CN104338510A - Method for removing radioactive iodine from gas cooled reactor - Google Patents

Method for removing radioactive iodine from gas cooled reactor Download PDF

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Publication number
CN104338510A
CN104338510A CN201310326820.5A CN201310326820A CN104338510A CN 104338510 A CN104338510 A CN 104338510A CN 201310326820 A CN201310326820 A CN 201310326820A CN 104338510 A CN104338510 A CN 104338510A
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molecular sieve
silver
adsorbent
except
temperature
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贺德华
褚泰伟
房超
刘会敏
程庆辉
杨维维
李泽军
朱秋锋
李宇明
吴昊
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Tsinghua University
Peking University
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Peking University
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/02—Treating gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a method for removing radioactive iodine from a gas at a high temperature, and belongs to the technical fields of environmental protection and the nuclear industry. The method is characterized in that a silver loaded adsorbent is adopted to remove radioactive iodine from a gas cooled reactor primary circuit at a high temperature of 350-650DEG C; the silver loaded adsorbent is prepared through dipping and high-temperature thermal treatment with silver as an adsorption component and a molecular sieve as a carrier; and the silver loaded adsorbent has high thermal stability and strong decontamination ability.

Description

A kind of method removing radioiodine in HTGR
Technical field
The present invention relates to a kind of Ag adsorbent for Adsorption of Radioactive iodine and preparation method thereof, belong to field of environment protection, also belong to nuclear industry technology and adsorbent manufacturing engineering technical field.
Background technology
Along with the development of nuclear industry, the radioactive substance in the exhaust of purification heap has become very important and distinct issues.Wherein, the purification of radioiodine is subject to the most attention of various countries.Radioiodine is a kind of volatile, thyrodesmic high toxicity nucleic; Radioiodine directly leaks in air will pollute surrounding environment.In order to ensure Environmental security, effective control techniques must be taked.The purification of iodine or iodide, usually adopts Adsorption or absorbs trapping technique.Active carbon or macroreticular resin are widely used in the removal of iodine under comparatively temperate condition or iodide, but active carbon and macroreticular resin are not suitable for processing procedure, the such as subsequent processes of nuclear fuel reactor under high temperature.On the other hand, carry the solid absorbent of silver, as carried silver-colored silica, carrying silver-colored aluminium oxide and silver molecular sieve etc., be widely used in the Adsorption process of iodine, be also applied in the process of nuclear fuel emission gases.
United States Patent (USP) (US4735786) number reports a kind of adsorbent of the molecular sieve carried silver for removing iodine or iodide; Another United States Patent (USP) (US6380428) discloses year silvermodenite molecular sieve made by ion-exchange, for removing the iodide in Korrosionsmedium; United States Patent (USP) (US4913850) also reports a kind of argentiferous faujasite molecular sieve adsorbent, and for adsorbing organic iodine in radiativity core waste gas and inorganic iodine, but these adsorbents are also use at the temperature about room temperature ~ 100 DEG C substantially.
Japan Patent (JP54-133299) reports the manufacturing technology of a kind of year silver-colored adsorbent: adopt aluminium oxide or silica to be carrier, using silver oxide, silver carbonate or silver sulfate as silver components, can be used for elemental iodine or CH in the waste gas of high humility 3i removes; Another Japan Patent (JP55027011) discloses a kind of with silver sulfite (Ag 2sO 3) be carried on SiO for main component 2or Al 2o 3or Al 2o 3-SiO 2what composite oxides apply simultaneously last layer organic matter film (as dioctyl phthalate or silicone oil etc.) carries silver-colored adsorbent, for high humility, removing containing iodine in iodine mist containing smog, but serviceability temperature is also be confined to comparatively low temperature (near room temperature).
Chinese patent (application number 200410052771.1) reports a kind of working load mercury, silver, the natural minerals foresite removal iodine of palladium and the method for iodide impurities, but it is mainly used for removing iodine contained in carboxylic acid or carboxylic acid anhydrides liquid and iodide impurities, and serviceability temperature is limited in 18 ~ 100 DEG C; Equally, Chinese patent (application number 200510111057.X) discloses a kind of use and carries iodide in silver-colored large pore molecular sieve removal acetic anhydride liquid, and serviceability temperature is 60 ~ 100 DEG C; Another Chinese patent (application number 03141605.5,03141604.7) reports a kind of high silver carrying ZSM-5 zeolite deiodination adsorbent, but is also mainly the removal for iodide in acetum, and serviceability temperature is room temperature ~ 110 DEG C.
Document Journal ofNuclear Science and Technology (31 (1994) 1073) reports a kind of silver nitrate impregnated alumina (silver content 24wt%) adsorbent, for removing iodomethane and iodine, but there is the low problem of operating temperature (150 DEG C).Document Journal of Radioanalytical and Nuclear Chemistry (256 (2003) 19) also reports silver molecular sieve adsorbent prepared by a kind of ion-exchange, for the removal of the radioiodine methane under higher temperature, but described maximum temperature is not also more than 300 DEG C.
Although existing technology can eliminate radioactive iodine to a certain extent or containing iodine compound, the serviceability temperature of adsorbent used is on the low side, is not suitable for using in HTGR.The present invention adopts silver to be carrier for absorbed component, molecular sieve, has prepared silver molecular sieve adsorbent through dipping and high-temperature heat treatment method.Use silver molecular sieve adsorbent of the present invention can radioiodine in 350 ~ 650 DEG C of Removal under High Temperature HTGRs.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the Ag adsorbent for Adsorption of Radioactive iodine.Ag adsorbent provided by the invention has heat-resisting quantity, has high absorption property, can at high temperature Adsorption of Radioactive iodine.
The preparation method of the Ag adsorbent for Adsorption of Radioactive iodine that the present invention proposes, is characterized in that: take molecular sieve as carrier, AgNO 3for the presoma of Ag, the method for employing dipping, high-temperature heat treatment prepares Ag/ adsorbent of molecular sieve.Use Ag adsorbent provided by the invention, there is heat-resisting quantity, can at high temperature Adsorption of Radioactive iodine.
Silver molecular sieve adsorbent provided by the invention has good heat-resistant stability, and at 350 ~ 650 DEG C, heat treatment 2 ~ 20 hours in air under normal pressure, still remains the crystal phase structure of carrier (molecular sieve), silver-colored crystal grain is less.Silver molecular sieve adsorbent provided by the invention also has good withstand voltage stability, and at the flowing helium of 4MPa pressure and 650 DEG C, heat treatment is after 100 hours, and the structure of corresponding carrier (molecular sieve) does not wreck.
The preparation method of the Ag-adsorbent of molecular sieve that the present invention relates to and as follows to the testing procedure of the absorption property of radioiodine:
(1) preparation of Ag/ adsorbent of molecular sieve
The present invention has mainly selected 13X molecular sieve, H-beta molecular sieve and Na-Y molecular sieve as carrier; granularity is 0.25 ~ 0.85mm (20 ~ 60 order) powder granule or 4mm spheric granules, and the molecular sieve selected heats 2 hours before use in atmosphere at 600 DEG C.The precursor of Ag selects AgNO 3.For Ag/13X, its preparation process is as follows:
Take a certain amount of AgNO 3, be dissolved in a certain amount of deionized water, stir.Take a certain amount of 13X molecular sieve, drop into above-mentioned AgNO 3in solution, stirred at ambient temperature floods 12 hours, then evaporative removal moisture, drying 12 hours at 110 DEG C.Dried sample is placed in Muffle furnace, rises to certain temperature with 2 DEG C/min speed from room temperature, and roasting Temperature fall after 2 hours, obtains Ag/13X adsorbent at this temperature.
The crystal phase structure of the adsorbent A g/13X prepared adopts X-ray diffraction (XRD) methods analyst, and compared with the crystal phase structure of carrier 13X molecular sieve.
(2) test of Ag/ molecular sieve adsorption radioiodine performance
Being adsorbed in the quartz ampoule adsorption column (internal diameter 12mm) being filled with Ag/ adsorbent of molecular sieve of radioiodine is carried out.Adsorbent is contained in quartz ampoule, loadings is 2g, with electric tube furnace, quartz ampoule adsorption column is heated to certain temperature; Adopt 131i 2-petroleum ether solution is as the source of radioiodine, and use micro-injection pump will 131i 2-petroleum ether solution injects adsorption column pipeline (flow velocity is 2.5mL/h), injection 131i 2-petroleum oil volume is 5mL (radiocounting added is approximately 100,000 Bakes), makes under the driving of certain flow rate helium carrier gas 131i 2steam flows through adsorption column bed; Flow out the tail gas of adsorption column by device for absorbing tail gas (containing 13X molecular sieve and saturated NaOH solution), completely not containing radioiodine in final helium of discharging.The FH463A type automatic scaler using Beijing Nuclear Instrument Factory to produce carries out radiocounting measurement (radiocounting in adsorbent and device for absorbing tail gas), calculates decontamination factor DF according to measurement result.
Decontamination factor DF calculates as follows (wherein A is the counting of the radioiodine in adsorbent, and B is the radioiodine counting in device for absorbing tail gas):
P ( % ) = A ( A + B ) × 100 % (wherein, DF = 1 1 - P / 100 )
Enforcement of the present invention, mainly carried out with the test of three kinds of molecular sieves (13X molecular sieve, H-beta molecular sieve, the Na-Y molecular sieve) detergency ability of silver molecular sieve adsorbent under two kinds of different helium flow velocitys that be carrier, result of implementation (table 1) shows:
1) carry silver-colored 13X adsorbent of molecular sieve than the carrier 13X molecular sieve not carrying silver, decontamination factor wants high under the same conditions;
2) carry silver-colored 13X adsorbent of molecular sieve from 350 DEG C to 650 DEG C Adsorption of Radioactive iodine, along with the rising of temperature, decontamination factor slightly declines;
3) 15wt% and 20wt% silver content carry silver-colored 13X adsorbent of molecular sieve decontamination factor along with helium change in flow little;
4) under the same conditions, silver content is more, and the detergency ability carrying silver-colored 13X adsorbent of molecular sieve will be got well, but the detergency ability difference of carrying silver-colored 13X adsorbent of molecular sieve of 15wt% and 20wt% silver content is little;
5) by 15wt%Ag/13X molecular sieve in Muffle furnace respectively at 550 DEG C and 650 DEG C of roasting temperatures, the time is respectively 2h, 10h, 20h, then measure its absorption iodine performance:
1. the detergency ability of 550 DEG C of 15wt%Ag/13X processed only has slight reduction, still keeps good absorption property;
2. the detergency ability of 650 DEG C of 15wt%Ag/13X processed also is slightly reduce;
6) the comprehensive result implemented, the clean effect of 15%Ag/13X is relatively good, performance is more stable, is suitable for removing of radioiodine in HTGR primary Ioops.
Accompanying drawing explanation
The X-ray diffraction spectrogram of Fig. 1 carrier 13X and 10 ~ 20%Ag/13X
The X-ray diffraction spectrogram of Figure 21 5%Ag/13X after 550 DEG C of process
The X-ray diffraction spectrogram of Figure 31 5%Ag/13X after 650 DEG C of process
The X-ray diffraction spectrogram of Fig. 4 carrier H-Beta and 10%Ag/H-Beta
The X-ray diffraction spectrogram of Fig. 5 carrier Na-Y and 10%Ag/Na-Y
Detailed description of the invention
Below by embodiment, the present invention is described further.
Embodiment 1
(1) preparation of 15%Ag/13X adsorbent
Take 9.45g AgNO 3, be dissolved in 200mL deionized water, stir.Take the 13X molecular sieve (20/60 order powder granule) of 40g, drop into above-mentioned AgNO 3in solution, stirred at ambient temperature floods 12 hours, then evaporative removal moisture, drying 12 hours at 110 DEG C.Dried sample is placed in Muffle furnace, 450 DEG C are risen to from room temperature with 2 DEG C/min speed, roasting Temperature fall after 2 hours at 450 DEG C, obtains the 15%Ag/13X adsorbent mass percent of Ag/13X (15% be), is labeled as 15%Ag/13X (450C/2h).
The crystal phase structure of carrier 13X molecular sieve and adsorbent 15%Ag/13X (450C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 1, result shows that sample 15%Ag/13X (450C/2h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 15%Ag/13X Adsorption of Radioactive iodine performance
It is in the quartz ampoule of 12mm that the 15%Ag/13X of 2g (450C/2h) is seated in internal diameter, passes into helium (flow velocity is 69mL/min), with electric tube furnace, quartz ampoule adsorption column bed is heated to 450 DEG C in quartz ampoule adsorption column; Use micro-injection pump by I 2(contain 131i 2)-petroleum ether solution 5mL (about 100,000 Bake) injects adsorption column (flow velocity is 2.5mL/h), I 2(contain 131i 2) steam flows through adsorption column bed under the driving of helium carrier gas; Flow out the tail gas of adsorption column by device for absorbing tail gas (containing 13X molecular sieve and saturated NaOH solution).Measure the radiocounting in adsorbent and device for absorbing tail gas, calculating decontamination factor DF according to measuring the radiocounting obtained, the results are shown in table 1.
Embodiment 2
Except adsorption column bed temperature is 550 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 3
Except adsorption column bed temperature is 650 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 4
Except adsorption column bed temperature is 350 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 5
Except helium flow velocity is 104mL/min, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 6
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 550 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 7
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 650 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 8
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 350 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 9
(1) preparation of 20%Ag/13X adsorbent
Except using the 13X molecular sieve (4mm spheric granules) of 30g, other step is with the step (1) of embodiment 1, obtain the 20%Ag/13X adsorbent mass percent of Ag/13X (20% be), be labeled as 20%Ag/13X (450C/2h).
The crystal phase structure of adsorbent 20%Ag/13X (450C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 1, result shows that sample 20%Ag/13X (450C/2h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 20%Ag/13X Adsorption of Radioactive iodine performance
Except using 20%Ag/13X (450C/2h) adsorbent of 2g, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 10
Except adsorption column bed temperature is 550 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 11
Except adsorption column bed temperature is 650 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 12
Except adsorption column bed temperature is 350 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 13
Except helium flow velocity is 104mL/min, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 14
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 550 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 15
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 650 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 16
Except helium flow velocity be 104mL/min, adsorption column bed temperature is except 350 DEG C, other are with embodiment 9.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 17
(1) preparation of 10%Ag/13X adsorbent
Except using the 13X molecular sieve (4mm spheric granules) of 60g, other step is with the step (1) of embodiment 1, obtain the 10%Ag/13X adsorbent mass percent of Ag/13X (10% be), be labeled as 10%Ag/13X (450C/2h).
The crystal phase structure of adsorbent 10%Ag/13X (450C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 1, result shows that sample 10%Ag/13X (450C/2h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 10%Ag/13X Adsorption of Radioactive iodine performance
Except 10%Ag/13X (450C/2h) adsorbent, the adsorption column bed temperature that use 2g are except 350 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 18
(1) preparation of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 550 DEG C roasting 2 hours)
Except 15%Ag/13X (450C/2h) adsorbent further at 550 DEG C except roasting 2 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (450C/2h+550C/2h).
The crystal phase structure of adsorbent 15%Ag/13X (450C/2h+550C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 2, result shows that sample 15%Ag/13X (450C/2h+550C/2h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 550 DEG C roasting 2 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (450C/2h+550C/2h), the adsorption column bed temperature that use 2g are except 550 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 19
Except helium flow velocity is 104mL/min, other are with embodiment 18.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 20
(1) preparation of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 550 DEG C roasting 10 hours)
Except 15%Ag/13X (450C/2h) adsorbent further at 550 DEG C except roasting 10 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (450C/2h+550C/10h).
The crystal phase structure of adsorbent 15%Ag/13X (450C/2h+550C/10h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 2, result shows that sample 15%Ag/13X (450C/2h+550C/10h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 550 DEG C roasting 10 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (450C/2h+550C/10h), the adsorption column bed temperature that use 2g are except 550 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 21
Except helium flow velocity is 104mL/min, other are with embodiment 20.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 22
(1) preparation of 15%Ag/13X adsorbent (at 550 DEG C roasting 20 hours)
Except 15%Ag/13X adsorbent at 550 DEG C except roasting 20 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (550C/20h).
The crystal phase structure of adsorbent 15%Ag/13X (550C/20h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 2, result shows that sample 15%Ag/13X (550C/20h) remains the crystal phase structure of 13X molecular sieve to spectrogram.
(2) test of 15%Ag/13X adsorbent (at 550 DEG C roasting 20 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (550C/20h), the adsorption column bed temperature that use 2g are except 550 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 23
Except helium flow velocity is 104mL/min, other are with embodiment 22.Measure and the decontamination factor DF calculated as table 1 institute not.
Embodiment 24
(1) preparation of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 650 DEG C roasting 2 hours)
Except 15%Ag/13X (450C/2h) adsorbent further at 650 DEG C except roasting 2 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (450C/2h+650C/2h).
The crystal phase structure of adsorbent 15%Ag/13X (450C/2h+650C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 3, result shows that sample 15%Ag/13X (450C/2h+650C/2h) remains the crystal phase structure of 13X molecular sieve to spectrogram.(2) test of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 650 DEG C roasting 2 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (450C/2h+650C/2h), the adsorption column bed temperature that use 2g are except 650 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 25
Except helium flow velocity is 104mL/min, other are with embodiment 24.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 26
(1) 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 650 DEG C roasting 10 hours) preparation except 15%Ag/13X (450C/2h) adsorbent further at 650 DEG C except roasting 10 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (450C/2h+650C/10h).
The crystal phase structure of adsorbent 15%Ag/13X (450C/2h+650C/10h) adopts XRD (X-ray diffraction) methods analyst, spectrogram as shown in Figure 3, result shows that sample 15%Ag/13X (450C/2h+650C/10h) remains the crystal phase structure of 13X molecular sieve, the diffraction maximum belonging to silver-colored crystalline phase also detected simultaneously.
(2) test of 15%Ag/13X adsorbent (at 450 DEG C at roasting 2 hours and 650 DEG C roasting 10 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (450C/2h+650C/10h), the adsorption column bed temperature that use 2g are except 650 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 27
Except helium flow velocity is 104mL/min, other are with embodiment 26.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 28
(1) preparation of 15%Ag/13X adsorbent (at 650 DEG C roasting 20 hours)
Except 15%Ag/13X adsorbent at 650 DEG C except roasting 20 hours, other are with embodiment 1.The adsorbent obtained is labeled as 15%Ag/13X (650C/20h).
The crystal phase structure of adsorbent 15%Ag/13X (650C/20h) adopts XRD (X-ray diffraction) methods analyst, spectrogram as shown in Figure 3, result shows that sample 15%Ag/13X (650C/20h) remains the crystal phase structure of 13X molecular sieve, the diffraction maximum belonging to silver-colored crystalline phase also detected simultaneously.
(2) test of 15%Ag/13X adsorbent (at 650 DEG C roasting 20 hours) Adsorption of Radioactive iodine performance
Except the 15%Ag/13X (650C/20h), the adsorption column bed temperature that use 2g are except 650 DEG C, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 29
Except helium flow velocity is 104mL/min, other are with embodiment 28.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 30
(1) preparation of 10%Ag/H-beta adsorbent
Except using the H-beta molecular sieve of 60g, other same embodiment 1, obtains the 10%Ag/H-beta adsorbent mass percent of Ag/H-beta (10% be), is labeled as 10%Ag/H-beta (450C/2h).
The crystal phase structure of carrier H-beta molecular sieve and adsorbent 10%Ag/H-beta (450C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 4, result shows that sample 10%Ag/H-beta (450C/2h) remains the crystal phase structure of H-beta molecular sieve to spectrogram.
(2) test of 10%Ag/H-beta Adsorption of Radioactive iodine performance
Except the 10%Ag/H-beta (450C/2h), the helium flow velocity that use 2g are except 104mL/min, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 31
Except adsorption column bed temperature is 550 DEG C, other are with embodiment 30.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 32
Except adsorption column bed temperature is 650 DEG C, other are with embodiment 30.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 33
Except adsorption column bed temperature is 350 DEG C, other are with embodiment 30.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 34
(1) preparation of 10%Ag/NaY adsorbent
Except using the NaY molecular sieve of 60g, other same embodiment 1, obtains the 10%Ag/NaY adsorbent mass percent of Ag/NaY (10% be), is labeled as 10%Ag/NaY (450C/2h).
The crystal phase structure of carrier NaY molecular sieve and adsorbent 10%Ag/NaY (450C/2h) adopts XRD (X-ray diffraction) methods analyst, as shown in Figure 5, result shows that sample 10%Ag/NaY (450C/2h) remains the crystal phase structure of NaY molecular sieve to spectrogram.
(2) test of 10%Ag/NaY Adsorption of Radioactive iodine performance
Except the 10%Ag/NaY (450C/2h), the helium flow velocity that use 2g are except 104mL/min, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 35
Except adsorption column bed temperature is 550 DEG C, other are with embodiment 34.To measure and the decontamination factor DF calculated is as shown in table 1.
Embodiment 36
Except adsorption column bed temperature is 350 DEG C, other are with embodiment 34.To measure and the decontamination factor DF calculated is as shown in table 1.
Comparative example 1
Except use carrier 13X molecular sieve, other are with embodiment 1.To measure and the decontamination factor DF calculated is as shown in table 1.
Comparative example 2
Except use carrier 13X molecular sieve, other are with embodiment 2.To measure and the decontamination factor DF calculated is as shown in table 1.
The each embodiment condition of table 1 and decontamination factor
Legend:
The X-ray diffraction spectrogram of Fig. 1 carrier 13X and Ag/13X
The X-ray diffraction spectrogram of Figure 21 5%Ag/13X after 550 DEG C of process
The X-ray diffraction spectrogram of Figure 31 5%Ag/13X after 650 DEG C of process
The X-ray diffraction spectrogram of Fig. 4 carrier H-Beta and 10%Ag/H-Beta
The X-ray diffraction spectrogram of Fig. 5 carrier Na-Y and 10%Ag/Na-Y

Claims (9)

1. at high temperature remove a method for radioiodine in HTGR, it is characterized in that: described method adopts carries silver-colored adsorbent, and it is take silver as absorbed component, molecular sieve is carrier, and employing is flooded, the method for high-temperature heat treatment prepares.
2. in accordance with the method for claim 1, it is characterized in that, within described year, silver-colored adsorbent adopts AgNO 3as the presoma of silver, take molecular sieve as carrier, the method for employing dipping, high-temperature heat treatment prepares, and its preparation process is followed successively by:
(1) described molecular sieve is crystallinity alumina silicate, as 13X molecular sieve, 5A molecular sieve, Y zeolite, beta molecular sieve;
(2) adopt the method for existing aqueous impregnation, molecular sieve be impregnated in AgNO 3in the aqueous solution, after heating evaporating water, obtain silver molecular sieve presoma;
(3) adopt the method for high-temperature heat treatment to activate above-mentioned silver molecular sieve presoma, obtain silver molecular sieve adsorbent.
3. in accordance with the method for claim 1, it is characterized in that, described high-temperature heat treatment method is heated in atmosphere within the scope of 450 ~ 650 DEG C by silver molecular sieve presoma, and adopt the method for temperature programming to heat up from room temperature, and described programmed rate is 2 DEG C/min.
4. in accordance with the method for claim 3, it is characterized in that, the described high-temperature heat treatment time is 2 ~ 20 hours.
5. in accordance with the method for claim 1, it is characterized in that, describedly at high temperature to remove, refer to that the described silver-colored adsorbent that carries carries out removing of radioiodine in gas at 350 ~ 650 DEG C.
6. in accordance with the method for claim 1, it is characterized in that, described year silver-colored adsorbent removing for radioiodine in high temperature gas-cooled nuclear reactor.
7. in accordance with the method for claim 1, it is characterized in that, the chemical form of described radioiodine, comprise iodine and methyl iodide (CH 3i).
8. in accordance with the method for claim 1, it is characterized in that, described radioiodine is iodine-125, iodo-129, iodine-131.
9. in accordance with the method for claim 1, it is characterized in that, the described gas containing radioiodine is helium or nitrogen or argon gas.
CN201310326820.5A 2013-07-31 2013-07-31 Method for removing radioactive iodine from gas cooled reactor Pending CN104338510A (en)

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CN105688807A (en) * 2016-01-21 2016-06-22 广西大学 Preparation method of micro-pore type active carbon adsorbed by organic iodine
CN108939811A (en) * 2018-08-03 2018-12-07 中国核动力研究设计院 A kind of gaseous iodine extracting method
CN110496588A (en) * 2019-06-20 2019-11-26 中国科学院长春应用化学研究所 A kind of adsorption method of radioiodine
CN112023874A (en) * 2020-09-18 2020-12-04 上海复旭分子筛有限公司 Zeolite molecular sieve adsorbent for deeply removing iodide in gas-phase medium and preparation method and application thereof

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EP0175435A1 (en) * 1984-04-25 1986-03-26 Toray Industries, Inc. Adsorbent for and method of removing iodine compounds
EP0608057A1 (en) * 1993-01-18 1994-07-27 Hitachi, Ltd. Iodine adsorbent for removing iodine from a gas
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105688807A (en) * 2016-01-21 2016-06-22 广西大学 Preparation method of micro-pore type active carbon adsorbed by organic iodine
CN108939811A (en) * 2018-08-03 2018-12-07 中国核动力研究设计院 A kind of gaseous iodine extracting method
CN108939811B (en) * 2018-08-03 2021-05-18 中国核动力研究设计院 Gaseous iodine extraction method
CN110496588A (en) * 2019-06-20 2019-11-26 中国科学院长春应用化学研究所 A kind of adsorption method of radioiodine
CN112023874A (en) * 2020-09-18 2020-12-04 上海复旭分子筛有限公司 Zeolite molecular sieve adsorbent for deeply removing iodide in gas-phase medium and preparation method and application thereof

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Application publication date: 20150211