CN112760665B - Method and device for recovering deuterium in deuterium-containing waste gas - Google Patents
Method and device for recovering deuterium in deuterium-containing waste gas Download PDFInfo
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Abstract
The invention relates to a method and a device for recovering deuterium in deuterium-containing waste gas, and belongs to the technical field of deuterium-containing waste gas treatment. The method comprises the steps of humidifying waste gas containing inert gas and deuterium gas by using heavy water, then electrolyzing, collecting pure deuterium gas at a cathode, and collecting deuterium-depleted inert gas at an anode.
Description
Technical Field
The invention relates to a method and a device for recovering deuterium in deuterium-containing waste gas, and belongs to the technical field of deuterium-containing waste gas treatment.
Background
The optical fiber can generate disordered Si-O free radicals during the drawing process, and Si-OH is easily generated with H and easily aged. Therefore, various full-wave optical fibers can withstand the corrosion of a hydrogen-containing environment for a long time after being subjected to deuterium treatment after being drawn.
In the preparation process of the optical fiber, the optical fiber is typically placed in a static mixture of deuterium in inert gas, usually nitrogen contains 1-10% by volume of deuterium, the concentration of deuterium is very important for the diffusion process, and glass absorbs deuterium through diffusion, but the amount of deuterium entering the glass in the mixture is very small, which means that deuterium is a large cost in the production of the optical fiber, and therefore, how to recycle deuterium in the deuterium-containing gas mixture is very important.
The existing method for recovering deuterium in deuterium-containing gas mixture generally adopts a pressure swing adsorption method or a temperature swing adsorption method, and pressure or temperature change operation is required during recovery so as to regenerate the adsorbent, so that the operation is complicated, continuous work cannot be realized, and the recovery rate of deuterium gas is low.
Disclosure of Invention
The invention aims to provide a method and a device for recovering deuterium in deuterium-containing waste gas, aiming at overcoming the defects existing in the prior art, the deuterium-containing waste gas is humidified by heavy water and then electrolyzed, and pure deuterium gas can be collected at a cathode.
The purpose of the invention is realized by the following technical scheme.
A method for recovering deuterium from deuterium containing exhaust gas, said method comprising the steps of:
(a) humidifying the waste gas containing inert gas and deuterium gas by using heavy water;
(b) introducing the humidified waste gas into an anode chamber of an electrochemical hydrogen pump for electrolysis, wherein the electrolysis temperature is not more than 80 ℃, and the current density is 100mA/cm2～450mA/cm2Collecting deuterium depleted inert gas from the anode and deuterium from the cathode;
(c) drying and removing water from the collected deuterium-depleted inert gas and deuterium respectively, and storing for later use.
Wherein the flow rate of deuterium in the exhaust gas entering the anode chamber is not more than 8L/min.
Further, in the step (a), preferably, a plate-type membrane humidifier or a tubular membrane humidifier is used to humidify the waste gas, the temperature for humidifying the waste gas by using heavy water is preferably 50-60 ℃, the relative humidity of the waste gas after being humidified by the heavy water is preferably 50-100%, and the humidification of the waste gas can improve the conductivity of the proton exchange membrane in the electrochemical hydrogen pump, improve the electrolysis efficiency, maintain the conductivity of the proton exchange membrane at a certain humidity, avoid the conductivity reduction of the proton exchange membrane, and simultaneously avoid the flooding phenomenon caused by overhigh humidity.
Furthermore, in the step (b), after the waste gas is introduced into the anode chamber, the pressure in the anode chamber is preferably 0.1MPa to 0.3MPa, so that the reduction of the purity of the finished gas caused by the inert gas permeating the proton exchange membrane due to overhigh pressure is avoided.
Further, in the step (b), the electrolysis temperature is preferably 50 to 65 ℃ and the current density is preferably 250mA/cm2～400mA/cm2The proper current density and electrolysis temperature can keep the utilization rate of the proton exchange membrane and avoid the influence on the electrolysis efficiency.
Furthermore, the volume fraction of deuterium in the waste gas is preferably 1-20%, the flow rate of waste gas entering the anode chamber is preferably 10-30L/min, the improvement of deuterium content can improve the electrolysis efficiency and recovery rate, and if the content is too low, the recovery efficiency is poor, and the recovery value is not high.
Further, in order to secure purity and pressure, it is preferable to use an electrochemical hydrogen pump including at least three hydrogen pump units.
Further, drying and dehydrating the collected deuterium-depleted inert gas and deuterium respectively by using a drying tower filled with molecular sieves.
Furthermore, after the molecular sieve in the drying tower is adsorbed and saturated, the gas can be regenerated and recycled at 160-280 ℃, and the heavy water obtained after the desorbed gas is condensed by a condenser in the regeneration process can be recycled.
The device comprises a humidifier, an electrochemical hydrogen pump, a first steam-water separator, a second steam-water separator, a first drying tower and a second drying tower;
the air outlet of the humidifier is connected with the air inlet of the electrochemical hydrogen pump, the anode air outlet of the electrochemical hydrogen pump is connected with the air inlet of the first water-vapor separator, the air outlet of the first water-vapor separator is connected with the first drying tower, dry deuterium-depleted inert gas is collected from the air outlet of the first drying tower, the cathode air outlet of the electrochemical hydrogen pump is connected with the air inlet of the second water-vapor separator, the air outlet of the second water-vapor separator is connected with the second drying tower, dry deuterium gas is collected from the air outlet of the second drying tower, and the liquid discharge port of the first water-vapor separator and the liquid discharge port of the second water-vapor separator are respectively connected with the water injection port of the humidifier.
Has the advantages that:
(1) the method can enrich deuterium gas with lower concentration to higher concentration, the enriched deuterium with high concentration can be recycled, and the collected deuterium-depleted inert gas can also be recycled, so that resources can be fully utilized, and the cost is reduced; the method only needs to carry out electrolysis treatment on the humidified deuterium-containing waste gas, does not need pressure swing or temperature swing operation, does not need an adsorbent, and is simple to operate; in addition, the recovery rate of deuterium can reach 98% by optimizing process parameters;
(2) the recovery device disclosed by the invention is simple in structure, strong in operability, suitable for industrial production, capable of realizing long-time continuous and stable operation and good in industrial application prospect.
Drawings
FIG. 1 is a schematic structural diagram of the recycling apparatus in the embodiment.
The system comprises a humidifier 1, an electrochemical hydrogen pump 2, a first steam-water separator 3, a second steam-water separator 4, a first drying tower 5 and a second drying tower 6.
Detailed Description
The present invention is further illustrated by the following figures and detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples, when recovering deuterium gas from an exhaust gas containing nitrogen gas and deuterium gas, the recovery apparatus used includes a humidifier 1, an electrochemical hydrogen pump 2, a first steam-water separator 3, a second steam-water separator 4, a first drying tower 5, and a second drying tower 6, as shown in fig. 1;
the humidifier 1 is the prior art, and can be a plate-type membrane humidifier or a tubular membrane humidifier, and specifically can select a membrane humidifier for a fuel cell disclosed in chinese patent CN 209926519U;
the electrochemical hydrogen pump 2 is the prior art, mainly comprises a gas diffusion electrode, a flow field plate, a catalyst and a proton exchange membrane, and specifically can use the electrochemical hydrogen pump disclosed in Chinese patent CN 110747486A; deuterium gas reacts in the anode chamber as follows: d2→2D++2e-The cathode chamber reaction is: 2D++2e-→D2；
The first drying tower 5 and the second drying tower 6 are both drying towers filled with molecular sieves, and specifically, 13X molecular sieves can be used; in addition, after the molecular sieve is adsorbed and saturated, the molecular sieve can be regenerated and recycled at 160-180 ℃, and heavy water obtained after the desorbed gas is condensed by a condenser in the regeneration process can be recycled and added into the humidifier 1 for recycling;
as shown in fig. 1, the connection relationship between the components is as follows: the air outlet of the humidifier 1 is connected with the air inlet of the electrochemical hydrogen pump 2, the anode air outlet of the electrochemical hydrogen pump 2 is connected with the air inlet of the first water-vapor separator 3, the air outlet 3 of the first water-vapor separator is connected with the first drying tower 5, dry deuterium-depleted nitrogen is collected from the air outlet of the first drying tower 5, the cathode air outlet of the electrochemical hydrogen pump 2 is connected with the air inlet of the second water-vapor separator 4, the air outlet of the second water-vapor separator 4 is connected with the second drying tower 6, dry deuterium is collected from the air outlet of the second drying tower 6, and the liquid discharge port of the first water-vapor separator 3 and the liquid discharge port of the second water-vapor separator 4 are respectively connected with the water filling port of the humidifier 1.
Example 1
The specific steps for recovering deuterium gas from an off-gas containing 97 vol% nitrogen and 3 vol% deuterium gas based on the recovery apparatus described in fig. 1 are as follows:
(a) introducing the waste gas into a humidifier 1 at the flow rate of 10L/min, and humidifying the waste gas by using heavy water at the temperature of 50 ℃;
(b) the humidified waste gas with the relative humidity of 50 percent enters an electrochemical hydrogen pump at the flow rate of 10L/min2, the pressure in the anode chamber is 0.1MPa, the electrolysis temperature is 50 ℃, and the current density is 200mA/cm2The poor deuterium nitrogen generated after the waste gas passes through the anode flow field enters the first water-vapor separator 3, and the deuterium generated after the waste gas passes through the cathode flow field passes through the second water-vapor separator 4;
(c) the deuterium depleted nitrogen gas passing through the first water-vapor separator 3 enters the first drying tower 5, and the dried deuterium depleted nitrogen gas is collected from the gas outlet of the first drying tower 5; the deuterium gas passing through the second water vapor separator 4 enters the second drying tower 6, and the dried deuterium gas is collected from the gas outlet of the second drying tower 6.
The deuterium gas recovered in the embodiment has the dew point of-90 ℃, the purity of 98.9 percent, the recovery rate of deuterium of 90 percent and the output pressure of 20 MPa; the recovered deuterium depleted nitrogen has a deuterium content of 0.3 vol%.
Example 2
The specific steps for recovering deuterium gas from an exhaust gas containing 80 vol% nitrogen and 20 vol% deuterium gas based on the recovery apparatus shown in fig. 1 are as follows:
(a) introducing the waste gas into a humidifier 1 at the flow rate of 30L/min, and humidifying the waste gas by using heavy water at the temperature of 60 ℃;
(b) the humidified waste gas with the relative humidity of 60 percent enters an anode chamber of the electrochemical hydrogen pump 2 at the flow rate of 30L/min for electrolysis, the pressure in the anode chamber is 0.2MPa, the electrolysis temperature is 60 ℃, and the current density is 350mA/cm2The poor deuterium nitrogen generated after the waste gas passes through the anode flow field enters the first water-vapor separator 3, and the deuterium generated after the waste gas passes through the cathode flow field passes through the second water-vapor separator 4;
(c) the deuterium depleted nitrogen gas passing through the first water-vapor separator 3 enters the first drying tower 5, and the dried deuterium depleted nitrogen gas is collected from the gas outlet of the first drying tower 5; the deuterium gas passing through the second water vapor separator 4 enters the second drying tower 6, and the dried deuterium gas is collected from the gas outlet of the second drying tower 6.
The deuterium gas recovered in the embodiment has the dew point of-85 ℃, the purity of 99 percent, the recovery rate of the deuterium of 98 percent and the output pressure of 20 MPa; the recovered deuterium depleted nitrogen has a deuterium content of 0.4 vol%.
Example 3
The specific steps for recovering deuterium gas from an off-gas containing 95 vol% nitrogen and 5 vol% deuterium gas based on the recovery apparatus described in fig. 1 are as follows:
(a) introducing the waste gas into a humidifier 1 at the flow rate of 20L/min, and humidifying the waste gas by using heavy water at the temperature of 55 ℃;
(b) the humidified waste gas with the relative humidity of 100 percent enters an anode chamber of an electrochemical hydrogen pump 2 at the flow rate of 20L/min for electrolysis, the pressure in the anode chamber is 0.3MPa, the electrolysis temperature is 55 ℃, and the current density is 300mA/cm2The poor deuterium nitrogen generated after the waste gas passes through the anode flow field enters the first water-vapor separator 3, and the deuterium generated after the waste gas passes through the cathode flow field passes through the second water-vapor separator 4;
(c) the deuterium depleted nitrogen gas passing through the first water-vapor separator 3 enters the first drying tower 5, and the dried deuterium depleted nitrogen gas is collected from the gas outlet of the first drying tower 5; the deuterium gas passing through the second water vapor separator 4 enters the second drying tower 6, and the dried deuterium gas is collected from the gas outlet of the second drying tower 6.
The deuterium gas recovered in the embodiment has the dew point of-89 ℃, the purity of 99 percent, the recovery rate of the deuterium of 98 percent and the output pressure of 20 MPa; the recovered deuterium depleted nitrogen has a deuterium content of 0.1 vol%.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for recovering deuterium from deuterium-containing exhaust gas, comprising: the steps of the method are as follows,
(a) humidifying the waste gas containing inert gas and deuterium gas by using heavy water;
(b) introducing the humidified waste gas into an anode chamber of an electrochemical hydrogen pump for electrolysis, wherein the electrolysis temperature is not more than 80 DEGoC, current density of 100mA/cm2~450 mA/cm2Collecting deuterium depleted inert gas from the anode and deuterium from the cathode;
(c) drying and dehydrating the collected deuterium-depleted inert gas and deuterium respectively, and storing for later use;
wherein, the flow rate of deuterium in the waste gas entering the anode chamber is not more than 8L/min; in the step (a), the relative humidity of the waste gas after being humidified by the heavy water is 50-100%; in the step (b), after the waste gas is introduced into the anode chamber, the pressure in the anode chamber is 0.1 MPa-0.3 MPa; the volume fraction of deuterium in the exhaust gas is 1% -20%.
2. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: in the step (a), a plate type membrane humidifier or a tubular membrane humidifier is adopted to humidify the waste gas.
3. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: in the step (a), the temperature for humidifying the off-gas with the heavy water is 50 DEGoC~60 oC。
4. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: in step (b), the electrolysis temperature is 50oC~65 oC, the current density is 250mA/cm2~400 mA/cm2。
5. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: the flow rate of the waste gas entering the anode chamber is 10L/min-30L/min.
6. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: an electrochemical hydrogen pump is used that contains at least three hydrogen pump cells.
7. The method as claimed in claim 1, wherein said deuterium recovery step comprises the steps of: drying and dehydrating the collected deuterium-depleted inert gas and deuterium by adopting a drying tower filled with a molecular sieve; after the molecular sieve in the drying tower is adsorbed and saturated, 160 ℃ is carried outoC~280 oAnd C, performing regeneration and recycling, and condensing the desorbed gas in the regeneration process through a condenser to obtain heavy water for recycling.
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| CN1834002A (en) * | 2005-03-15 | 2006-09-20 | 大连世纪欣科高新技术开发有限公司 | Method of producing super-high pure tritium gas by utilizing heavy-water as raw material |
| CN101306302B (en) * | 2008-01-31 | 2011-08-31 | 上海交通大学 | Hydrogen containing industrial waste gas separation and purification method |
| CN106342104B (en) * | 2008-12-09 | 2011-09-14 | 中国船舶重工集团公司第七一八研究所 | A kind of heavy water electrolysis is prepared the method for high-purity deuterium gas |
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