CN104769679A - Method for eliminating radioactive cesium and method for producing burned product - Google Patents
Method for eliminating radioactive cesium and method for producing burned product Download PDFInfo
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- CN104769679A CN104769679A CN201280076693.1A CN201280076693A CN104769679A CN 104769679 A CN104769679 A CN 104769679A CN 201280076693 A CN201280076693 A CN 201280076693A CN 104769679 A CN104769679 A CN 104769679A
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- calcined material
- radiocesium
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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
- G21F9/28—Treating solids
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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
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/32—Processing by incineration
Abstract
Provided is a method for easily and efficiently eliminating radioactive cesium from a waste material contaminated by radioactive cesium. The method for eliminating radioactive cesium includes a heating step for heating a CaO source and/or an MgO source with a waste material contaminated by radioactive cesium to 1200-1350 DEG C, vaporizing the radioactive cesium in the waste material. In the heating step, the type and fraction admixed of each of the waste material, the CaO source, and the MgO source are determined in a manner so that the respective masses of CaO, MgO, and SiO2 satisfy ((CaO+1.39*MgO)/SiO2) = 1.0 to 2.5 (in the formula, CaO, MgO, and SiO2 respectively represent the mass of calcium in terms of the oxide, the mass of magnesium in terms of the oxide, and the mass of silicon in terms of the oxide).
Description
Technical field
The present invention relates to method for removing radiocesium from the discarded object polluted by radiocesium and for using the discarded object that polluted by radiocesium as raw material to manufacture the method for harmless calcined material (such as, cement additive, aggregate, earthwork material).
Background technology
If the radiocesium be released to because of the Accident of Large-scale of nuclear power plant in external environment condition containing in discarded object or soil, then can cause problem.The half life period of radiocesium (Ce 137) is 30 years, can bring adverse effect to human body for a long time, therefore, in most cases requires to be removed by radiocesium from discarded object etc.
As the method for removing radiocesium, such as describe the disposal route of following radioactive waste, it comprises the steps: to possess the hot-wire coil that is wound in its outside, be there is the radioactive waste dissolving will existed with the form of nitrate by electromagnetic induction heating in the cooled containers of slit, metal oxide nitrates decompose being generated by electromagnetic pinch force is collected at container surroundings, the platinum family element of reduction is made to be collected at container central portion, then cool, condensation, then, reclaim the firming body generated, in the disposal route of described radioactive waste, the long lived nuclides such as the caesium volatilized by radioactive waste in electromagnetic induction heating are separated, reclaim (patent documentation 1).
But, the method that the method for patent documentation 1 is not is object to be discharged into the radiocesium in external environment condition because of accident, but with the method that the radioactive waste produced in the region limited in nuclear power plant etc. is object, therefore, be not suitable for the process of the contaminated soil of substantial amounts etc., in addition, also there is the problem that device is complicated and expensive, cost is high.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-157897 publication
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide can easily and from the discarded object polluted by radiocesium, remove the method for radiocesium efficiently.In addition, the present invention also aims to be provided for use the discarded object that polluted by radiocesium as raw material to manufacture the method for harmless calcined material (such as, cement additive, aggregate, earthwork material).
For solving the means of problem
The present inventor conducts in-depth research to solve above-mentioned problem, found that, by being heated with specific blending ratio in the discarded object polluted by radiocesium and CaO source and/or MgO source, can achieve the above object, thus complete the present invention.
That is, the present invention, provides following [1] ~ [9] item.
[1] a kind of removing method of radiocesium, it comprises and is heated at 1200 ~ 1350 DEG C and make the heating steps that the radiocesium in described discarded object volatilizees in the discarded object polluted by radiocesium and CaO source and/or MgO source, the feature of the removing method of described radiocesium is
In described heating steps, to make CaO, MgO and SiO
2the mode that respective quality meets following formula (1) determines the respective kind in described discarded object, CaO source and MgO source and blending ratio,
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
In formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon.
The removing method of the radiocesium [2] according to above-mentioned [1], wherein, in described heating steps, also uses chloride.
The removing method of the radiocesium [3] according to above-mentioned [1] or [2], wherein, in described heating steps, heats under reducing atmosphere.
[4] a kind of manufacture method of calcined material, comprise and the discarded object polluted by radiocesium and CaO source and/or MgO source are heated at 1200 ~ 1350 DEG C and the radiocesium in described discarded object is volatilized thus obtains the heating steps of calcined material, the feature of the manufacture method of described calcined material is
In described heating steps, to make CaO, MgO and SiO
2the mode that respective quality meets following formula (1) determines the respective kind in described discarded object, CaO source and MgO source and blending ratio,
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
In formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon.
The manufacture method of the calcined material [5] according to above-mentioned [4], wherein, in described heating steps, heats under reducing atmosphere.
The manufacture method of the calcined material [6] according to above-mentioned [4] or [5], wherein, comprises the mixed processes calcined material obtained by described heating steps and at least one be selected from the group that is made up of reductive agent and adsorbent being carried out mixing.
[7] cement additive, it is pulverized by the calcined material manufacture method of the calcined material utilized according to any one of above-mentioned [4] ~ [6] obtained and obtains.
[8] aggregate, it comprises the calcined material obtained by the manufacture method of the calcined material according to any one of above-mentioned [4] ~ [6].
[9] earthwork material, it comprises the calcined material obtained by the manufacture method of the calcined material according to any one of above-mentioned [4] ~ [6].
The effect of invention
According to the removing method of radiocesium of the present invention, easily and removed from the discarded object polluted by radiocesium by radiocesium efficiently, radioactive waste volume can be reduced.
In addition, according to the manufacture method of calcined material of the present invention, the harmless calcined material of the radiocesium that can be removed.This calcined material can be used for rebuilding of a large amount of needs from now on and use concrete (dyke, seawall and Wave-dissipating block etc.) as cement additive, aggregate, can realize the protection of natural resources.In addition, can as earthwork material for removing the backfilling material etc. in the soil after soil.
Embodiment
Below, the present invention is described in detail.
The removing method of radiocesium of the present invention is the removing method of following radiocesium, it comprises and is heated at 1200 ~ 1350 DEG C and make the heating steps that the radiocesium in above-mentioned discarded object volatilizees in the discarded object polluted by radiocesium and CaO source and/or MgO source, the feature of the removing method of above-mentioned radiocesium is, in above-mentioned heating steps, to make CaO, MgO and SiO
2the mode that respective quality meets following formula (1) determines the respective kind in above-mentioned discarded object, CaO source and MgO source and blending ratio.
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
(in formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon)
Handling object thing of the present invention is the discarded object polluted by radiocesium.
Herein, the discarded object polluted by radiocesium such as soil, downflow sludge dry powder, city garbage burning ash, derive from the disaster such as industrial waste, the rubble discarded object such as the common discarded object such as slag, shell, vegetation, downflow sludge, sewage grit, clean water sludge, construction mud of rubbish, be the discarded object containing radiocesium.These discarded objects can be used alone one, also can combinationally use two or more.In addition, that part (such as, when soil being sand, stone) removing hardly containing radiocesium obtained in advance, that radiocesium is concentrated discarded object (intermediate treatment thing) is also contained in the concept of " discarded object by radiocesium pollutes " in the present invention.
In addition, as CaO source, such as, can enumerate calcium carbonate, lime stone, unslaked lime, lime hydrate, lime stone, rauhkalk, blast furnace slag etc.As MgO source, such as, can enumerate magnesium carbonate, magnesium hydroxide, rauhkalk, serpentinite, Rhometal slag etc.These illustrative materials can be used alone one, also can combinationally use two or more.
In the present invention, CaO source and MgO source can use both, also only can use any one, but from volatile aspect of radiocesium, preferably only mixed C aO source.
In addition, CaO source and MgO source preferably use the powder after pulverizing.
In the present invention, radiocesium refers to radioisotopic Cesium 134 as caesium and Ce 137.These radiocesiums are the radiomaterials be discharged into due to the accident of nuclear power plant in external environment condition, and its half life period is respectively about 2 years and about 30 years.
In the present invention, the radiocesium as removing object is together discharged into external environment condition from the nuclear power plant had an accident with the form of cesium iodide etc. and radioiodine, and drops to ground surface from overhead.The boiling point of cesium iodide is more than 1200 DEG C, compared with the caesium simple substance being about 700 DEG C, has the character being difficult to volatilize with boiling point.And the radiocesium dropping to ground surface is sealing in the clay mineral contained by soil, becomes the state being difficult to be separated from soil, and form also changes sometimes.In addition, be attached on the disaster discarded objects such as rubble, or the radiocesium that drops to ground surface is concentrated in the process of lower water treatment by rain-out, produces the downflow sludge etc. containing radiocesium with high concentration thus.In addition, vegetation by radioactive contamination, by containing in these burning ashs produced by the castoff burning of the vegetation of radioactive contamination, has radiocesium in middle envelopes such as glass due to the radiocesium absorbed contained by soil sometimes.In the present invention, the radiocesium compound that these are in reluctant state to be separated, be reclaimed.
For the above-mentioned discarded object that polluted by radiocesium and CaO source and/or MgO source, with the calcium oxide (CaO), magnesium oxide (MgO) and the silicon dioxide (SiO that make in obtained potpourri
2) the respective quality mode that meets following formula (1) determines the kind in above-mentioned discarded object and CaO source and/or MgO source and the basis of blending ratio mix.
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
(in formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon)
From the viewpoint of the volatile quantity increasing radiocesium, by above-mentioned CaO, MgO and SiO
2the lower limit of the numerical value that respective quality and above-mentioned formula (1) derive is preferably more than 1.2, is more preferably more than 1.4, and more preferably more than 1.7, more preferably more than 1.8, be particularly preferably the value being greater than 1.9.
In addition, from the radiocesium volatilization made potpourri and reduce potassium in potpourri, the aspect of volatile quantity of sodium considers, the higher limit of the numerical value of being derived by above-mentioned formula (1) is preferably less than 2.4, be more preferably less than 2.3, more preferably less than 2.2, more preferably less than 1.9, be particularly preferably less than 1.8.
It should be noted that, the quality of the quality of 1 mole of CaO and 1.39 moles of MgO is suitable, therefore, in above-mentioned formula (1), the quality of MgO is multiplied by 1.39.
When this mass ratio is less than 1.0, along with calcining heat reaches a high temperature, easily produce liquid phase, the volatile quantity of radiocesium reduces.When this mass ratio is more than 2.5, the total volatile quantity of the potassium in the potpourri in the discarded object polluted by radiocesium and CaO source and/or MgO source, sodium increases, and increases as the be cooled amount of the discarded object containing radiomaterial of the solid constituent that obtains of waste gas.
In order to promote the chloridizing volatilization of radiocesium and reduce volatilization regenerant volume, as the material of said mixture, lime chloride (CaCl can be used further
2), the chloride such as potassium chloride (KCl), sodium chloride (NaCl).Wherein, from the aspect promoting chloridizing volatilization, preferably calcium chloride.
Muriatic amount is the amount making the mol ratio of chlorine and caesium and potassium (Cl/ (Cs+K)) preferably reach less than 1.00, more preferably reach 0.010 ~ 0.60, preferably reach 0.015 ~ 0.40 further, particularly preferably reach 0.03 ~ 0.30.When this mol ratio is less than 1.0, potassium, sodium is non-volatile and radiocesium volatilizees in a large number, therefore, it is possible to realize the volume of the discarded object reduced containing radiomaterial.
In addition, the chlorine dose in said mixture is preferably below 1500mg/kg.When chlorine dose is below 1500mg/kg, even if at high temperature also not easily produce liquid phase, radiocesium volatilizees in a large number.
Preferred above-mentioned mol ratio (Cl/ (Cs+K)) be less than 1.0 and chlorine dose in said mixture be below 1500mg/kg, further preferred above-mentioned mol ratio be less than 0.5 and chlorine dose in said mixture is below 1250mg/kg time, the caesium of volatilization becomes the form of cesium chloride and easily volatilizees, and the volume that can realize regenerant described later reduces.
When above-mentioned discarded object mixes with CaO source and/or MgO source, fragmentation, pulverizing etc. can be carried out as required while mixing, or, disintegrating machine or comminutor and mixer are combined to carry out two stage process.When the kiln stated after a procedure carries out calcining, in kiln, each material is rotated mixing, therefore, a part for above-mentioned CaO source, MgO source and discarded object etc. directly can be put into kiln tail.In addition, said mixture is preferably less than the shot-like particle of about 5mm.In addition, while carrying out washing, the removings such as the stone of more than the 5mm of a large amount of caesium will can not contained in advance.
The heating-up temperature of the potpourri in the discarded object polluted by radiocesium and CaO source and/or MgO source is 1200 ~ 1350 DEG C, is preferably 1200 ~ 1300 DEG C.
By heating within the scope of said temperature, the radiocesium contained in discarded object can be made to volatilize efficiently.When heating-up temperature is lower than 1200 DEG C, the volatile quantity of radiocesium reduces.During more than 1350 DEG C, forming liquid phase, making radiocesium not volatile by sealing thus, therefore not preferred.
From the viewpoint of the sufficient volatile quantity obtaining radiocesium, the heat time of potpourri is preferably more than 15 minutes, be more preferably more than 30 minutes.The upper limit of heat time is not particularly limited, but is preferably less than 180 minutes, is more preferably less than 120 minutes.When heat time was more than 180 minutes, the radiocesium in the volatile quantity of potassium, sodium and potpourri together increases.
When the raw materials such as kiln rotate, the contact rate of gas and radiocesium increases, and thermal conductivity also becomes good, therefore, it is possible to obtain high volatility with the calcination time shorter than static conditions.
As heating arrangement, any one device in continous way and batch-type can be used.
As the example of continous way heating arrangement, kiln etc. can be enumerated.
As the example of batch-type heating arrangement, incinerator, electric furnace, microwave heating equipment etc. can be enumerated.
Wherein, from the viewpoint of improving treatment effeciency, preferred use continous way heating arrangement in the present invention.Particularly kiln easily can provide and be suitable for the heating-up temperature of radiocesium volatilization and the residence time of discarded object, therefore preferably.
As atmosphere during heating, when the heated under air containing water vapor, the volatile quantity of alkaline metal (potassium and sodium) can be reduced and the volatile quantity of increase radiocesium, therefore preferably.
On the other hand, when heating under the air (pure air) not containing water vapor, although the volatile quantity of alkaline metal (potassium and sodium) also increases, more radiocesium can be made to volatilize.
Steam vapour amount during by regulating above-mentioned muriatic amount, heating-up temperature, time and heating, can reduce the volatile quantity of alkaline metal (potassium and sodium), increase the volatile quantity of radiocesium simultaneously.
In addition, in the discarded object polluted by radiocesium containing chromium, likely containing 6 valency chromium (Cr in the calcined material obtained
6+).
When such calcined material being used as cement additive, aggregate, earthwork material etc. (particularly when as the earthwork materials'use), the 6 valency chromium contained in calcined material may stripping and cause water pollution, soil pollution etc.
Therefore, in above-mentioned heating steps, can heat under reducing atmosphere.By heating under reducing atmosphere, even if containing chromium in above-mentioned discarded object, also the generation of the 6 valency chromium easily generated under oxidizing atmosphere can be prevented, and, even if discarded object temporarily generates 6 valency chromium because heating under oxidizing atmosphere in the operation heated by discarded object, 3 valency chromium (Cr also can be reduced to
3+), therefore, it is possible to obtained calcined material is used safely as earthwork material etc.It should be noted that, also the above-mentioned method carrying out heating under containing the air of water vapor can be carried out with the Combination of Methods carrying out heating under reducing atmosphere.Below, for the method for carrying out under reducing atmosphere heating, to use internal-combustion type device (internal combustion type kiln etc.) and the situation of device explains orally for reverse-flow (in the burning of material outlet side), but the present invention is not limited to these modes.
As the example of the method for discarded object heating will polluted by radiocesium under reducing atmosphere, can enumerate will the heating of above-mentioned discarded object time inflammable substance is burnt method.By making inflammable substance burn, surrounding's maintenance reducing atmosphere of discarded object can be made.In addition, even if containing chromium in above-mentioned discarded object, the generation of 6 valency chromium also can be prevented, and, even if generate 6 valency chromium in the operation heated by discarded object, also 6 valency chromium can be reduced to 3 valency chromium.
Herein, inflammable substance such as can be enumerated: coal, coke, activated charcoal, by culled wood, waste plastics, heavy oil sludge, the compression of municipal refuse the like waste and/or the rejected material solid block etc. of solidification.
The supply method of inflammable substance, can be pre-mixed in the discarded object polluted by radiocesium, when using kiln as when adding the device hankering using, inflammable substance can be supplied from the midway of the entrance side of discarded object, outlet side or kiln.
When inflammable substance is pre-mixed in raw material, as long as can not remain in the scope in the calcined material obtained by heating with unburned state at inflammable substance, then preferably the combined amount of inflammable substance is many, and also the particle diameter of preferred inflammable substance is large.
Herein, the situation for the entrance side of the discarded object at kiln or the midway supply inflammable substance of kiln is described.
In this case, inflammable substance preferably can maintain the inflammable substance of reducing atmosphere for a long time.Specifically, such as can enumerate: the inflammable substance that burning rate is slower than the main fuel of kiln or there is the burning rate same with main fuel and the particle inflammable substance thicker than main fuel.Specifically, petroleum coke, coal coke, smokeless char etc. can be enumerated.Burning rate is slower, inflammable substance can be made thinner, therefore preferably.
The mean grain size of inflammable substance is preferably 0.5 ~ 20mm, is more preferably 1 ~ 5mm.When this mean grain size is less than 0.5mm, aflame extremely early stage with regard to after-flame, therefore sometimes cannot maintain reducing atmosphere for a long time.When this mean grain size is more than 20mm, the inflammable substance of a large amount of residual unburned state in the calcined material obtained, therefore, cause the waste of supplied inflammable substance, in addition, when this calcined material being used as cement additive or aggregate, residual unburned carbon can adsorb AE agent, thus, following problem is produced sometimes: the bleed deterioration of mortar concrete; Or unburned carbon appears at surface and causes the appearance degradation of mortar concrete when consolidation; Deng.
The amount of inflammable substance is preferably 5 ~ 40kg with respect to heating the every 1000kg of calcined material obtained, and is more preferably 10 ~ 40kg, is particularly preferably 12 ~ 40kg.When this amount is less than 5kg, sometimes little by forming the effect brought of reducing atmosphere.When this amount is more than 40kg, the inflammable substance of a large amount of residual unburned state in the calcined material obtained, when using this calcined material, this uses as cement additive or aggregate, bleed, the outward appearance of mortar concrete are sometimes deteriorated.
It should be noted that, when the midway supply inflammable substance of kiln, in kiln, preferably reach the midway supply inflammable substance of position to the entrance side of discarded object of the highest temperature.
The aspect never making inflammable substance disappear immediately is considered, the oxygen (O in stove during burn combustible material
2) concentration is preferably below 5 quality %, is more preferably below 3 quality %.
By regulating above-mentioned condition and the residence time etc., the generation of 6 valency chromium can be prevented, and inflammable substance can be made to remain.In addition, when obtained calcined material being used as cement additive or aggregate, the mode of adverse effect is brought to regulate above-mentioned condition and the residence time etc. with the bleed not to mortar concrete, outward appearance.
Then, the situation for the outlet side supply inflammable substance from discarded object is described.
Inflammable substance can use air from the outlet side of discarded object easily force feed in stove.In addition, special input port can be set at the outlet side of kiln.In addition, thick inflammable substance (mean grain size is about the inflammable substance of 1mm ~ 10mm) also can be made to fall as a part for the fuel of main burner.
Inflammable substance preferably can form the inflammable substance than the reducing condition stronger when the entrance side of discarded object or the midway of kiln supply.Specifically, the burning rate inflammable substance faster than the main fuel of kiln can such as be enumerated.As the inflammable substance that burning rate is fast, such as, can enumerate the rejected material solid block etc. by the compression of culled wood, waste plastics, heavy oil sludge and municipal refuse the like waste and/or solidification.
The mean grain size of inflammable substance is preferably 0.1 ~ 10mm, is more preferably 1 ~ 5mm.When this mean grain size is less than 0.1mm, extremely early stage with regard to after-flame in calcining, therefore cannot maintain reducing atmosphere sometimes.When this mean grain size is more than 10mm, the inflammable substance of a large amount of residual unburned state in the calcined material obtained, cause the waste of supplied inflammable substance, in addition, when this calcined material being used as cement additive or aggregate, bleed, the outward appearance of mortar concrete are sometimes deteriorated.It should be noted that, the time that can maintain reducing atmosphere can be regulated by the mean grain size of inflammable substance.Such as, for the inflammable substance that burning rate is fast, by making mean grain size increase (thicker), the time that can maintain reducing atmosphere can be extended.
About the heat of inflammable substance, the mode that can be generally 2 ~ 40% with the heat of the fuel entirety used relative to main burner uses.When the heat of inflammable substance is less than 2%, sometimes little by forming the effect brought of reducing atmosphere.When the heat of inflammable substance is more than 40%, the inflammable substance of a large amount of residual unburned state in the calcined material obtained, cause the waste of supplied inflammable substance, when this calcined material being used as cement additive or aggregate, bleed, the outward appearance of mortar concrete are sometimes deteriorated.
With above-mentioned, supply compared with the situation of inflammable substance at the entrance side of discarded object or the midway of kiln, when supplying from the outlet side of discarded object, the part in the just stove of reducing atmosphere is formed in kiln, therefore, in order to maintain reducing atmosphere for a long time and form reducing atmosphere in the high temperate zone that reduction rate is fast, preferably the supply position (lowering position) of inflammable substance is adjusted to than reaching the position of maximum temperature in kiln more by the position of the entrance side of discarded object.It is darker position, the place of 4D that supply position to be preferably when the internal diameter of drying oven being set to D usually than the distance of the outlet apart from drying oven.In addition, when the position that the condition by setting main burner etc. makes to reach in drying oven maximum temperature is more by outlet side, being preferably than the distance of the outlet of distance drying oven is darker position, the place of 3D.Supply position (lowering position) regulates preferably by the position of the angle of the input port of inflammable substance, input port, the density that drops into the speed of inflammable substance, the granularity of inflammable substance and inflammable substance.
The aspect never making inflammable substance disappear immediately is considered, the oxygen (O in stove when adding inflammable substance
2) concentration is preferably below 5 quality %, is more preferably below 3 quality %.
Preferably by the generation regulating above-mentioned condition to prevent 6 valency chromium, and inflammable substance can not be remained.
As under reducing atmosphere by the additive method that the discarded object polluted by radiocesium heats, the method making above-mentioned discarded object directly contact flame can be enumerated.
Specifically, in the device (internal heat type kiln etc.) of internal-combustion type, carry out calcining (hereinafter also referred to " flame film is calcined ") with the mode of the direct flame contact of burner to make to add the discarded object etc. polluted by radiocesium hankering (in calcining).As the method using internal heat type kiln to carry out the calcining of flame film, following method can be enumerated: heating main burner is arranged on bottom by (a), lick the mode of licking discarded object etc. to make flame and carry out heating (calcining); B () makes flame disperse by adjust fuel amount, air velocity, lick the mode of licking discarded object etc. carry out heating (calcining) to make flame; C () makes flame elongated downward by making the angle of main burner, lick the mode of licking discarded object etc. carry out heating (calcining) to make flame; Deng.In addition, except heating main burner, the auxiliary burner of flame film calcining can also be set.Make discarded object etc. longer with the duration of contact of flame by the adjustment of each condition, then reduction effect more improves.In addition, even if containing chromium in above-mentioned discarded object, also can prevent the generation of 6 valency chromium, and even if generate 6 valency chromium in the operation heated by discarded object, 6 valency chromium are also reduced to 3 valency chromium.
From the viewpoint of producing more flame film, the oxygen concentration carried out when flame film is calcined is preferably below 5 quality %, is more preferably below 3 quality %.
By regulating above-mentioned condition, the effect preventing 6 valency chromium strippings can be increased further.It should be noted that, the burning of above-mentioned inflammable substance and flame film can be calcined and share.
In addition, also reducing atmosphere can be formed by atmosphere when regulating heating.
Such as, as under reducing atmosphere by the additive method that the discarded object polluted by radiocesium heats, the method for the fuel combustion utilizing the air capacity fewer than theoretical air requirement that heating is used can be enumerated.
Specifically, following method can be enumerated: in the device (internal heat type kiln etc.) of internal-combustion type, be 0.8 ~ 1.0 making the air ratio in stove (air supply amount is relative to the ratio of theoretical air requirement) or under making the oxygen concentration in stove be the condition of below 1 quality %, make above-mentioned fuel combustion; Or, while making the carbonomonoxide concentration in stove be held in 0.1 ~ 1.0 quality %, make fuel combustion; Deng.
Air ratio in stove lower than 0.8 or carbonomonoxide concentration more than 1.0 quality %, be sometimes difficult to the burning needed for heating.Air ratio in stove is more than 1.0, oxygen concentration more than when making fuel combustion when 1 quality % or while making the carbonomonoxide concentration in stove be held in lower than 0.1 quality %, reduction effect reduces.
About the fuel that heating is used, as main fuel (fuel of burner), heavy oil, micro mist charcoal, reclaimed oil, LPG, NPG and combustible waste etc. can be enumerated, use the fuel that have adjusted granularity in order to burn in space.
In addition, also the burning of above-mentioned inflammable substance and/or the calcining of flame film can be share.
In addition, can enumerate in the device (external-heating revolving kiln, electric furnace etc.) used in heating and use the inert gases such as nitrogen to carry out the method replacing or make above-mentioned inert gas to circulate.In addition, the gas being mixed with the reducibility gas such as CO gas in above-mentioned inert gas also can be made to carry out replacing or circulating.
The radiocesium of the volatilization in the waste gas produced by above-mentioned heating means can, after cooling becomes solid, use precipitron or scrubber etc. to reclaim.In addition, when being provided with primary heater in drying oven, the part that also can contain the waste gas of the radiocesium of volatilization by extraction with high concentration also cools the radiocesium be recycled into as solid.The radiocesium reclaimed can undertaken after further volume reduces to dispose by washing, absorption etc. as required, is airtightly kept in the container etc. of concrete manufacture.Thereby, it is possible to carry out volume reduction, preservation when the discarded object containing radiomaterial can not be made to leak into outside.
Add muriatic situation in the potpourri in discarded object and CaO source and/or MgO source under, radiocesium can be reclaimed with the state of radioactivity cesium chloride.This radioactivity cesium chloride can be easily water-soluble, also can reclaim in form of an aqueous solutions.
The calcined material obtained after heating can be pulverized as required, is used as cement additive, aggregate (the reinforcement of concrete aggregate, pitch aggregate), earthwork material (backfilling material, banking material, roadbed material etc.) etc.
The calcined material obtained after heating is that Absolute Dry Density is preferably 1.5 ~ 3.0g/cm
3, be more preferably 2.0 ~ 3.0g/cm
3calcined material.
In addition, the free lime amount of this calcined material is preferably below 1.0 quality %, is more preferably below 0.5 quality %, more preferably below 0.2 quality %.When free lime amount is more than 1.0 quality %, during using calcined material as the reinforcement of concrete aggregate, earthwork materials'use, there is the possibility that concrete expansion destroys or calcined material generation itself is collapsed.
Can for cement additive etc. after the granularity, concreteness etc. required for considering is regulated the granularity of this calcined material by screening etc.
In addition, in discarded object containing chromium, except carry out the method that heats under reducing atmosphere in above-mentioned heating steps except, by carrying out following process to obtained calcined material, 6 valency chromium strippings from calcined material can be prevented.Particularly when using calcined material as the earthwork materials'use, from the viewpoint of preventing water pollution and soil pollution, preferably implement the stripping countermeasure of 6 valency chromium.Below, the concrete grammar of the stripping countermeasure of 6 valency chromium is described.
In obtained calcined material containing 6 valency chromium, as the stripping countermeasure of 6 valency chromium, the method calcined material of the high temperature obtained by heating steps mixed with inflammable substance can be enumerated.By being mixed with inflammable substance by the high-temperature calcination thing after heating steps and cooling, 6 valency chromium in calcined material are reduced to 3 valency chromium, can reduce 6 valency chromium in calcined material.
Specifically, following method can be enumerated: the method calcined material after heating steps mixed with inflammable substance while the temperature of calcined material is held in high temperature in heat generator; High-temperature calcination thing after heating steps and inflammable substance are put into, are filled into container, the method left standstill while the temperature of the potpourri making calcined material and inflammable substance is held in high temperature.
In addition, in the refrigerating work procedure of the air quenched refrigeratory of use, rotary cooler etc. that also can carry out after the heating step, the calcined material of high temperature is mixed with inflammable substance.Wherein, preferably use and to contact less with oxygen and the high rotary cooler of the mixability of inflammable substance.
When being mixed by inflammable substance in refrigerating work procedure, the mixed method of inflammable substance is not particularly limited, and from the viewpoint of long-time hot conditions and the reducing atmosphere of maintaining, preferably mixes immediately after the heating step.Such as, when using kiln to heat, inflammable substance is preferably made to drop to the blow-off pipe of kiln and the method for mixing.
The temperature of calcined material during mixing inflammable substance is higher, and the minimizing effect of 6 valency chromium is larger, is preferably more than 800 DEG C, is more preferably more than 1000 DEG C.It should be noted that, when using kiln to heat, by making the calcining heat in kiln reach the position of maximum temperature close to blow-off pipe side, can improve in the temperature of turning round calcined material when mixing in refrigeratory.
After mixing inflammable substance, the time to calcined material cooling is longer, and the minimizing effect of 6 valency chromium is larger, and the time from the temperature to calcined material after mixing reaches below 600 DEG C is preferably more than 1 minute, is more preferably more than 3 minutes.
Inflammable substance mixes following amount: relative to the heat of the potpourri entirety of calcined material and inflammable substance, be preferably equivalent to the heat of 2 ~ 20%.When this amount is equivalent to the heat being less than 2%, the minimizing effect of 6 valency chromium reduces.When this amount is equivalent to more than the heat of 20%, the inflammable substance of a large amount of residual unburned state in cooled calcined material.
As inflammable substance, such as can enumerate coal, coke, activated charcoal, by culled wood, waste plastics, heavy oil sludge, the compression of municipal refuse the like waste and/or the rejected material solid block etc. of solidification.Wherein, the inflammable substance of stronger reducing condition can preferably be formed.Specifically, the fast inflammable substance of burning rate can be enumerated.As the inflammable substance that burning rate is fast, such as, can enumerate the rejected material solid block etc. by the compression of culled wood, waste plastics, heavy oil sludge and municipal refuse the like waste and/or solidification.
The mean grain size of inflammable substance is preferably 0.1 ~ 10mm, is more preferably 1 ~ 5mm.During more than 10mm, a large amount of residual inflammable substance in cooled calcined material.When being less than 0.1mm, the minimizing effect of 6 valency chromium reduces, and disperses because of the wind speed of cooling-air etc. when dropping into, and the amount mixed with calcined material reduces.
The mean grain size of the inflammable substance that above-mentioned burning rate can be made fast increases (thicker).By increasing mean grain size, the time that can maintain reducing atmosphere can be extended, and because of the wind speed etc. of cooling-air, inflammable substance be dispersed when can prevent from dropping into.
Oxygen concentration during mixing inflammable substance is not particularly limited.In addition, from the viewpoint of reducing and the contact of oxygen or the addition reducing inflammable substance, in the conceived case, waste gas can be utilized.
Preferably large with the minimizing effect of 6 valency chromium and the mode that combustible can not remain regulates above-mentioned condition.In addition, when calcined material is used as cement additive, preferably regulate as follows: by making reducing atmosphere excessively strong, the color of the cement employing this calcined material is not changed.
In addition, as the stripping countermeasure of 6 valency chromium, can enumerate the calcined material obtained by heating steps is heated further, the method for melting.
By by calcined material melting, 6 valency chromium contained by calcined material are enclosed in glass, and when for earthwork material etc., the stripping quantity of 6 valency chromium reaches below environmental benchmark value.
Calcined material is heated further, after melting, this fused mass is cooled and become shot-like particle.The granular fused mass water-intake rate obtained is low and for high strength, therefore, it is possible to use as the reinforcement of concrete aggregate.It should be noted that, the cooling of fused mass also can be able to be slow cooling for quenching.
In addition, from the aspect of cost of energy, calcined material (calcined material after such as, just taking out from drying oven) the directly melting of the state of high temperature preferably will obtained by heating steps.
In addition, as the stripping countermeasure of 6 valency chromium, the mixed processes that more than at least one in the group calcined material obtained by heating steps and being selected from be made up of reductive agent and adsorbent carries out mixing can be carried out.
Such as, by calcined material is mixed with reductive agent, can by the 6 valency chromium contained in calcined material or from calcined material 6 valency chromium of stripping be reduced to 3 valency chromium.
As reductive agent, such as, can enumerate ferrous (II) salt, sodium thiosulfate, the iron powder such as the sulphite such as sodium sulphite, ferrous sulphate (II), iron protochloride (II) etc.
In addition, by calcined material being mixed with adsorbent, 6 valency chromium of stripping from calcined material can be adsorbed, can make 6 valency chromium insoluble or suppress stripping.
As adsorbent, such as, can enumerate: zeolite; Clay mineral; The layered double-hydroxide that the hydrotalcite compound of Mg-Al system, Mg-Fe system etc. is such; The Ca-Al based compounds such as Ca-Al system oxyhydroxide, entringite, monosulfate; The hydrous oxides such as iron oxide (haematite), bismuth oxide; The magnesium compounds such as magnesium hydroxide, magnesia unslacked, dolime, magnesium oxide; The iron compounds such as iron sulfide, iron powder, schwertmannite, FeOOH; One or more potpourri in monox, aluminium oxide, iron oxide etc. or calcined material; Compound etc. containing cerium and rare earth element.
Reductive agent and adsorbent can be used alone one, also can combinationally use two or more.
As the method that calcined material is mixed with reagent (reductive agent and/or adsorbent), calcined material can be mixed with pulverous reagent, following method can also be enumerated: mixed with water in advance by reagent, make slurry or aqueous solution (hereinafter also referred to " after slurry etc. "), calcined material being mixed with slurry etc., being sprayed to by slurry etc. in calcined material or calcined material being impregnated in slurry etc.; Deng.
About the consumption of mentioned reagent, be preferably 0.01 ~ 10kg with the amount of the slaine relative to every 100kg calcined material, be more preferably 0.1 ~ 7kg, be particularly preferably the mode of 0.2 ~ 5kg and regulate the spray amount of the concentration, slurry etc. of the amount, slurry etc. of pulverulent reagent and calcined material to the input amount in slurry etc.When being less than 0.01kg relative to the amount of the slaine of every 100kg calcined material, the effect reducing the stripping quantity of 6 valency chromium reduces.When this amount is more than 10kg, the effect reducing the stripping quantity of 6 valency chromium is saturated, therefore uneconomical.
The temperature of calcined material during mixing is preferably 100 ~ 800 DEG C, is more preferably 125 ~ 600 DEG C, is particularly preferably 150 ~ 400 DEG C.When the temperature of calcined material is more than 800 DEG C, calcined material cracks etc. or calcined material micronize, cause the reduction of intensity thus, therefore not preferred.During lower than 100 DEG C, reagent is difficult to the surface being attached to calcined material, therefore not preferred.
Make reagent be attached to the surface of calcined material the method that the slurry containing reagent etc. is sprayed in the calcined material of high temperature and not easily peel off, therefore preferably.In addition, when there is pore in calcined material, method calcined material be impregnated in slurry etc. makes reagent infiltrate into inside well, and is attached to surface, therefore preferably.
In addition, as the stripping countermeasure of 6 valency chromium, can also enumerate the method for the calcined material washing obtained by heating steps.
As method for washing, following method can be enumerated: the calcined material that (i) utilizes sprinkler etc. to be spread to by cleaning fluid in container or on belt conveyor is carried out the method for cleaning; (ii) enter calcined material and cleaning fluid at container content, after calcined material is flooded certain hour in cleaning fluid, discharge the cleaning fluid after dipping, supply new cleaning fluid, repeat the method that aforesaid operations carries out cleaning; (iii) while calcined material is impregnated in cleaning fluid by use rotary screen (trommel) etc., the cleaning method of calcined material is substituted successively; Deng.
Cleaning fluid can be common tap water, also can use the aqueous solution of above-mentioned reagent (reductive agent or adsorbent).Cleaning fluid after washing can recycle as cleaning fluid, also can discard after treatment.
The consumption of the cleaning fluid that washing time, washing times, washing are used is not particularly limited, and carries out washing until the stripping quantity of 6 valency chromium meets environmental benchmark value (No. 46th, Environmental Agency's bulletin).
These methods can be carried out with the Combination of Methods that carries out under reducing atmosphere heating in above-mentioned heating steps.
It should be noted that, the ability that heavy metal (lead, arsenic etc.) beyond 6 valency chromium is fixed on its inside by the calcined material obtained by heating steps of the present invention is excellent, therefore, if carry out the above-mentioned process preventing 6 valency chromium strippings, then can be suitable as a cubic metre of earth material (backfilling material, banking material, roadbed material etc.) and use.
The calcined material obtained by heating steps can be pulverized and use as cement additive.In addition, relative to crushed material 100 mass parts of calcined material, also can contain with SO
3be scaled the gypsum of 1 ~ 6 mass parts.
Breaking method is not particularly limited, such as, use bowl mill etc. to utilize usual way to pulverize.
From the aspect reducing mortar, concrete bleeding and mobility, manifesting property of intensity, the Blain specific surface of the crushed material of preferred calcined material is 2500 ~ 5000cm
2/ g.
Calcined material, cement clinker and gypsum can be pulverized simultaneously.From the aspect reducing mortar, concrete bleeding and mobility, manifesting property of intensity, the Blain specific surface of cement when preferably simultaneously pulverizing is 2500 ~ 4500cm
2/ g.
When this cement additive and cement mixing are obtained cement composition, the heat of hydration of cement composition can be reduced, and make good fluidity.
The calcined material obtained by heating steps can carry out pulverizing as required or classification is used as aggregate (aggregate of the reinforcement of concrete aggregate, pitch), earthwork materials'use.
Will containing the calcined material of 6 valency chromium as in the used situation of aggregate, 6 valency chromium be enclosed in cement solidification thing, therefore, by the conveying of carrying out aggregate time, the time of preservation rainproof, the stripping of 6 valency chromium can be prevented.In addition, the above-mentioned process preventing 6 valency chromium strippings can also be carried out.
The calcined material obtained may be used in fine aggregate and coarse aggregate any one.When using as coarse aggregate, by screening etc., granularity is adjusted to more than 5mm to use.
In addition, when as the earthwork materials'use, consider concreteness etc., be adjusted to 0.1 ~ 100mm to use.
When using as aggregate, the Absolute Dry Density of calcined material is preferably 2.0 ~ 3.0g/cm
3.This Absolute Dry Density is lower than 2.0g/cm
3time, concrete intensity may reduce.In addition, the water-intake rate of calcined material is preferably less than 15%.When this water-intake rate is greater than 15%, concrete intensity may reduce.
Particularly when using as the reinforcement of concrete aggregate, the Absolute Dry Density of preferred calcined material is 2.5 ~ 3.0g/cm
3and water-intake rate is less than 3%.
Free lime amount is preferably below 1.0 quality %, is more preferably below 0.5 quality %.When this amount is more than 1.0 quality %, concrete may expansion damage.
[embodiment]
Below, specifically describe the present invention by embodiment, but the present invention is not limited to these embodiments.
[synthesis example 1: the making of caesium adsorbing clays A]
Bentonitic clay 500g is contained in the concentration risen with 250mg/ in the aqueous solution 2 liters of caesium and flood after 1 day, reclaim solid constituent by centrifuging, and then this solid constituent is washed, again carry out centrifuging.Thus, the caesium adsorbing clays A containing caesium with the concentration of 1060mg/kg is obtained.
[synthesis example 2: the making of caesium adsorbing clays B]
Bentonitic clay 500g is contained in the concentration risen with 500mg/ in the aqueous solution 2 liters of caesium and flood after 1 day, reclaim solid constituent by centrifuging, and then this solid constituent is washed, again carry out centrifuging.Thus, the caesium adsorbing clays B containing caesium with the concentration of 2200mg/kg is obtained.
[embodiment 1]
The caesium adsorbing clays A6.6g obtained in synthesis example 1 is mixed with limestone powder 13.2g.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[embodiment 2]
The caesium adsorbing clays A6.6g obtained in synthesis example 1 is mixed with limestone powder 13.2g.Using tubular electric furnace to be heated 60 minutes at 1300 DEG C under the air (liquid water content 7%) obtained by carrying out bubbling from the water of 60 DEG C by obtained potpourri, obtaining calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
It should be noted that, be that the object carrying out under the air of 7% heating is to simulate the heating in reality in heating kiln stove at liquid water content.
[embodiment 3]
The caesium adsorbing clays A8g obtained in synthesis example 1 is mixed with limestone powder 12g.Using tubular electric furnace to be heated 60 minutes at 1300 DEG C under the air (liquid water content 7%) obtained by carrying out bubbling from the water of 60 DEG C by obtained potpourri, obtaining calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[embodiment 4]
The caesium adsorbing clays A9g obtained in synthesis example 1 is mixed with limestone powder 11g.Using tubular electric furnace to be heated 60 minutes at 1300 DEG C under the air (liquid water content 7%) obtained by carrying out bubbling from the water of 60 DEG C by obtained potpourri, obtaining calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[embodiment 5]
The caesium adsorbing clays A10g obtained in synthesis example 1 is mixed with limestone powder 10g.Using tubular electric furnace to be heated 60 minutes at 1300 DEG C under the air (liquid water content 7%) obtained by carrying out bubbling from the water of 60 DEG C by obtained potpourri, obtaining calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[embodiment 6]
The caesium adsorbing clays A6.6g obtained in synthesis example 1 is mixed with limestone powder 13.2g.Use tubular electric furnace to be heated 60 minutes at 1200 DEG C under pure air by obtained potpourri, obtain calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[embodiment 7]
The caesium adsorbing clays A11g obtained in synthesis example 1 is mixed with limestone powder 9g.Use tubular electric furnace heats 60 minutes under obtained potpourri being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1200 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[comparative example 1]
Use tubular electric furnace to be heated 60 minutes at 1000 DEG C under pure air by the caesium adsorbing clays A obtained in synthesis example 1, obtain calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.It should be noted that, caesium adsorbing clays is calcined at 1200 DEG C as a result, sample melting, adhere on container, therefore cannot reclaim.
[comparative example 2]
The caesium adsorbing clays A6.6g obtained in synthesis example 1 is mixed with limestone powder 13.2g.Use tubular electric furnace to be heated 60 minutes at 1000 DEG C under pure air by obtained potpourri, obtain calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 1.
[table 1]
From the embodiment 1 ~ 7 of table 1, by the calcium oxide (CaO) in potpourri, magnesium oxide (MgO) and silicon dioxide (SiO
2) respective quality and ((CaO+1.39 × MgO)/SiO
2) formula derive numerical value be about 1.0 ~ 1.8, and, by heating at about 1200 ~ 1300 DEG C, caesium can be made to volatilize.
In addition, known when embodiment 1 and embodiment 2 ~ 5 being compared (particularly embodiment 1 and embodiment 2), by the heated under air containing water vapor, the volatility of potassium, sodium can be reduced, the volatility of raising caesium.
[embodiment 8]
The caesium adsorbing clays B30g, limestone powder 60g and the lime chloride 0.0246g that obtain in synthesis example 2 are pulverized and mixed.Use tubular electric furnace heats 60 minutes under obtained potpourri 20g being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1300 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[embodiment 9]
The caesium adsorbing clays B30g, limestone powder 60g and the lime chloride 0.0492g that obtain in synthesis example 2 are pulverized and mixed.Use tubular electric furnace heats 60 minutes under obtained potpourri 20g being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1300 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[embodiment 10]
The caesium adsorbing clays B30g, limestone powder 60g and the lime chloride 0.0492g that obtain in synthesis example 2 are pulverized and mixed.Use tubular electric furnace heats 120 minutes under obtained potpourri 20g being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1300 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[embodiment 11]
The caesium adsorbing clays B30g, limestone powder 60g and the lime chloride 0.0984g that obtain in synthesis example 2 are pulverized and mixed.Use tubular electric furnace heats 60 minutes under obtained potpourri 20g being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1300 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[embodiment 12]
The caesium adsorbing clays B30g, limestone powder 60g and the lime chloride 0.246g that obtain in synthesis example 2 are mixed.Use tubular electric furnace heats 60 minutes under obtained potpourri 20g being the air (liquid water content 7%) in the water of 60 DEG C after bubbling at 1300 DEG C, obtains calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[embodiment 13]
The caesium adsorbing clays B10g, limestone powder 10g and the lime chloride 0.49g that obtain in synthesis example 2 are mixed.Use tubular electric furnace to be heated 60 minutes at 1200 DEG C under pure air by obtained potpourri, obtain calcined material.The content of calcined material Cs and Cl separately that the potpourri before using damp process to measure heating and heating obtain, obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 2.
[table 2]
From the embodiment 8 ~ 13 of table 2, even if add chloride, caesium also can volatilize.Particularly from embodiment 8,9 and 11, be about 0.09 ~ 0.26 in the mol ratio (Cl/ (Cs+K)) of chlorine and caesium and potassium, the amount of chlorine be about 410 ~ 1210mg/kg and the heat time is about 60 minutes, under the state that the volatility of sodium and potassium is low, the volatility of caesium is high.
[embodiment 14]
Except heating except 120 minutes at 1300 DEG C under not steam-laden air (pure air), obtain calcined material similarly to Example 1.Calcined material caesium separately (Cs), chlorine (Cl), Na that potpourri before measuring heating similarly to Example 1 and heating obtain
2o and K
2each content of O, obtains the volatility (quality %) of Cs, Na and K.Result is shown in table 3.
[embodiment 15]
Except heating except 30 minutes at 1300 DEG C under not steam-laden air (pure air), obtain calcined material similarly to Example 1.Calcined material caesium separately (Cs), chlorine (Cl), Na that potpourri before measuring heating similarly to Example 1 and heating obtain
2o and K
2each content of O, obtains the volatility (quality %) of Cs, Na and K.Result is shown in table 3.
[embodiment 16]
Except heating except 60 minutes at 1250 DEG C under not steam-laden air (pure air), obtain calcined material similarly to Example 1.Calcined material caesium separately (Cs), chlorine (Cl), Na that potpourri before measuring heating similarly to Example 1 and heating obtain
2o and K
2each content of O, obtains the volatility (quality %) of Cs, Na and K.Result is shown in table 3.
[embodiment 17]
Except heating except 120 minutes at 1250 DEG C under not steam-laden air (pure air), obtain calcined material similarly to Example 1.Calcined material caesium separately (Cs), chlorine (Cl), Na that potpourri before measuring heating similarly to Example 1 and heating obtain
2o and K
2each content of O, obtains the volatility (quality %) of Cs, Na and K.Result is shown in table 3.
[embodiment 18]
Except heating except 30 minutes at 1350 DEG C under not steam-laden air (pure air), obtain calcined material similarly to Example 1.Calcined material caesium separately (Cs), chlorine (Cl), Na that potpourri before measuring heating similarly to Example 1 and heating obtain
2o and K
2each content of O, obtains the volatility (quality %) of Cs, Na and K.Result is shown in table 3.
[table 3]
[embodiment 19]
The caesium adsorbing clays A30g obtained in synthesis example 1 is mixed with limestone powder 68g.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 20]
The caesium adsorbing clays A30g obtained in synthesis example 1 is mixed with limestone powder 77g.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 21]
The caesium adsorbing clays A30g, limestone powder 77g and the lime chloride 0.122g that obtain in synthesis example 1 are mixed.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 22]
The caesium adsorbing clays A30g, limestone powder 77g and the lime chloride 0.122g that obtain in synthesis example 1 are mixed.Use tubular electric furnace to be heated 60 minutes at 1250 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 23]
The caesium adsorbing clays A30g obtained in synthesis example 1 is mixed with limestone powder 90g.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 24]
The caesium adsorbing clays A30g obtained in synthesis example 1 is mixed with limestone powder 90g.Use tubular electric furnace to be heated 60 minutes at 1250 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 25]
The caesium adsorbing clays A30g, limestone powder 90g and the lime chloride 0.039g that obtain in synthesis example 1 are mixed.Use tubular electric furnace to be heated 60 minutes at 1300 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[embodiment 26]
The caesium adsorbing clays A30g, limestone powder 90g and the lime chloride 0.039g that obtain in synthesis example 1 are mixed.Use tubular electric furnace to be heated 60 minutes at 1250 DEG C under not steam-laden air (pure air) by obtained potpourri, obtain calcined material.The content of the calcined material caesium separately (Cs) that the potpourri before using damp process to measure heating and heating obtain and chlorine (Cl), obtains the volatility (quality %) of Cs.In addition, fluorescent x-ary analysis (XRF) is used to measure Na
2o and K
2o amount separately, obtains the volatility (quality %) of Na and K.Result is shown in table 4.
[table 4]
Claims (9)
1. the removing method of a radiocesium, it comprises and is heated at 1200 ~ 1350 DEG C and make the heating steps that the radiocesium in described discarded object volatilizees in the discarded object polluted by radiocesium and CaO source and/or MgO source, the feature of the removing method of described radiocesium is
In described heating steps, to make CaO, MgO and SiO
2the mode that respective quality meets following formula (1) determines the respective kind in described discarded object, CaO source and MgO source and blending ratio,
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
In formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon.
2. the removing method of radiocesium according to claim 1, wherein, in described heating steps, also uses chloride.
3. the removing method of radiocesium according to claim 1 and 2, wherein, in described heating steps, heats under reducing atmosphere.
4. the manufacture method of a calcined material, it comprises and is heated at 1200 ~ 1350 DEG C in the discarded object polluted by radiocesium and CaO source and/or MgO source and the radiocesium in described discarded object volatilized thus obtains the heating steps of calcined material, the feature of the manufacture method of described calcined material is
In described heating steps, to make CaO, MgO and SiO
2the mode that respective quality meets following formula (1) determines the respective kind in described discarded object, CaO source and MgO source and blending ratio,
((CaO+1.39×MgO)/SiO
2)＝1.0～2.5…(1)
In formula, CaO, MgO, SiO
2the quality being converted into oxide of the quality being converted into oxide of respective expression calcium, the quality being converted into oxide of magnesium, silicon.
5. the manufacture method of calcined material according to claim 4, wherein, in described heating steps, heats under reducing atmosphere.
6. the manufacture method of the calcined material according to claim 4 or 5, wherein, comprises the mixed processes calcined material obtained by described heating steps and at least one be selected from the group that is made up of reductive agent and adsorbent being carried out mixing.
7. a cement additive, it is pulverized by the calcined material manufacture method of the calcined material utilized according to any one of claim 4 ~ 6 obtained and obtains.
8. an aggregate, it comprises the calcined material obtained by the manufacture method of the calcined material according to any one of claim 4 ~ 6.
9. an earthwork material, it comprises the calcined material obtained by the manufacture method of the calcined material according to any one of claim 4 ~ 6.
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| JPPCT/JP2012/077909 | 2012-10-29 | ||
| PCT/JP2012/077909 WO2014068643A1 (en) | 2012-10-29 | 2012-10-29 | Method for removing radioactive cesium, and method for producing fired material |
| PCT/JP2012/083594 WO2014068800A1 (en) | 2012-10-29 | 2012-12-26 | Method for eliminating radioactive cesium and method for producing burned product |
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| EP (1) | EP2913826B1 (en) |
| JP (3) | JPWO2014068800A1 (en) |
| KR (1) | KR102004580B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417286A (en) * | 2018-03-14 | 2018-08-17 | 清华大学 | A method of it impregnates and prepares simulation pollucite source core |
| CN109111108A (en) * | 2018-10-22 | 2019-01-01 | 深圳市优力凯环保生物技术有限公司 | A kind of foamed glass material and preparation method thereof improving soil |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5875721B1 (en) * | 2015-02-26 | 2016-03-02 | 株式会社神鋼環境ソリューション | Radiocesium removal method and radioactive cesium removal system |
| JP5872092B1 (en) * | 2015-06-23 | 2016-03-01 | 株式会社神鋼環境ソリューション | Radioactive substance removal method and radioactive substance removal system |
| JP6602822B2 (en) * | 2017-07-14 | 2019-11-06 | 日立造船株式会社 | Radiocesium removal method and treatment facility |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4671898A (en) * | 1983-08-04 | 1987-06-09 | Studsvik Energiteknik Ab | Process for treatment of a spent, radioactive, organic ion exchange resin |
| JPS63187199A (en) * | 1987-01-30 | 1988-08-02 | 財団法人 電力中央研究所 | Accumulation reducing method of radioactivity in radioactive waste incinerator |
| JPH06230186A (en) * | 1993-02-08 | 1994-08-19 | Hitachi Ltd | Processing system and method of radioactive waste |
| JP2005249587A (en) * | 2004-03-04 | 2005-09-15 | Takayuki Watanabe | Waste processing method of low-level radioactive ion exchange resin |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK153320C (en) * | 1976-08-20 | 1988-11-14 | Tashkent Ni I Pi Stroitel | CEMENT AND PROCEDURE FOR MANUFACTURING THEREOF |
| JPS60142297A (en) * | 1983-12-28 | 1985-07-27 | 大同特殊鋼株式会社 | Method of treating radioactive waste |
| JP3018684B2 (en) | 1991-12-04 | 2000-03-13 | 住友金属工業株式会社 | Radioactive waste treatment method |
| CN100427425C (en) * | 2002-03-22 | 2008-10-22 | 太平洋水泥株式会社 | Cement admixture |
| JP2003315499A (en) * | 2002-04-26 | 2003-11-06 | Mitsubishi Heavy Ind Ltd | Method and device for treating ion-exchange resin |
| FR2841370B1 (en) * | 2002-06-19 | 2004-08-06 | Technip France | METHOD FOR IMMOBILIZING METAL SODIUM IN THE FORM OF GLASS |
| JP2004292198A (en) * | 2003-03-26 | 2004-10-21 | Taiheiyo Cement Corp | Coarse aggregate for concrete, and concrete |
| JP4471110B2 (en) * | 2005-02-25 | 2010-06-02 | 清水建設株式会社 | Method for recycling activated concrete |
| JP2006348176A (en) * | 2005-06-16 | 2006-12-28 | Daiei Kogyo:Kk | Caking material |
| JP2008273993A (en) * | 2006-08-09 | 2008-11-13 | Ts Solution Inc | Heavy metal elution inhibitor and heavy metal elution-inhibiting construction method |
| JP5624722B2 (en) * | 2006-10-24 | 2014-11-12 | 太平洋セメント株式会社 | Cement clinker and cement |
| JP2009132564A (en) * | 2007-11-30 | 2009-06-18 | Taiheiyo Material Kk | Method of manufacturing artificial aggregate |
| JP2009172495A (en) * | 2008-01-23 | 2009-08-06 | Mhi Environment Engineering Co Ltd | Method of treating material comprising heavy metals by incineration, and incinerator for incinerating material comprising heavy metals |
| JP2010168256A (en) * | 2009-01-26 | 2010-08-05 | Taiheiyo Cement Corp | Cement additive and cement composition |
| FR2943835B1 (en) * | 2009-03-31 | 2011-04-29 | Onectra | PROCESS FOR CONDITIONING RADIOACTIVE WASTE IN THE FORM OF A SYNTHETIC ROCK |
| JP2013076690A (en) * | 2011-09-13 | 2013-04-25 | Taiheiyo Cement Corp | Method for removing radioactive cesium and method for manufacturing burned product |
| JP5159971B1 (en) * | 2011-09-15 | 2013-03-13 | 太平洋セメント株式会社 | Method for removing radioactive cesium and method for producing fired product |
| JP5896836B2 (en) * | 2011-09-30 | 2016-03-30 | 太平洋セメント株式会社 | Method for producing fired product |
-
2012
- 2012-10-29 WO PCT/JP2012/077909 patent/WO2014068643A1/en active Application Filing
- 2012-12-26 KR KR1020157001651A patent/KR102004580B1/en active IP Right Grant
- 2012-12-26 CN CN201280076693.1A patent/CN104769679B/en active Active
- 2012-12-26 WO PCT/JP2012/083594 patent/WO2014068800A1/en active Application Filing
- 2012-12-26 CA CA2889738A patent/CA2889738A1/en not_active Abandoned
- 2012-12-26 EP EP12887510.1A patent/EP2913826B1/en active Active
- 2012-12-26 JP JP2014544206A patent/JPWO2014068800A1/en active Pending
-
2016
- 2016-07-11 JP JP2016136637A patent/JP6628282B2/en active Active
- 2016-07-11 JP JP2016136646A patent/JP6243484B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4671898A (en) * | 1983-08-04 | 1987-06-09 | Studsvik Energiteknik Ab | Process for treatment of a spent, radioactive, organic ion exchange resin |
| JPS63187199A (en) * | 1987-01-30 | 1988-08-02 | 財団法人 電力中央研究所 | Accumulation reducing method of radioactivity in radioactive waste incinerator |
| JPH06230186A (en) * | 1993-02-08 | 1994-08-19 | Hitachi Ltd | Processing system and method of radioactive waste |
| JP2005249587A (en) * | 2004-03-04 | 2005-09-15 | Takayuki Watanabe | Waste processing method of low-level radioactive ion exchange resin |
Non-Patent Citations (1)
| Title |
|---|
| DEL DEBBIO JA: "Removal of Cesium From a High-level Calcined Waste by High Temperature Volatilization:INEL-94/028", 《CEC:LUXEMVOURG》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417286A (en) * | 2018-03-14 | 2018-08-17 | 清华大学 | A method of it impregnates and prepares simulation pollucite source core |
| CN108417286B (en) * | 2018-03-14 | 2020-11-27 | 清华大学 | Method for preparing simulated pollucite source core by soaking |
| CN109111108A (en) * | 2018-10-22 | 2019-01-01 | 深圳市优力凯环保生物技术有限公司 | A kind of foamed glass material and preparation method thereof improving soil |
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| JPWO2014068800A1 (en) | 2016-09-08 |
| EP2913826A4 (en) | 2016-05-18 |
| KR102004580B1 (en) | 2019-07-26 |
| KR20150079546A (en) | 2015-07-08 |
| JP6628282B2 (en) | 2020-01-08 |
| WO2014068800A1 (en) | 2014-05-08 |
| CN104769679B (en) | 2017-06-06 |
| JP2016224055A (en) | 2016-12-28 |
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| JP2016191716A (en) | 2016-11-10 |
| EP2913826A1 (en) | 2015-09-02 |
| WO2014068643A1 (en) | 2014-05-08 |
| CA2889738A1 (en) | 2014-05-08 |
| EP2913826B1 (en) | 2020-06-17 |
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