
| CN104743532B (en) | Surrounding air Kr-85 concentration device under room temperature | |
| CN111458253B (en) | Method and device for testing retrograde condensate oil saturation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |