CN1125888A - Catalytic hydrogen-eliminating technological process for nuclear energy system - Google Patents
Catalytic hydrogen-eliminating technological process for nuclear energy system Download PDFInfo
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- CN1125888A CN1125888A CN94114291A CN94114291A CN1125888A CN 1125888 A CN1125888 A CN 1125888A CN 94114291 A CN94114291 A CN 94114291A CN 94114291 A CN94114291 A CN 94114291A CN 1125888 A CN1125888 A CN 1125888A
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- hydrogen
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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Abstract
The process for using catalytic oxidation method to remove explosive gas (hydrogen) from LOCA atomosphere of pressurized-water reactor in the condition of coexistance of more compounds features that the alkaline compound having permanent damage to catalyst is first removed in settling tube and rest of LOCA atomosphere takes part in H2-O2 compound reaction through catalytic bed where gamma-alumina supported noble metal catalyst is used, returning the non-condensed gas with hydrogen content less than 0.1 V% back to safe shell. Its advantage is no exhaustion of radioactive substance.
Description
The present invention relates to a kind of in nuclear power system the catalytic hydrogen-eliminating process.System utilizes catalysis H
2-O
2Composite algorithm is eliminated the hydrogen in the nuclear power system containment.
Be one of main path of interior quite over a long time from now on solution energy shortage problem progressively with nuclear energy replacement and additional limited mineral fuel and waterpower equal energy source.One of subject matter that fears are entertained that at present is the safe reliability of nuclear power device.Concerning pressurized-water reactor, in case chilled water shortage accident (LOCA) takes place, because the reaction of zirconium and water vapour etc., can within a few hours, discharge the hydrogen of a great deal of (can reach hundreds of kilograms) and concentrate in the containment, can surpass explosion limits.At this moment, any sudden factor all can cause the nuclear power station blast.Therefore, control hydrogen discharges and the measure of eliminating hydrogen in the shell all is the important component part of nuclear power station regulating system.The method of control hydrogen concentration in the past has three kinds, i.e. inert gas dilution method, scavenging method (Zhang Qixia etc., " the chemical problem of pressurized water reactor " Atomic Energy Press, 1984) and ignition method (J.O.Henrie, U.S.P.4000978,1977; R.K.Kumar, Nuclear Engineering and Disign, 113,149,1989).More than three kinds of methods since a variety of causes will progressively be eliminated.And catalytic oxidation is to allow the airflow of hydrogen by beds H take place
2-O
2The catalytic reaction of compound (Cheng Shui) is come the method for dehydrogenation, and its advantage is to realize the outer loop of gas in the shell, does not cause the radioactive contamination to environment, and initiation temperature and hydrogen concentration are all very low, and device is simple, and is safe and reliable.But used usually oxidation catalyst for removing hydrogen is easily poisoned inactivation by water vapour at ambient temperature, thereby can not be used for the regulation and control of hydrogen concentration under the humid atmosphere in the LOCA containment.In recent years, the Soviet Union (В. Д. К e л л e р, et al. А Т о М Н а я Э Н e р г и я, 67 (5), 335,1989 years), West Germany (A.K.Chakraborty a. Kerntechnik, 1,53,1988, b.Ger.Offen.DE 3826503, nineteen ninety) and this laboratory (Wang Yan, scholar etc. in crossing, environmental science, 5 (2), 18,1984) work prove, passive catalytic dehydrogenation system can lean on the mode of natural convection to play a role under humid atmosphere, but this is only applicable to hydrogen concentration control in little space, and the hydrogen concentration that control in the whole containment just need increase catalyst surface area pro rata, the height of its cost, efficient low be difficult to received.Above-mentioned Chakraborty etc. once overcame contained CO, I in the atmosphere with the aluminium foil that adds coating (Pd-V-Pd-Pt or Ru)
2, poisonous substance such as water vapor is to H on the catalyzer
2-O
2The depression effect of recombination reaction.Not only complicated process of preparation, and cost also is very high.Once with improving the reaction bed temperature, the way that increases catalyst surface simultaneously made poisonous substance (boric acid, I to Berndt etc. (Chemie-Technik, 9 (2), 63,1980 years)
2Deng) from catalyst surface desorption as early as possible, and prevent that catalyst surface from being covered fully by the poisonous substance of desorption not, though under the condition of drafting, can keep dehydrogenation effect preferably, behind the short term tests, Pd/ γ-Al
2O
3Activity of such catalysts obviously reduces.The Soviet Union and Canada (W.R.C.Graham, Preprint of IAEA/CECWorkshop on Hydrogen Behavior and Mitigationin Water Reactors, Brussels, March, 4-8,1991) atomic energy research unit all be the H of moisture resistance
2-O
2Composite catalyst, but about the antitoxin thing of catalyzer (as H
3BO
3, I
2, alkali metal salt etc.) but report seldom of research work.Therefore, studying the antitoxin performance of this class catalyzer is to realize the key technical problem of LOCA hydrogen in the catalysis composite algorithm elimination nuclear power plant containment shell in the world today with finding out the operating conditions that makes composite catalyst energy long-term stable operation when loss of-coolant accident (LOCA) under the atmosphere of containment top.
The objective of the invention is: utilization can be suitable for forced circulation duct type (also being applicable to what natural convection drove) catalyzer hydrogen recombiner, gamma ray resistant irradiation, the technological process of appropriate design and each unit operations condition thereof, keep catalyzer under possible LOCA condition, high activity long-time running, residual hydrogen concentration are satisfied and to be returned containment requirement (≤0.1%).
The detailed description of the invention:
The present invention is directed to the plurality of impurities that coexists in the LOCA atmosphere, adopt the sedimentation process flow process to remove the component harmful to catalyzer, both guarantee high activity of catalyst, running steady in a long-term, saved huge water scrubber device (having avoided radioactive contamination of water simultaneously) again.
The present invention's several steps in the following order carries out:
(1) unstrpped gas (micro-boric acid is arranged simultaneously, NaOH, iodine, all the other are air) that contains hydrogen 1-3.8V% enters the settler that temperature is controlled at 140～160 ℃ from the top, part high-boiling-point impurity (NaOH, H
3BO
3) solution be deposited in the bottom.
(2) gas is discharged from the settler top exit and is entered the catalytic recombiner that temperature is controlled at 200～235 ℃, is containing active constituent platinum-palladium 0.3～0.05% (wt), and auxiliary agent is alkaline metal or earth alkali metal, and carrier is Al
2O
3The beds effect under carry out Hydrogen Oxygen reaction.
(3) reaction end gas is isolated H through condenser condenses
3BO
3, I
2Deng aqueous solution, inconduc is discharged from lower part outlet.
Settler of the present invention adds hot jacket by temperature control, the evaporation setting chamber, and compositions such as liquid level control valve and basin, its center of top has the charging nanubrium, and top one side has escape pipe.
Catalytic recombiner of the present invention adds hot jacket by temperature control, compositions such as beds, and its air intake opening is at the top, and the gas outlet is in the bottom.
Catalyzer of the present invention is with sphere, column type or fibrous Al
2O
3Be carrier, its active constituent is except that metallic state palladium and platinum, at least a other elements (alkaline metal or earth alkali metal) can also be arranged as auxiliary agent, the preparation method can adopt infusion process, immobilized method of organic compound or ion exchange process, catalyst shape can be granular (Φ 2.5～3.5mm) or fibrous.In order to reduce cost, can be the noble metal overall control at 0.3～0.05wt%.Compared with the prior art, the substantive distinguishing features that the present invention has: 1. in technological process, designed the sedimentation pipe that to hold back most of poisonous substance, pipe outer wall adjustable electric hot jacket temperature control, when operating conditions is suitable, most of impurity in its unstripped gas, the alkali compounds such as NaOH that particularly can cause the permanent poisoning of catalyzer then all are trapped within the pipe, poisonous substance solution concentrates gradually and separates out until solid, gas after the sedimentation does not have can make the permanent alkali metal compound of poisoning of catalyzer, can contain a spot of boric acid, impurity such as iodine, and under suitable condition, pass through beds.The plurality of impurities coexistence sedimentation process that this flow process adopts has saved huge water scrubber equipment, "dead" sewage discharge, energy consumption is low, install little, economical rationality.2. the used H of the present invention
2-O
2Composite catalyst belongs to loaded noble metal catalyst, and its active constituent is Metal Palladium and platinum, also contains one or more auxiliary elements, carrier Al
2O
3, the content of its noble metal is at 0.3～0.05wt%.Under wet environment, start H
2-O
2The temperature of recombination reaction is low, has very high catalytic activity, anti-H under suitable condition
3BO
3, I
2Deng the murder by poisoning of impurity, and to stand accumulated dose be 1.11 * 10
6Active constant after the gamma-rays radiation of rad.3. under possible LOCA condition, sedimentation pipe of the present invention and H
2-O
2The composite catalyzing device cooperates suitable technological process, making in the LOCA atmosphere has the impurity of permanent murder by poisoning all to be trapped to catalyzer, the most of reversible poison of sedimentation simultaneously, only there is the small part reversible poison under suitable condition, not influence it and removes hydrogen activity by beds, thereby guarantee catalyzer running steady in a long-term, make the interior residual hydrogen concentration of containment be lower than explosion limits all the time.In order to understand the present invention better, Fig. 1 is done following being described more specifically: impurity unstrpped gas enters settler 1 by air inlet nanubrium 5, and temperature control adds hot jacket 2 makes vaporization chamber 8 temperature under 140～160 ℃, part high-boiling-point impurity (NaOH, H
3BO
3Deng) solution 7 is deposited over the bottom with condensate water, discharges condensed fluids to waste material basin 4 by liquid level control valve 3.Reacting gas 6 enters catalytic recombiner 9 through the gas outlet, add at temperature control and to make the recombiner temperature be controlled at 200～235 ℃ under the hot jacket effect, gas carries out oxyhydrogen reaction by beds 10, can guarantee under this operating conditions in the air-flow the catalyzer oxious component (as H
2O, H
3BO
3, I
2) have no deposition at catalyst surface, thus it kept to H
2-O
2The high catalytic activity of reaction makes the residual hydrogen concentration long term maintenance of recombiner tail gas at≤0.1V%.Reaction end gas is isolated H through condenser condenses
3BO
3, I
2Deng aqueous solution, also put into waste material basin 4, inconduc enters containment, thereby the hydrogen concentration of control in the containment guarantees nuclear plant safety production below explosion limits.
The following constitutive material gas of embodiment example 1. preparations is as simulating LOCA gas: hydrogen,
1.0～3.8v%; Boric acid, 1.5wt%; NaOH, 0.6wt%;
Iodine, 4 * 10
-5Wt%; Relative humidity 10～100%, all the other are air.
Adopt the 0.15%Pd-Pt/Al of an amount of immersion process for preparing
2O
3Catalyzer,
140～160 ℃ of control sedimentation pipe temperature, reaction bed temperature 200～
In the time of 235 ℃, can hold back permanent poison effectively, guarantee that catalyzer is high alive
The property long-term operation, in continuous operation 2200h, residual hydrogen in the reaction end gas
Concentration is always less than 0.1v%.Example 2. is carried out irradiation treatment to catalyzer described in the example 1 earlier, and radiation source is Co
60
The gamma-rays in plate source, intensity are 7.5 * 10
4Rad/h, accumulative total irradiation 14
Hours 50 minutes, accumulated dose reached 1.1 * 10
6Among the rad, same day use-case 1.
Unstripped gas, experimental provision and operating conditions urge doing through the sample of irradiation
Change the composite performance evaluation, the result shows, its catalytic activity with without γ-spoke
The fresh catalyst of penetrating does not have detectable difference.Measure with the BET method
The specific surface area of predose rear catalyst is used H
2-O
2Titration and TEM (sample
Product are through the HF solution corrosion) measure the dispersion degree of noble metal, all do not have basically
Difference (table 1.) is arranged, as seen, at the integral dose γ of designing requirement irradiation
Scope in, do not cause that catalyst surface structure and catalytic performance can examine
The variation of surveying.
The character of NR-18 catalyzer before and after table 1. γ-radiation
| Sample | Specific surface area (m 2/g) | Metal dispersity (%) | ?H 2-O 2Composite reactive (%) |
| Predose | ????155.7 | ?????36 | ?????100 |
| Behind the irradiation | ????155.0 | ?????36 | ?????100 |
Claims (2)
1. catalytic hydrogen-eliminating technological process at the high hydrogen concentration atmosphere that is produced in the nuclear power station LOCA accident, the core of this process is by selecting poisonous substance sedimentation pipe, H
2-O
2Composite catalyzing reactor and tail gas condensation separation are partly formed, this process several steps in the following order carries out: the unstrpped gas that contains hydrogen 1-3.8V% that (1) is drawn by containment top (has micro-boric acid, NaOH, iodine simultaneously, all the other are air) enter the settler that temperature is controlled at 140～160 ℃ from the top, make partial impurities solution be deposited in the bottom; (2) gas enters the catalytic recombiner that temperature is controlled at 200～235 ℃ from settler top escape hole, is containing active constituent platinum-palladium 0.3～0.05% (wt), and auxiliary agent is alkaline metal or earth alkali metal, and carrier is Al
2O
3The beds effect under carry out hydrogen oxygen composite reaction; Under above-mentioned controlled condition, can make in the unstripped gas institute's boronic acid containing, iodine, water vapour etc. by bed, keep this catalyzer and have very high H for a long time
2-O
2Composite reactive guarantees the residual hydrogen of tail gas≤0.1%.(3) reaction end gas is through condenser condenses, removing foreign matter solution; Inconduc is discharged from lower part outlet, returns containment.
2. as the said process of claim 1, settler adds hot jacket by temperature control, the evaporation setting chamber, and liquid level control valve and basin are formed, and it is characterized in that center of top has the charging nanubrium, and top one side has escape pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114291A CN1125888A (en) | 1994-12-28 | 1994-12-28 | Catalytic hydrogen-eliminating technological process for nuclear energy system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114291A CN1125888A (en) | 1994-12-28 | 1994-12-28 | Catalytic hydrogen-eliminating technological process for nuclear energy system |
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| Publication Number | Publication Date |
|---|---|
| CN1125888A true CN1125888A (en) | 1996-07-03 |
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| CN94114291A Pending CN1125888A (en) | 1994-12-28 | 1994-12-28 | Catalytic hydrogen-eliminating technological process for nuclear energy system |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849412B (en) * | 2003-09-12 | 2011-01-05 | 拜尔材料科学股份公司 | Method for electrolyzing aqueous hydrogen chloride solution or aqueous alkali chloride solution |
| CN102247838A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Supported palladium catalyst with characteristic of specific infrared absorption |
| CN101811013B (en) * | 2009-02-20 | 2012-01-25 | 中国核电工程有限公司 | Catalysis type hydrogen compounding process method in nuclear power plant |
| CN101625908B (en) * | 2009-07-22 | 2012-06-27 | 中国广东核电集团有限公司 | Boron recovery system of nuclear power plant |
| CN102671717A (en) * | 2012-06-05 | 2012-09-19 | 四川材料与工艺研究所 | Precious metal alkaline solution and preparation method thereof |
| CN101777392B (en) * | 2009-11-17 | 2012-10-10 | 华北电力大学 | Accident buffering and removing device for nuclear power station by supercritical CO2 |
| CN103033591A (en) * | 2012-12-20 | 2013-04-10 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN104220166A (en) * | 2012-04-02 | 2014-12-17 | 科莱恩产品（德国）有限公司 | Hydrogen oxidation catalyst, use thereof, and method for hydrogen recombination |
| CN104541331A (en) * | 2012-08-01 | 2015-04-22 | 阿海珐有限公司 | Containment protection system for a nuclear facility and associated operating method |
| CN105556613A (en) * | 2013-11-26 | 2016-05-04 | 阿科姆工程合资(控股)公司 | System for purifying a gaseous medium of hydrogen and method for the use thereof |
| CN105895183A (en) * | 2016-04-21 | 2016-08-24 | 中广核研究院有限公司 | Carbon-14-containing waste gas treatment method and system |
| CN108364698A (en) * | 2018-01-03 | 2018-08-03 | 中广核研究院有限公司 | The small space of nuclear power station disappears hydrogen methods and system |
| CN112185593A (en) * | 2020-09-30 | 2021-01-05 | 中国核动力研究设计院 | Pressure difference filtering type built-in dehydrogenation treatment device and method |
| CN113797748A (en) * | 2021-09-28 | 2021-12-17 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Flow direction conversion microwave catalytic hydrogen eliminator and hydrogen elimination method |
-
1994
- 1994-12-28 CN CN94114291A patent/CN1125888A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849412B (en) * | 2003-09-12 | 2011-01-05 | 拜尔材料科学股份公司 | Method for electrolyzing aqueous hydrogen chloride solution or aqueous alkali chloride solution |
| CN101811013B (en) * | 2009-02-20 | 2012-01-25 | 中国核电工程有限公司 | Catalysis type hydrogen compounding process method in nuclear power plant |
| CN101625908B (en) * | 2009-07-22 | 2012-06-27 | 中国广东核电集团有限公司 | Boron recovery system of nuclear power plant |
| CN101777392B (en) * | 2009-11-17 | 2012-10-10 | 华北电力大学 | Accident buffering and removing device for nuclear power station by supercritical CO2 |
| CN102247838A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Supported palladium catalyst with characteristic of specific infrared absorption |
| CN104220166A (en) * | 2012-04-02 | 2014-12-17 | 科莱恩产品（德国）有限公司 | Hydrogen oxidation catalyst, use thereof, and method for hydrogen recombination |
| CN102671717A (en) * | 2012-06-05 | 2012-09-19 | 四川材料与工艺研究所 | Precious metal alkaline solution and preparation method thereof |
| CN104541331A (en) * | 2012-08-01 | 2015-04-22 | 阿海珐有限公司 | Containment protection system for a nuclear facility and associated operating method |
| CN103033591B (en) * | 2012-12-20 | 2015-02-18 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN103033591A (en) * | 2012-12-20 | 2013-04-10 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN105556613A (en) * | 2013-11-26 | 2016-05-04 | 阿科姆工程合资(控股)公司 | System for purifying a gaseous medium of hydrogen and method for the use thereof |
| CN105895183A (en) * | 2016-04-21 | 2016-08-24 | 中广核研究院有限公司 | Carbon-14-containing waste gas treatment method and system |
| CN108364698A (en) * | 2018-01-03 | 2018-08-03 | 中广核研究院有限公司 | The small space of nuclear power station disappears hydrogen methods and system |
| CN108364698B (en) * | 2018-01-03 | 2020-05-22 | 中广核研究院有限公司 | Hydrogen elimination method and system for small space of nuclear power station |
| CN112185593A (en) * | 2020-09-30 | 2021-01-05 | 中国核动力研究设计院 | Pressure difference filtering type built-in dehydrogenation treatment device and method |
| CN113797748A (en) * | 2021-09-28 | 2021-12-17 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Flow direction conversion microwave catalytic hydrogen eliminator and hydrogen elimination method |
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