CN106693704B - A kind of displacement chromatography hydrogen isotope enrichment and separation method - Google Patents
A kind of displacement chromatography hydrogen isotope enrichment and separation method Download PDFInfo
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- CN106693704B CN106693704B CN201710081992.9A CN201710081992A CN106693704B CN 106693704 B CN106693704 B CN 106693704B CN 201710081992 A CN201710081992 A CN 201710081992A CN 106693704 B CN106693704 B CN 106693704B
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Abstract
The invention discloses a kind of methods of displacement chromatography hydrogen isotope concentration and separation, the following steps are included: (1) cools down: molecular sieve column is fabricated to helical coiled tube, liquid nitrogen is contained in a container, molecular sieve column is totally immersed into liquid nitrogen, and molecular sieve temperature is allowed to be maintained at liquid nitrogen temperature；(2) it adsorbs: being passed through hydrogen into molecular sieve column, metering is passed through the amounts of hydrogen of molecular sieve, and after the pressure that the air pressure in molecular sieve reaches certain, stopping is passed through hydrogen；(3) heating separation: spiral helicine molecular sieve column is lifted upwards, so that molecular sieve column is detached from liquid nitrogen liquid level, is heated using air to molecular sieve column；It controls molecular sieve column and proposes that the speed of liquid nitrogen liquid level is 0.5-5cm/min；(4) detect and collect: for molecular sieve column discharge hydrogen, rear end using hydrogen oxygen recombination device by oxidation of hydrogen be liquid water, then use magnetic Mass Spectrometer Method D abundance therein.Displcement chromatography tritium enrichment and separation method of the invention, the variation in the cooling and temperature-rise period of control have continuity, separate the ultrahigh in efficiency of hydrogen isotope, good separating effect.
Description
Technical field
The invention belongs to separation purifying technique fields, are related to a kind of isotope separation method, in particular to a kind of same position of hydrogen
Plain separation method.
Background technique
The fusion reactor of superconducting Tokamak is considered as the fusion reactor of most practical application potentiality, can be with
Realize the green nuclear energy technology of extremely low radiation pollution, global every country has all put into a large amount of manpower and material resources and answered
With research.The demand of hydrogen isotope as fusion reactor fuel --- deuterium and tritium in research application is very big, and
The yield of the application once thermonuclear fusion reactor formally puts into production, existing deuterium and tritium will become limitation thermonuclear reactor and answer
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 can be directly isolated to obtain deuterium required for fusion reaction with its distinctive high-purity feature
And tritium, existing part can obtain the deuterium and tritium of higher degree research shows that dodging separation method by liquid, but specifically separation
There are no the exact schemes for industrializing implementation for method.
Again with the efficiency highest of cryogenic rectification hydrogen isotope separation method in concentration and separation technology, not only there is treating capacity
Greatly, the larger advantage of facility compact separation factor, and generate that cost is relatively low in separation process, application potential is big.It is existing
In concentration and separation technology, mainly includes the components such as application response device, electromagnetic heater, need in reaction process to separation unit
Part is heated and is regenerated, wherein the matching relationship between the heating part and reactor applied mainly directly heats comprehensively.
Heating 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 separation.In separation process, for items
The Adjustment precision of discrete state parameter is lower, only from the big separation effect theoretically analyzed in cryogenic rectification separation process
Fruit, comprehensive accurate research when separation for cryogenic rectification, proposes the efficiency in later practical popularization and application
It is limited to rise research help, in other words, can not preferably play the separative efficiency of cryogenic rectification separation hydrogen isotope.
Summary of the invention
It is an object of the invention to overcome to lack feasible efficient hydrogen isotope separation technology in the prior art, one kind is provided
Displacement chromatography hydrogen isotope enrichment and separation method.Method of the invention can be efficiently quickly isolated from natural pure hydrogen
The isotope of hydrogen --- deuterium and tritium have the characteristics that implementation is simple and convenient efficient, it is tired can to effectively improve deuterium tritium separation and concentration
Difficult problem provides sufficient reactive fuel for thermonuclear fusion reactor.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes:
A kind of method of displacement chromatography hydrogen isotope concentration and separation, comprising the following steps:
(1) cool down: molecular sieve column is fabricated to helical coiled tube, liquid nitrogen is contained in a container, molecular sieve column all soaks
Enter into liquid nitrogen, molecular sieve temperature is allowed to be maintained at liquid nitrogen temperature；
(2) it adsorbs: being passed through hydrogen into molecular sieve column, metering is passed through the amounts of hydrogen of molecular sieve, when the air pressure in molecular sieve
After reaching certain pressure, stopping is passed through hydrogen.Wherein, air pressure is preferably controlled to an atmospheric pressure, the requirement for equipment
It is lower, it is easier to implement, and separating effect is preferable.The hydrogen contains deuterium/tritium of natural abundance.
(3) heating separation: spiral helicine molecular sieve column is lifted upwards, so that molecular sieve column is detached from liquid nitrogen liquid level, is utilized sky
Gas heats molecular sieve column.Molecular sieve column is preferably slowly lifted, increases the temperature of molecular sieve column slowly.It is lifting
During, spiral helicine molecular sieve column heats by air and realizes thermal release, especially can be achieved on segmentally heating, makes score
The temperature section of son sieve column gradually rises.It controls molecular sieve column and proposes that the speed of liquid nitrogen liquid level is 0.5-5cm/min, preferably lift
Speed is 1-2.5cm/min, slowly completes the heating process of molecular sieve column.
(4) it detects and collects: for the hydrogen of molecular sieve column discharge, being by oxidation of hydrogen using hydrogen oxygen recombination device in rear end
Then liquid water uses magnetic Mass Spectrometer Method D abundance therein.Detect splitter (molecular sieve column) of the hydrogen by different number
The concentration of deuterium later determines efficiency that every level-one pillar separates hydrogen deuterium with this.Clearly separate column length, filler etc. because
Element guarantees required for obtaining when carrying out deuterium enriched for that can optimize to splitter after the influence of segregation ratio
The product of concentration.
Displcement chromatography deuterium/tritium enrichment and separation method of the invention, has been arranged to helical coiled tube structure for molecular sieve column, outside
Shape is similar to spring, cools down the temperature for controlling molecular sieve column in extremely low level first with low temperature liquid nitrogen, then passes through lifting
Mode make molecular sieve column slowly leave 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, realizes the centrifugation for the isotope in hydrogen.The hydrogen being wherein passed through is
The hydrogen of deuterium, tritium containing natural abundance is also possible to be greater than by the certain deuterium of enrichment processing and/or the abundance of tritium general
Natural hydrogen Artificial gas's (manually pre-processing hydrogen) or nuclear reactor by-product contain 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, controls simultaneously
Cooling and temperature-rise period in variation have continuity, temperature consecutive variations, which may be implemented, ensure that the efficiency of separation so that
Isolated better effect.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 round, and the amount for filling molecular sieve is maximum, and structure is the most stable.
Further, in step (1), the molecular sieve column is prepared molecular sieve filled in stainless steel tube.It will
Molecular sieve be bonded compression moulding post package column, strip helical pipe in, the continuous molecular sieve column of composition be realize
There is continuous long pipeline continuous multi-stage separation tower structure may be implemented for the key factor of hydrogen isotope separation, control molecular sieve column
The concentration and separation for extremely low concentration deuterium is completed, and the deuterium that high concentration may be implemented is further purified enrichment.Preferably may be used
To use helix tube to carry out the molecular sieve material that filling molecular sieve is formed by bonding, mixing packed density more preferably, can more fill
The natural hydrogen of absorption divided completes the separation and concentration for deuterium and/or tritium.
Further, in step (1), the molecular sieve of the described molecular sieve column filling be one of 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 dry, separation, purifying
Work.Molecular sieve is artificial synthesized zeolite, and the crystal of silicate, at 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 aperture is close with molecular diameter, and non-
Often uniformly.Molecular sieve is a kind of adsorbent that pore-size distribution is most concentrated in all kinds of adsorbents.It can inhale the molecule for being less than aperture
Into in hole, the molecule for being greater than aperture is kept off outside hole, therefore there is very strong adsorption selectivity.Due to the original of hydrogen isotope
Protonatomic mass is different, and there are small difference for the suction-operated in molecular sieve, 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, the hydrogen isotope in molecular sieve column can be made
Quickly separate.
Further, in step (2), the hydrogen is natural hydrogen, wherein deuterium/tritium containing natural abundance, if
Use the purpose that enrichment also may be implemented as raw material rich in deuterium/tritium hydrogen, and the deuterium being enriched in obtained rich deuterium hydrogen
Content ratio it is higher.Deuterium containing 150ppm in general natural hydrogen handles available higher degree by enrichment
Rich deuterium hydrogen or even pure deuterium.
Adsorption technology is widely used in fusion reactor deuterium, tritium and fuel recycle, such as gas is discharged in doughnut plasma
Pumping, plasma discharge gas in tritium cleaning, the impurity containing tritium go it is tritiated processing, 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, hydrogen is first passed through into constant volume container, then
It is passed into molecular sieve column from constant volume container by hydrogen again, to realize that accurate quantification is passed through the purpose of hydrogen.Preferably, using point
The method for walking ventilation, hydrogen is passed through into molecular sieve, control pressure is not so high, and hydrogen is avoided to penetrate 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
The gas pulsation that constant volume container is controlled in journey is smaller, prevents hydrogen from being compressed, so that the total amount meter of the hydrogen of injection molecular sieve column
It is more accurate, also avoid the problem of high pressure hydrogen permeates.
Specific operating process is as follows: in order to accurately measure the amounts of hydrogen for being passed through molecular sieve, a constant volume is arranged in front end
Container.Hydrogen is first passed through constant volume container, records pressure value at this time, is then passed through again by constant volume container into 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.It is fixed to guarantee
The pressure held in container is consistently higher than an atmospheric pressure, when the pressure drops, inflates toward constant volume container.Record supplement gas every time
Front and back and the pressure difference value ventilated to molecular sieve.Due to environmental temperature fluctuation very little, so it can be considered as in isoperibol.Institute
It states during substep ventilation refers to and be passed through hydrogen, hydrogen is passed through to molecular sieve column by constant volume container several times, statistics is repeatedly
The gas pressure change numerical value of constant volume container calculate the total amount for being passed through gas in conjunction with the volume of constant volume container.
When detecting that the pressure in molecular sieve column is more than an atmospheric pressure, it is believed that at this time uptake through being saturated.Record
Under all pressure drop Δ P at this time, the amounts of hydrogen of absorption can be calculated.By calculate pressure drop Δ P multiplied by constant volume container volume,
The amounts of hydrogen of absorption can be quickly calculated, control gas pressure is lower, is no more than an atmospheric pressure, guarantees measurement result
Accurate reliability.
Further, the molecular sieve column includes many-level molecule sieve column, is set as continuously dividing between many-level molecule sieve column
Son sieve column.End to end structure can be set between many-level molecule sieve column, when first order molecular sieve column completes adsorbing separation
After, gas enters rear stage molecular sieve column and continues separating treatment.Be designed in this way can according to separation the case where, separation
The different molecular sieve column composite structure of purpose adjusted design reaches the adjustment control for the whole continuous length of molecular sieve column.
Higher separative efficiency may be implemented by increasing many-level molecule sieve rod structure.Preferably, hose is used between many-level molecule sieve column
It connects, stepped heating separating treatment may be implemented.
Further, step (3) heating separation:
The separation process that heats up is as follows:
It is heated using the mode of lifting (promotion), molecular sieve column is made slowly to be detached from liquid nitrogen, temperature gradually rises.Molecule
The hydrogen adsorbed in sieve is detached from after liquid nitrogen temperature increases in molecular sieve column to be started to discharge.One end valve is closed, after desorbing gas
Pressure difference, since preceding end molecule sieve column successively lift, by Q2 successively from preceding end molecule sieve column driven into the pillar of rear end.Add
Radiation heat transfer can be completed thermal process at room temperature, and low energy consumption.
Different pull rate can obtain different separative efficiencies.Optimal work parameter is obtained by Test Summary.Experiment card
It is bright, since molecular sieve adsorption temp is very low, so even if the temperature of room temperature and 20K still have the very big temperature difference in winter, point
Separation process can be realized after being detached from liquid nitrogen from column.
Molecular sieve is being saturated with and is being heated to liquid nitrogen temperature or more later, preferentially discharges protium, followed by deuterium, is finally only tritium.
For 5A molecular sieve, the separation temperature of molecular sieve is -100 DEG C, and heating system only needs to arrive by promoting splitter
On liquid nitrogen liquid level, splitter segmentally heating can be realized by air heating.The ascending suit in layer of splitter.Examination
It tests initially, original gas is filled with innermost splitter.It is then lifted out splitter.Respectively according to 1cm/min, the speed of 2cm/min
Degree is promoted, and molecular sieve column is detached from liquid nitrogen in lifting process, is heated by upper air, is heated up naturally.Until all columns
Body (molecular sieve column) leaves liquid nitrogen surface.The hydrogen of first pillar (molecular sieve column) completes to be separated for the first time.And it can be by
Second pillar (molecular sieve column) absorbs.
Further, the molecular sieve column has multiple, and multiple molecular sieve columns interconnect, isolated from previous molecular sieve column
Hydrogen can enter next molecular sieve column have the function that continuous separation and concentration.
A pillar, two pillars and three pillars are tested respectively to the separating effect of isotope.Experiments have shown that single column
Sub (molecular sieve column), for the deuterium of the natural abundance of 150ppm after separation, enrichment end has reached 650ppm, two pillars in hydrogen
When reached 1000ppm, whens three pillars, has reached 2300ppm.
It can continue Optimum Experiment process by changing promotion speed, finally obtain optimal heating sequence (rate).Examination
Verifying separation column length, heating method, influence of the heating speed to separating property can be continued by testing.
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 lesser level, easier can be put into liquid nitrogen tank, carries out cooling processing using liquid nitrogen.And
And spiral helicine molecular sieve column can also carry out non-contact thermal by intermediate frequency coil, spiral helicine structure makes molecular sieve
The heating temperature of each end position of column is consistent substantially, overcomes the temperature difference to influence, separating effect is more preferably.
Test objective is to verify molecular sieve segmentally heating method to the separating effect of hydrogen isotope.The absorption of molecular sieve
Amount has been described in the literature, but according to different partial size and type of feed, actual uptake still allow it needs to be determined that.First
It needs to be determined that the Q2 amount of sum is saturated in actual experiment in molecular sieve.Q2 indicates the hydrogen isotope gaseous mixture scale of construction, is common expression shape
Formula.It can be estimated by the data in document, other test parameters are determined with this.
Further, the tube body material for manufacturing molecular sieve column is stainless steel material, preferably 316 stainless steels.Corrosion resistance is excellent
It is good, while there is preferable high-temperature behavior, it can satisfy the temperature change Stress Control in molecular sieve column heating process, make score
Performance of the son sieve column when temperature programming separates 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 better holding meanss structure
Overall stability, improve that separate temperature program/scheme more advantageous for improving separating effect and subsequent adjustment.
Further, in step (4), when test molecule sieves the hydrogen of column discharge, the analyzing detecting method of use is indirect
Detection.Specifically, detection method is first by the hydrogen of molecular sieve column discharge by hydrogen oxygen recombination device, by oxidation of hydrogen at liquid
Then water is detected by nucleus n-ness spectrum.It, can be by the precision of the detection and analysis of deuterium content in hydrogen using the method detected indirectly
It is increased to the left and right of 5ppm.Correspondingly, it is preferred that the mode sampled in indirect detection process is interval sampling, preferably fixed time interval
Sampling analysis.
After gas is separated, how to carry out accurate measurement to the gas after separation is an important problem.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,
When test, by hydrogen oxygen recombination device, by oxidation of hydrogen at liquid water, then by magnetic Mass Spectrometer Method, pair for separation is realized
5ppm can be improved in the accurate detection and analysis of the low concentration of elephant, the precision of detection and analysis.
Preferably, it is sampled when sampling using fixed time interval, then unifies to detect water sample using nucleus n-ness spectrum.As a result
Show to separate by 2-3 times, 2 kinds of splitters may make natural abundance to be concentrated to 2000ppm or more.
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 variation in the cooling and temperature-rise period controlled has continuity, and the guarantee of temperature consecutive variations may be implemented
The ultrahigh in efficiency of cryogenic separation hydrogen isotope guarantees separating effect 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 realization hydrogen isotope point
From enrichment, the potentiality with high industrial applications.
Detailed description of the invention:
Fig. 1 is the schematic diagram of low-temperature displacement chromatography tritium concentration and separation technological system of the invention.
Marked in the figure: 1- constant volume container, 2- molecular sieve column separator, 3- hydrogen oxygen recombination device, 4- mass spectrograph, 5- vacuum
Pump.
Specific embodiment
Below with reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
It is all that this is belonged to based on the technology that the content of present invention is realized for the scope of the above subject matter of the present invention is limited to the following embodiments
The range of invention.
Embodiment 1
Prepare molecular sieve column:
Prepare molecular sieve column when, select internal diameter be 12mm stainless steel tube as molecular sieve column main structure.Make
After mixing with adhesive and 5A molecular sieve, it is filled into above-mentioned stainless steel tube, fills out after being filled with, it will using bend pipe machine
Stainless steel tube bends to spiral coil structure, and the diameter of spiral coil is that can be put into the size of liquid nitrogen tank, must both test
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, can be more convenient it is cooled down using liquid nitrogen.
Displcement chromatography tritium concentration and separation:
Molecular sieve column is all immersed in liquid nitrogen, the temperature of molecular sieve column is made to be reduced to the temperature of liquid nitrogen.To constant volume
It is injected in container natural hydrogen (deuterium containing natural abundance), after constant volume container pressure is stablized, closes injection valve, then open
Valve between constant volume container and molecular sieve column is passed into natural hydrogen in molecular sieve column, after stable gas pressure, closes valve
Door.Separation is started to warm up, heating separation process is gradually to propose molecular sieve column on liquid nitrogen liquid level, utilizes liquid nitrogen ullage
Air heat molecular sieve column, realize the heating of splitter, promotions 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, and isotope that enrichment obtains separately is received
Collect and detects isotope abundance therein.
By the way that molecular sieve column to be dipped into liquid nitrogen, liquid nitrogen quickly cools down molecular sieve column, cooling speed
Degree is exceedingly fast, since the spiral coil structure of molecular sieve column keeps it big with the contact surface of liquid nitrogen, good cooling results and it is fast.Spiral coil
During the molecular sieve column of structure is cooling in liquid nitrogen, on the surface of molecular sieve column Quick-gasifying, the gas of formation occur for liquid nitrogen
Bubble can generate good stirring action to liquid nitrogen solution, promote the excellent that cools of liquid nitrogen.
Embodiment 2
X molecular sieve material, difference promote isolated influence of the speed for hydrogen isotope
Prepare the molecular sieve of X-type, squeezes into strips, be filled in molecular sieve column after adhesive is added.By this molecular sieve
Column is all immersed in liquid nitrogen, and molecular sieve column is totally submerged by liquid nitrogen, and the temperature of molecular sieve column is made to be reduced to the temperature of liquid nitrogen.
Natural hydrogen (deuterium containing natural abundance) is injected into 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 made to be passed into molecular sieve column
In, after stable gas pressure, valve is closed, adsorbs its hydrogen adequately 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 and is held
In device 1, the Hydrogen Vapor Pressure in constant volume container 1 is controlled in an atm higher, facilitates the exact value for calculating hydrogen usage.It opens
Vacuum pump 5 is opened, the evacuating air in molecular sieve column separation equipment 2 in molecular sieve column is discharged.Molecular sieve column is immersed into liquid nitrogen
In solution, molecular sieve column is cooled down using liquid nitrogen solution, until the temperature of the two is equal.Utilize 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, and the overall presure drop numerical value for calculating constant volume container 1 is obtained multiplied by the volume of constant volume container 1
The total amount Q2 of hydrogen is injected out.Slowly lift molecular sieve column, it is made to be partially disengaged liquid nitrogen solution, it is heated using air
Processing enters in hydrogen oxygen recombination device 3 from the gas of molecular sieve column separation discharge from pipeline, and oxidation is converted into aqueous solution, utilizes
Mass spectrograph 4 is analyzed by mass spectrometry, and quickly determines the deuterium content in the hydrogen of discharge, collects the higher component of deuterium content, is determined most
Excellent separation and Extraction parameter.
Specific heating separation program is as follows: heating separation process is gradually to propose molecular sieve column on liquid nitrogen liquid level,
Molecular sieve column is heated using the air of liquid nitrogen ullage, realizes the heating of splitter, promotion 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 passes through hydrogen-oxygen
Then recombiner is detected by sampling oxidation of hydrogen at liquid water by nucleus n-ness spectrum.As the variation of disengaging time is (when heating
Between change), the isotope ratio in the gas of discharge changes, because what is first separated from molecular sieve column is protium, so
After be deuterium and tritium.Using the method detected indirectly, the precision that the content detection of deuterium and/tritium analysis in hydrogen is discharged can be improved
To the left and right of 5ppm, for studying isolated efficiency, the method for optimizing separation is of great significance.
During promotion, when the molecular sieve column of helical disk tubulose leaves liquid nitrogen liquid level, promotes speed and does not have to too fastly,
Be when actually spiral coil leaves liquid nitrogen it is a-circle-by-a-circle continuously leave, it is practical although it is unhappy to promote speed
The part of spiral coil heating is simultaneously many, and it is faster for also allowing for the rate of heating.Simultaneously because spiral coil has continuously
Structure, low temperature of the hydrogen isotope in the high temperature and liquid nitrogen of air heating part in molecular sieve column in the process of ascension
Part quickly continuous flowing transfer, acts on by a series of alternate analysis, so that actually wrapping in single molecular sieve column
A large amount of centrifugation repeatedly is contained, can quickly reach and its separative efficiency outstanding.
Influence of a variety of different pull rate for the separative efficiency of hydrogen isotope in molecular sieve column is compared, is during which controlled
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 has significant impact for the separation of the hydrogen isotope in molecular sieve column.According to promotion speed
Control situation, can also realize the improvement result of different separative efficiencies because when promoted speed control when lower, in liquid
The separating effect of nitrogen interface is more prominent, and separating effect is better.It is had studied in the embodiment of the present invention specific different
Influence of the speed for separating effect is promoted, as a result, it has been found that when promoting speed control when 2cm/min, single molecular sieve column
Separative efficiency can achieve the degree of enrichment of 2364ppm.If promoting speed increases to 8cm/min, since 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 equipped with a hydrogen oxygen recombination device (oxidation unit) before detecting instrument, deuterium gas is oxidized to deuterated
Water, in order to measure amount containing deuterium therein with nucleus n-ness spectrum, to measure isotopic separation efficiency.
Embodiment 3
Analyze influence of the inner diameter size for separative efficiency of different size of stainless-steel pipe
The molecular sieve for preparing A type, is filled in 316 stainless-steel pipes of internal diameter 12mm and molecular sieve column is made.By this molecule
Sieve column is all immersed in liquid nitrogen, and the temperature of molecular sieve column is made to be reduced to the temperature of liquid nitrogen.Emptying molecular sieve is replaced with hydrogen
In gas, then to which in molecular sieve column, then vacuumize process, makes to keep vacuum in molecular sieve column.Into constant volume container
It injects natural hydrogen (deuterium containing natural abundance), after constant volume container pressure reaches an atmospheric pressure and stablizes, closes injection
Then valve opens the valve between constant volume container and molecular sieve column, is passed into natural hydrogen in molecular sieve column, steady to air pressure
After fixed, valve is closed.Start to warm up separation: heating separation process is gradually to propose molecular sieve column on liquid nitrogen liquid level, is utilized
The air of liquid nitrogen ullage heats molecular sieve column, realizes the heating of splitter, and promotion speed control is 5cm/min, slowly
Complete the heating process of molecular sieve column.During separation, by the hydrogen of molecular sieve column discharge by hydrogen oxygen recombination device, by hydrogen
It is oxidized to liquid water, is then detected by nucleus n-ness spectrum, the same position of hydrogen of molecular sieve column separation and concentration is determined by the result of detection
The collection opportunity of element.
Selecting internal diameter is respectively 316 stainless-steel pipes of 6mm, 10mm, 14mm, 18mm, using the filling point of same method
Pipe diameter molecular sieve column of different sizes is prepared in son sieve filler processing, bends to the later molecular sieve column of coil shape
Coil radius is identical, and the length of each molecular sieve column is 45m.During test, whole molecular sieve columns are cold using liquid nitrogen
Freeze 20 minutes, be passed through the natural hydrogen (deuterium content 150ppm) of 1bar by constant volume vessel buffers, absorption after ten 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.
The result shows that the molecular sieve column that the stainless-steel pipe for using different calibers is prepared into obtains separation and concentration
The abundance of hydrogen isotope have a certain difference, the size of caliber is not significantly to correspond to separative efficiency, works as caliber
When excessive, isolated efficiency is bad instead, and the effect of separation can be improved if same control small diameter tube in a certain range
Rate, but more than after certain range, separative efficiency begins to significantly reduce.So being finally in control displcement chromatography
The stainless-steel pipe internal diameter of the molecular sieve column of application is between 10-14mm, and separating effect is preferable, and single is filled with Hydrogen Separation
Total amount is larger.
Further, wherein heating separation initial stage obtained hydrogen is separately collected and needs the ground using purified hydrogen as other
Side avoids emptying from wasting.
Embodiment 4
Displcement chromatography tritium concentration and separation, influence of the different size of molecular sieve filling for separative efficiency
Firstly, 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
The molecular sieve column of 45m long.Then this molecular sieve column is totally immersed into liquid nitrogen, molecular sieve temperature is allowed to be maintained at liquid nitrogen temperature.
Then, the hydrogen containing natural abundance deuterium is passed through into molecular sieve column, the air pressure for controlling molecular sieve column reaches 1bar, and keeps permanent
3 minutes fixed, 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 start to warm up separation: slow-paced according to 2cm/min propose molecular sieve column on liquid nitrogen liquid level, so that
The temperature of molecular sieve column increases (note: 24 DEG C of room temperature).For the hydrogen of molecular sieve column discharge, examined in rear end with analysis and detecting instrument
The variation for surveying deuterium content ratio therein, detect molecular sieve column discharge hydrogen in deuterium content it is relatively high when, such as
Greater 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.
The result shows that having one for the separative efficiency of hydrogen isotope when using the Molecular sieve raw material of different-grain diameter
Fixed influence, when partial size is less than 5 μm, the influence of separative efficiency is minimum, only when molecular sieve partial size is greater than 15 μm
The decaying that just will appear separative efficiency is waited, this is related with molecular sieve specific surface area reduction, simultaneously because needing during preparation
Using a certain amount of bonding agent is arrived, glued dose of part of the surface of molecular sieve is destroyed when bonding, so partial size reduction pair
Not significant in the castering action performance of specific surface area, preferable separation can be obtained at 3-8 μm for the range of preferably control partial size
Efficiency, the molecular sieve that more preferable 5-8 μm of overall cost.
Embodiment 5
The realization situation of 1-4 based on the above embodiment, researching and designing one optimal hydrogen isotope separation control method
Prepare molecular sieve column:
X-type molecular sieve raw material is selected, suitable adhesive is added in the raw material of 2-3 μm of partial size of screening, is uniformly mixed, then
It is filled in 316 stainless-steel pipes of internal diameter 12mm.By filled stainless-steel pipe bending machine, it is processed into the radius of spin
1.5 meters of spiral bending tube (structure is similar to spring), 45 meters of stainless steel tube total length.
Hydrogen isotope separation:
(1) cool down: above-mentioned molecular sieve column being dipped into the container for containing liquid nitrogen, liquid nitrogen is made to flood molecular sieve column, keep
Molecular sieve temperature is allowed to be reduced to liquid nitrogen temperature within 10 minutes or more.
(2) it adsorbs: using the constant volume container of a fixed volume, is passed through into molecular sieve column indirectly containing natural abundance deuterium
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) heating separation: spiral helicine molecular sieve column is lifted upwards, so that molecular sieve column is detached from liquid nitrogen liquid level, is utilized sky
Gas heats molecular sieve column.It controls molecular sieve column and proposes that the speed of liquid nitrogen liquid level is 2.5cm/min, slowly complete molecule
The heating process for sieving column heats by air and realizes segmentally heating separation.Hydrogen is heated in molecular sieve column and drives, isotope
For deuterium because the separation factor in molecular sieve is different from protium, separative efficiency of the two in place of air heating is different, and hydrogen is dividing
It is continuously moved in son sieve column, forms different separation factor control intensity.
(4) it detects and collects: for the hydrogen of molecular sieve column discharge, being by oxidation of hydrogen using hydrogen oxygen recombination device in rear end
Then liquid water uses magnetic Mass Spectrometer Method D abundance therein.It determines the efficiency that first order molecular sieve column separates hydrogen deuterium, calculates
Separation factor, separative efficiency etc. of the molecular sieve filling for hydrogen isotope out.
Final testing result is shown, later natural hydrogen is handled using above-mentioned hydrogen isotope separation method, by 1 time
Separation can achieve the deuterium concentration of 700ppm, the deuterium concentration that can achieve 1050ppm be separated by 2 times, after 3 separation
It can achieve the deuterium concentration of 2400ppm.
Claims (10)
1. a kind of method of displacement chromatography hydrogen isotope concentration and separation, comprising the following steps:
(1) cool down: molecular sieve column being 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) it adsorbs: being passed through hydrogen into 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) heating separation: spiral helicine molecular sieve column is lifted upwards, so that molecular sieve column is detached from liquid nitrogen liquid level, is utilized air pair
Molecular sieve column is heated；It controls molecular sieve column and proposes that the speed of liquid nitrogen liquid level is 0.5-5cm/min；
(4) detect and collect: for molecular sieve column discharge hydrogen, rear end using hydrogen oxygen recombination device by oxidation of hydrogen be liquid
Then water uses magnetic Mass Spectrometer Method D abundance therein.
2. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that in step (1), the molecular sieve
Column is that molecular sieve filling is filled in stainless steel tube to be prepared.
3. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that in step (1), the molecule
The molecular sieve of sieve column filling is the mixture of one or more of A, X or Y type molecular sieve.
4. the method for displcement chromatography tritium concentration and separation as claimed in claim 3, which is characterized in that in step (1), 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 described in claim 1, which is characterized in that in step (2), be passed through hydrogen:
It is first passed through hydrogen into constant volume container, is then passed into molecular sieve from constant volume container by hydrogen again.
6. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that in step (2), when in molecular sieve
Hydrogen Vapor Pressure reach an atmospheric pressure after, stopping be passed through hydrogen.
7. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that manufacture the tube body material of molecular sieve column
Material is stainless steel material.
8. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that in step (4), test molecule
When sieving the hydrogen of column discharge, the analyzing detecting method of use is to detect indirectly.
9. the method for displcement chromatography tritium concentration and separation as claimed in claim 8, which is characterized in that in step (4), detection method
It is, by oxidation of hydrogen at liquid water, then to be examined by nucleus n-ness spectrum first by the hydrogen of molecular sieve column discharge by hydrogen oxygen recombination device
It surveys.
10. the method for displcement chromatography tritium concentration and separation as described in claim 1, which is characterized in that separated when sampling using timing
Then sampling unifies to detect water sample using magnetic substance spectrum.
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| 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 |
| 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 |
| 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 |
| CN111569657B (en) * | 2020-04-22 | 2023-04-18 | 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 |
| 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 |
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