CN102286754B - Electrolysis and concentration device of tritium in water - Google Patents

Electrolysis and concentration device of tritium in water Download PDF

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Publication number
CN102286754B
CN102286754B CN201110247742A CN201110247742A CN102286754B CN 102286754 B CN102286754 B CN 102286754B CN 201110247742 A CN201110247742 A CN 201110247742A CN 201110247742 A CN201110247742 A CN 201110247742A CN 102286754 B CN102286754 B CN 102286754B
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electrolyzer
sample bottle
bottle
oxygen
water
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CN102286754A (en
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周睿东
杨旭富
林清
邓飞
黄乃明
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GUANGDONG ENVIRONMENT RADIATION MONITORING CENTER
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GUANGDONG ENVIRONMENT RADIATION MONITORING CENTER
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention relates to an electrolysis and concentration device of tritium in water. The electrolysis and concentration device comprises a reflux condensing pipe, a sample bottle and an SPE (solid polymer electrolyte) electrolyzer all of which are arranged in a cooling device from top to bottom. The device also comprises a direct current stabilized-current power supply for power supply of the electrolyzer and a control circuit, wherein the positive and negative electrodes of the SPE electrolyzer are connected with the positive and negative electrodes of the direct current stabilized-current power supply; the oxygen and hydrogen outlets of the electrolyzer are separately connected with the reflux condensing pipe through the sample bottle, and then are separately connected to the outside of the cooling device through oxygen and hydrogen exhaust pipes; the oxygen and hydrogen exhaust pipes are feeding ports; and the outlet connected with an oxygen sample bottle and the outlet connected with a hydrogen sample bottle are separately connected with the feeding ports of the electrolyzer through pipelines. The device also comprises a laser transmitter and a laser receiver both of which are oppositely located at both sides of one vertical pipeline of two branched pipelines for connecting the outlet of the oxygen sample bottle and the outlet of the hydrogen sample bottle, wherein the vertical pipeline part between the laser transmitter and laser receiver is transparent; and the laser receiver is used for outputting liquid level signal to the control circuit. The electrolysis and concentration device provided by the invention is efficient, stable and reliable.

Description

Tritium electrolytic enrichment device in the water
Technical field
The invention belongs to the activity measurement technical field of tritium in the water, be specifically related to a kind of device that can tritium in the water of low-level sample be carried out electrolytic enrichment.
Background technology
Electrolytic enrichment to tritium in the water of low-level sample among the GB 12375-1990 " analytical procedure of tritium in the water " is through alkali formula electrolytic process; Need use alkali formula electrolyzer, vacuum condensation distillation, liquid nitrogen etc., the main drawback of this method is: operation and complex disposal process, to the skilled operation degree require high, electrolysis time is long (generally need 150~200h), tool corrodibility, enrichment factor is limited.At present existing bibliographical information utilizes SPE (Solid polymer Electrolyte) solid polymerization film ionogen to carry out the spissated technology of electrolysis; This technology has the following advantages: (1) ionogen need not any reagent; Simple to operate; Owing to there is not any solute residue, there is not the limit in the volume enrichment factor of water.(2) oxygen that produces and hydrogen are isolated by semipermeable partition respectively can not produce detonation gas, safe.(3) SPE cationic exchange membrane resistance is minimum, and the contact surface of electrode and film can be because of bubble stop up, and is difficult to saturatedly through electric current, can carry out large-current electric and separate, and shortens electrolysis time.
Summary of the invention
The objective of the invention is to technical requirements, tritium electrolytic enrichment device in a kind of efficient, stable, reliable water is provided to tritium measurement in the low-level activity water.
For realizing above-mentioned purpose; Tritium electrolytic enrichment device in the water of the present invention; Comprise and be located in the heat sink and the reflux condensing tube, sample bottle and the SPE electrolyzer that are provided with from top to bottom; Also be included as the dc current stabilized power supply of electrolyzer with electricity and the pilot circuit of control electrolyzer power source and the start and stop of heat sink power supply; The positive and negative electrode of said SPE electrolyzer connects the positive and negative electrode of dc current stabilized power supply, and the oxygen of electrolyzer and hydrogen outlet are distinguished ventilatory assistance and hydrogen vapor pipe to heat sink more respectively through taking back the stream prolong behind the sample bottle; This oxygen and hydrogen vapor pipe also are the application of sample mouth simultaneously; The sample bottle outlet that connects oxygen and the sample bottle outlet that is connected hydrogen are connected to the injection port of electrolyzer respectively through pipeline, also comprise laser transmitter and laser pickoff, are located at the pipe tunnel both sides in connecting the outlet of oxygen sample bottle and being connected one of two laterals that the hydrogen sample bottle exports relatively; The pipe tunnel position that is between laser transmitter and the laser pickoff is transparent, and this laser pickoff output liquid level signal is to pilot circuit.
The sample bottle outlet of above-mentioned connection oxygen is connected to the injection port of being located at bottom of electrolytic tank with the sample bottle outlet that is connected hydrogen through three-way pipeline, and this injection port also is a nesting port simultaneously, and this nesting port is provided with drainage switch.
In one embodiment, above-mentioned heat sink is a refrigerator.
In another embodiment, above-mentioned heat sink comprises refrigerator and places cooling bottle, recycle pump and the water-cooled head in the refrigerator that said sample bottle and reflux condensing tube all place in the cooling bottle; There is the quench liquid inlet cooling bottle upper end; Be full of quench liquid in the cooling bottle, cooling bottle upper end is tightly connected with the reflux condensing tube upper end, and the lower end of reflux condensing tube is connected with the sample bottle upper end; The sample bottle lower end is tightly connected with cooling bottle lower end; Cooling bottle lower end has the import and export of quench liquid respectively, and said water-cooled head is located at electrolyzer, and quench liquid import and export, recycle pump and the water-cooled head of said cooling bottle lower end is communicated with into quench liquid circulation loop through the pipeline circulation successively.Also can comprise the wind-cooling heat dissipating case that places on the refrigerator inwall, this wind-cooling heat dissipating case is located between recycle pump and the water-cooled head.Quench liquid reaches cooling purpose in cooling bottle and water-cooled head, constantly circulating under the effect of recycle pump, and the wind-cooling heat dissipating case is discharged heat that quench liquid is with.
Above-mentioned water-cooled head the best is provided with two, is located at the tow sides of electrolyzer respectively.
Above-mentioned electrolyzer can be equipped with electronic thermometer probe, and this electronic thermometer probe output temperature transducing signal is to pilot circuit.
Above-mentioned laser transmitter is located at the pipe tunnel both sides in the lateral that is connected the outlet of oxygen sample bottle relatively with laser pickoff the best.
Laser transmitter of the present invention, laser pickoff and the transparent tube that is between relative laser transmitter and the laser pickoff have constituted the laser LLC; When the liquid level in the transparent tube was lower than the position of relative laser transmitter and laser pickoff, laser pickoff sent and stops electrolytic signal to pilot circuit.The relative laser transmitter and the position of laser pickoff are the setting liquid level of laser LLC just.
Pilot circuit is responsible for electrolytic beginning, end and to the protection of power supply and refrigerator circuit.The liquid level of water surpasses the setting liquid level of laser LLC in sample bottle; The laser LLC sends electrolyzable signal to pilot circuit; The power supply that pilot circuit is at first connected refrigerator, recycle pump and wind-cooling heat dissipating case begins refrigeration and cooling, freezes about 1 hour, and temperature is less than after 10 ℃ in the refrigerator; Connect dc current stabilized power supply again and give electrolyzer with electricity, the beginning electrolysis.Behind the electrolysis certain hour, the liquid level of water is lower than the setting liquid level of laser LLC in the sample bottle, laser LLC pilot circuit to the back-end sends and finishes electrolytic signal, closes all power supplys, and electrolysis finishes.
Practice shows that the volume that the present invention works as sample bottle is 1250ml, when the deionized water sample that once adds 500ml carries out electrolysis; Need 48 hours time; Sample volume concentrated and is that 20ml, the volume multiple that concentrates is 25 times after electrolysis was accomplished, and the concentration multiple that concentrates can reach 8 times; When once adding 1250ml, need 108 hours time, the concentration multiple that concentrates can reach 20 times.
Because laser LLC of the present invention can accurately control liquid level in desired location, can guarantee so each electrolysis accomplish after the residual volume of sample be the same; In whole electrolytic process, electrolyzer keeps stable cooling performance with the cooling bottle under the effect of refrigerator, recycle pump, wind-cooling heat dissipating case, water-cooled head; In electrolytic process, dc current stabilized power supply remains supplies with the stable electric current of electrolyzer simultaneously, thereby, guaranteed the stable and repeated of work of the present invention.
The present invention utilizes tritiated water (HTO) than water (H 2O) difficult electrolytic characteristics, through the sample bottle of SPE (Solid polymer Electrolyte) electrolyzer, laser LLC, dc current stabilized power supply, heat sink and comparatively large vol, can be more than 8 times with tritium concentration in the water.Whole device is through the system integration, and is rational in infrastructure, easy to operate, stability and good reproducibility, and the efficient that concentrates height is the treatment unit that concentrates that tritium is measured in the low-level activity water of a kind of ideal.
Description of drawings
Fig. 1 is the structural representation of the embodiment of the invention.
Among the figure: 1. the anodal 6. electrolyzer oxygen outlets of electronic thermometer probe 2. nesting ports 3. water-cooleds 4.SPE electrolyzer 5. electrolyzer 7. direct current adjustable constant current power supplys 8. pilot circuits 9. refrigerators 10. oxygen vapor pipes 11. hydrogen vapor pipes 12. quench liquid liquid adding holes 13. reflux condensing tubes 14. sample bottles 15. cool off bottle 16. laser transmitters and laser pickoff 17. electrolyzer negative poles 18. electrolyzer hydrogen outlets 19. recycle pumps 20. wind-cooling heat dissipating casees
Embodiment
Below in conjunction with accompanying drawing the embodiment of the invention is described in detail.
As shown in Figure 1; The embodiment of the invention comprises to be located in the heat sink and the reflux condensing tube 13, sample bottle 14 and the SPE electrolyzer 4 that are provided with from top to bottom; Also be included as the 0-30A direct current adjustable constant current power supply 7 of electrolyzer with electricity and the pilot circuit 8 of control electrolyzer power source and the start and stop of heat sink power supply; Heat sink comprises refrigerator 9 and places cooling bottle 15 in the refrigerator 9, recycle pump 19, water-cooled 3 and place the wind-cooling heat dissipating case 20 on refrigerator 9 inwalls that sample bottle 14 all places in the cooling bottle 15 with reflux condensing tube 13, and there is quench liquid inlet 12 cooling bottle 15 upper ends; Be full of quench liquid in the cooling bottle 15; Cooling bottle 15 upper ends and reflux condensing tube 13 upper ends are tightly connected, and the lower end of reflux condensing tube 13 is connected with sample bottle 14 upper ends, and sample bottle 14 lower ends are tightly connected with cooling bottle 15 lower ends; Cooling bottle 15 lower ends have the import and export of quench liquid respectively; Water-cooled 3 is provided with two, is located at the tow sides of electrolyzer 4 respectively, and quench liquid import and export, recycle pump 19, wind-cooling heat dissipating case 20 and the water-cooled of cooling bottle 15 lower ends 3 is communicated with into the quench liquid loop that circulates through the pipeline circulation successively.Positive pole 5 negative poles 17 of SPE electrolyzer 4 connect the positive and negative electrode of the direct current adjustable constant current power supply 7 of 0-30A; The oxygen outlet 6 of electrolyzer flows prolong 13 through taking back behind the sample bottle 14 respectively with hydrogen outlet 18; Distinguish outside ventilatory assistance vapor pipe 10 and hydrogen vapor pipe 11 to the refrigerator 9 again; This oxygen vapor pipe 10 also is the application of sample mouth with hydrogen vapor pipe 11 simultaneously; Sample bottle 14 outlets that connect oxygen export with the sample bottle that is connected hydrogen 14 and are connected to the injection port of being located at electrolyzer 4 bottoms through three-way pipeline, and this injection port also is a nesting port 2 simultaneously, and this nesting port 2 is provided with drainage switch.Also comprise laser transmitter and laser pickoff 16; Be located at the pipe tunnel both sides in the lateral that connects the outlet of oxygen sample bottle relatively; The pipe tunnel position that is between relative laser transmitter and the laser pickoff 16 is transparent; Be transparent glass tube, laser pickoff output liquid level signal is to pilot circuit.Electrolyzer 4 is equipped with electronic thermometer probe 1, this electronic thermometer probe 1 output temperature transducing signal to pilot circuit 8.
Laser transmitter, laser pickoff and the transparent glass tube that is between relative laser transmitter and the laser pickoff constitute the laser LLC, and the position of laser transmitter and laser pickoff is the setting liquid level of laser LLC just relatively.The laser LLC is a kind of device that utilizes laser to have the principle of different refraction angles to carry out tank level control at different transparent mediums; The liquid level of water can constantly descend because of electrolysis; When dropping to the setting liquid level, the laser LLC can send and stop electrolytic signal.Sample through electrolytic enrichment is accomplished is collected through the drainage switch of electrolyzer nesting port 2.Whole device all is positioned in the refrigerator 9 except direct current adjustable constant current power supply 7 and rear end pilot circuit 8.The rear end pilot circuit is responsible for electrolytic beginning, end and to the protection of direct current adjustable constant current power supply, refrigerator circuit.
When operating; At first be cleaning process: fill it up with sample bottle less than the deionized water of 1mS/m (as far as possible little) through the application of sample mouth with specific conductivity; The power supply of connection refrigerator 9 begins to freeze after about 1 hour (the refrigerator temperature is less than 10 ℃); The power supply of connecting recycle pump 19 and wind-cooling heat dissipating case 20 flows quench liquid in water-cooled 3 and cooling bottle 15, and then electrolyzer 4, sample bottle 14 and reflux condensing tube 13 are cooled off, and connects the direct supply of direct current adjustable constant current power supply 7 to electrolyzer 4 supply 20A; Beginning electrolytic cleaning 0.5 hour is discharged deionized water through electrolyzer nesting port 2 fully; Then be sample electrolytic enrichment process: specific conductivity is joined sample bottle less than the 500-1250ml sample of 1mS/m (as far as possible little); After connection refrigerator 9, recycle pump 19 and wind-cooling heat dissipating case 20 begin refrigeration and cool off 1 hour (the refrigerator temperature is less than 10 ℃); Connect direct current adjustable constant current power supply 7 and supply with the direct supply of 20A to electrolyzer 4; The beginning electrolytic enrichment, start-of-record electrolysis time and electrolyzer temperature; Behind the electrolysis certain hour, the liquid level of water is lower than the setting liquid level of laser LLC in the sample bottle, and laser LLC pilot circuit 8 to the back-end sends the electrolytic signal of end, closes all power supplys, and electrolysis finishes.Through electrolyzer nesting port 2 sample in electrolyzer, sample bottle and the pipeline is discharged fully, record remaining liq volume or weight, the sample that electrolysis is accomplished and the scintillation solution of certain volume are mixed and made into the sample of liquid flashing counting.

Claims (10)

1. tritium electrolytic enrichment device in the water; It is characterized in that: comprise and be located in the heat sink and the reflux condensing tube (13), sample bottle (14) and the SPE electrolyzer (4) that are provided with from top to bottom; Also be included as the dc current stabilized power supply (7) of electrolyzer with electricity and the pilot circuit (8) of control electrolyzer power source and the start and stop of heat sink power supply; The positive and negative electrode of said SPE electrolyzer (4) (5,17) connects the positive and negative electrode of dc current stabilized power supply (7); The oxygen of electrolyzer and hydrogen outlet (6,18) are respectively through taking back stream prolong (13) behind the sample bottle (14); Ventilatory assistance and hydrogen vapor pipe (10,11) are to heat sink respectively again, and this oxygen and hydrogen vapor pipe (10,11) also are the application of sample mouth simultaneously, and sample bottle (14) outlet that connects oxygen exports the injection port that is connected to electrolyzer (4) respectively through pipeline with the sample bottle that is connected hydrogen (14); Also comprise laser transmitter and laser pickoff (16); Be located at the pipe tunnel both sides that connect in the outlet of oxygen sample bottle and one of two laterals that are connected the outlet of hydrogen sample bottle relatively, the pipe tunnel position that is between laser transmitter and the laser pickoff (16) is transparent, and this laser pickoff is exported liquid level signal to pilot circuit.
2. the device that concentrates according to claim 1; It is characterized in that: the sample bottle of said connection oxygen (14) outlet is connected to the injection port of being located at electrolyzer (4) bottom with the sample bottle that is connected hydrogen (14) outlet through three-way pipeline; This injection port also is nesting port (2) simultaneously, and this nesting port (2) is provided with drainage switch.
3. the device that concentrates according to claim 1 is characterized in that: said heat sink is refrigerator (9).
4. the device that concentrates according to claim 1; It is characterized in that: said heat sink comprises refrigerator (9) and places cooling bottle (15), recycle pump (19) and the water-cooled head (3) in the refrigerator (9); Said sample bottle (14) and reflux condensing tube (13) all place in the cooling bottle (15), and there is quench liquid inlet (12) cooling bottle (15) upper end, is full of quench liquid in the cooling bottle (15); Cooling bottle (15) upper end is tightly connected with reflux condensing tube (13) upper end; The lower end of reflux condensing tube (13) is connected with sample bottle (14) upper end, and sample bottle (14) lower end is tightly connected with cooling bottle (15) lower end, and cooling bottle (15) lower end has the import and export of quench liquid respectively; Said water-cooled head is located at electrolyzer, and the quench liquid of said cooling bottle (15) lower end is imported and exported, recycle pump (19) is communicated with into quench liquid circulation loop through the pipeline circulation successively with water-cooled head (3).
5. the device that concentrates according to claim 4 is characterized in that: said heat sink also comprises the wind-cooling heat dissipating case (20) that places on refrigerator (9) inwall, and this wind-cooling heat dissipating case (20) is located between recycle pump (19) and the water-cooled head (3).
6. the device that concentrates according to claim 5 is characterized in that: said water-cooled head (3) is provided with two, is located at the tow sides of electrolyzer (4) respectively.
7. the device that concentrates according to claim 4 is characterized in that: said water-cooled head (3) is provided with two, is located at the tow sides of electrolyzer (4) respectively.
8. according to each described device that concentrates of claim 1 to 7, it is characterized in that: said electrolyzer (4) is equipped with electronic thermometer probe (1), and this electronic thermometer probe (1) output temperature transducing signal is to pilot circuit (8).
9. according to each described device that concentrates of claim 1 to 7, it is characterized in that: said laser transmitter is located at the pipe tunnel both sides in the lateral that is connected the outlet of oxygen sample bottle relatively with laser pickoff (16).
10. the device that concentrates according to claim 9 is characterized in that: said electrolyzer is equipped with electronic thermometer probe (1), and this electronic thermometer probe (1) output temperature transducing signal is to pilot circuit (8).
CN201110247742A 2011-08-26 2011-08-26 Electrolysis and concentration device of tritium in water Active CN102286754B (en)

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CN104318968A (en) * 2014-08-21 2015-01-28 中国工程物理研究院核物理与化学研究所 Process and device for treating tritium-containing water in nuclear power plant based on electrolysis and low-temperature distillation cascade process
CN106467975B (en) * 2015-08-20 2018-08-07 环境保护部核与辐射安全中心 Surabaya electrolytic enrichment device and method
CN106990427A (en) * 2017-03-21 2017-07-28 榆林学院 Electrolysis unit and detection method for detecting low-level tritium level in underground water

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