CN1213097C

CN1213097C - Method and equipment for processing waste materials

Info

Publication number: CN1213097C
Application number: CNB981176100A
Authority: CN
Inventors: 赤井芳惠; 松林义和; 山口恭志; 山田和矢; 小原敦
Original assignee: Toshiba Corp
Current assignee: Toshiba Corp
Priority date: 1997-08-20
Filing date: 1998-08-20
Publication date: 2005-08-03
Anticipated expiration: 2018-08-20
Also published as: CN100344386C; CN1683091A; CN1208938A

Abstract

A waste processing method decomposing an organic substance or an inorganic substance contained in organic wastes or inorganic wastes by holding a mixture of the organic wastes or the inorganic wastes and a medium, which is in its supercritical state, for a pre-determined time period, in which the hydrogen ion concentration of the medium is 10-4 mol or more to 1 kg of the medium. A waste processing method having a step of decomposing all or almost all of an organic substance included in organic wastes into lower-molecular-weight products by holding the organic wastes in a medium, which is in its supercritical state, for a pre-determined time and a step of oxidizing and decomposing the lower-molecular-weight products into carbon dioxide and/or water by holding a mixture of an oxidant and the lower-molecular-weight products in the medium, which is in its subcritical state, for a pre-determined time period.

Description

Refuse processing method and waste treatment apparatus

Technical field

The present invention relates to the treatment process and the treatment unit of organic waste, and the treatment process of inorganic waste and treatment unit.

Background technology

In recent years, the resin of polymer container, polyvinyl chloride etc., contain the processing of radioactive substance organic waste etc., global environment is caused very big problem.Usually, be to carry out burning disposal to organic waste, this treatment process can produce toxic substances such as dioxide, oxynitride, needs large-scale device and reclaim these toxic substances.

The inorganic waste in nuclear power field except containing radioactive substance, also contains a large amount of nitric acid sodium salts.These materials are embedded in the underground disposal field as cured body.Recently, according to underground environmental research, it was reported and find the underground low reductibility encirclement gas of oxygen partial pressure that is that nitrate ion may become ammonia.Like this, the nuclear substance of plutonium etc. forms ammonia and complex compound, may stripping from cured body.

In recent years, as the method for decomposing organic matter, adopt the method that surpasses the water (supercritical water) under the High Temperature High Pressure of water stagnation point (374 ℃ of temperature, pressure 22.1MPa) to be gazed at.

So-called supercritical state is meant the state that compound inherent physical quantity is the material under the above temperature and pressure of critical temperature and emergent pressure that is in.The material that is in this state is called supercutical fluid.

Organism, water and oxygen-bearing fluid are mixed, and in the supercritical state of the stagnation point that surpasses water, the method that oxidation operation is decomposed is known (" the oxidation operation method in the supercritical water ", the clear 56-68414 of Japanese Patent Application, registration number 1551862).Supercritical water mixes organism or oxygen etc. arbitrarily owing to have the middle character of liquids and gases, can effectively oxidation operation be decomposed at short notice.

But in the supercritical state, the solubleness of inorganics significantly reduces, and the inorganics that contains in the organic waste precipitate into reactor surface, with the reactor obturation.Particularly the oxide dissolution degree of inorganics is little, more is easy to generate above-mentioned problem.

For example, when handling the waste of nuclear power station generation, because radioactive substance is separated out, be not easy to handle, the maintenance of waste treatment apparatus needs more expense.

Therefore, wish to have and a kind ofly can utilize supercritical state and do not separate out the decomposition method and the device of the organic waste of inorganics.

As mentioned above, if there is ammonia in the cured body, then nuclear substance such as plutonium may stripping from cured body.Therefore,, make nitrate ion or nitrate in the waste become nitrogen, prevent that nitrate ion from sneaking into refuse processing method and the device in the cured body even wish to develop handling when only containing the waste of inorganics.

Summary of the invention

The present invention makes in view of the above problems, and its purpose is to provide a kind of method and apparatus that can be at short notice effectively organic waste or inorganic waste be decomposed.

For achieving the above object, the present invention takes following technical scheme:

Refuse processing method of the present invention is characterized in that, has lower molecular weight chemical industry preface and oxidation operation; In the lower molecular weight operation,, make whole or most of organism contained in the organic waste carry out lower molecular weightization with the mixture maintenance scheduled time of organic waste with the medium that are in supercritical state; In oxidation operation, the resultant that generates in described lower molecular weight chemical industry preface is mixed with oxygenant, and in being in the described medium of subcritical state, keep the scheduled time to carry out oxidation.

Described refuse processing method is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the medium of supercritical state and the mixture of organic waste have been become.

Described refuse processing method is characterized in that, above-mentioned organic waste contains more than 2 kinds of nitrate, vitriol, muriate, phosphoric acid salt or silicate or they.

Described refuse processing method is characterized in that, above-mentioned medium are water, carbonic acid gas or hydrocarbon or their mixtures more than 2 kinds.

Described refuse processing method is characterized in that, above-mentioned oxygenant is to use more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they; The consumption of these oxygenants is to make more than 1 times of the required stoichiometry of organic waste complete oxidation.

Described refuse processing method is characterized in that, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the above-mentioned overcritical medium of 1kg ^-4More than the mole.

Described refuse processing method is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned critical medium, and the hydrogen ion concentration of above-mentioned overcritical medium is that the overcritical medium above-mentioned with respect to 1kg are adjusted into 10 ^-4More than the mole.

Described refuse processing method is characterized in that, also has separation circuit, separates contained insoluble inclusion in the organic waste.

Described refuse processing method is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the described medium of supercritical state and the mixture of described organic waste have been become.

Described refuse processing method is characterized in that, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

Described refuse processing method is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned critical medium, and the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

Refuse processing method of the present invention, it is with the mixture maintenance scheduled time of waste with the medium that are in supercritical state, decomposes described waste, it is characterized in that, exist under the situation of oxygenant, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the above-mentioned medium of 1kg ^-4More than the mole.

Described refuse processing method is characterized in that, described waste is an organic waste, and organism contained in the described organic waste is decomposed.

Described method for organic waste disposal is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the described medium of supercritical state and the mixture of described organic waste have been become.

Described refuse processing method is characterized in that, above-mentioned overcritical medium contain oxygenant.

Described refuse processing method is characterized in that, above-mentioned overcritical medium contain more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they, and amount is to make more than 1 times of the required stoichiometry of described organic waste oxidation fully.

Described refuse processing method is characterized in that, described waste is an inorganic waste, and inorganics contained in the described inorganic waste is decomposed.

Described refuse processing method is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the described medium of supercritical state and the mixture of inorganic waste have been become.

Described refuse processing method is characterized in that, above-mentioned inorganic waste contains nitric acid and/or nitrate.

Described refuse processing method is characterized in that, above-mentioned overcritical medium contain more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they, and amount is to make more than 1 times of the required stoichiometry of described inorganic waste oxidation fully.

Described refuse processing method is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned overcritical medium, and the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

Waste treatment apparatus of the present invention is characterized in that having:

In the medium of supercritical state, make the contained whole or most of organism of organic waste carry out the reactor of lower molecular weightization;

Described organic waste is supplied with the organic waste feedway of described reactor;

Described medium are supplied with the medium feedway of described reactor;

Make the oxidation reactor of the resultant of described reactor generation in the subcritical state oxidation;

Oxygenant is supplied with the oxygenant feedway of described oxidation reactor;

Be used to be recovered in the resultant fluidic retrieving arrangement that described oxidation reactor generates.

Described waste treatment apparatus is characterized in that, has: the setting device of regulating hydrogen ion concentration in the described reactor.

Described waste treatment apparatus is characterized in that, above-mentioned reactor has the tripping device that separates contained insoluble inclusion in the described organic waste.

Described waste treatment apparatus, it is characterized in that, in above-mentioned organic waste feedway, described medium feedway, described oxygenant feedway, be respectively equipped with the pressurizing device and the primary heater unit that are used to pressurize with the organic gurry of preheating, medium, oxygenant;

In above-mentioned retrieving arrangement, be provided with the reliever and the refrigerative refrigerating unit that are used to make the fluid pressure that described reactor generates.

Described waste treatment apparatus is characterized in that, has the device that detects the media state in the described reactor.

Described waste treatment apparatus is characterized in that, above-mentioned reactor has the device of internal dress thing irradiation ultraviolet radiation or radioactive rays.

Described waste treatment apparatus is characterized in that, above-mentioned recycling and processing device has gas-liquid separation device, gas treatment equipment, fluid treatment appts.

Described waste treatment apparatus is characterized in that, the above-mentioned gas treatment unit has strainer and washer; Described strainer is used for removing solids, radioactive substance or the objectionable impurities of gas; Described washer is used for reclaiming the radioactive substance or the objectionable impurities of gas.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the device of the mineral ion coagulative precipitation that makes in the liquid.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the device of the solids in the separating liquid.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the ion exchange unit of removing liquid intermediate ion composition.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the liquid of making and contacts with extraction agent, with the extraction recycling and processing device of mineral ion in extraction and the recovering liquid.

Described waste treatment apparatus is characterized in that, adopts the thinner of carbonic acid gas as described extraction agent.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment and makes liquid or sludge exsiccant drying installation.

Described waste treatment apparatus is characterized in that, above-mentioned solidification equipment solidifies the batch mixing thing of liquid or sludge or their mixture and solidifying agent in container.

Waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, the reactor that waste is decomposed;

Waste supplying device with the described reactor of described waste supplying;

Described medium are supplied with the medium feedway of described reactor;

Oxygenant is supplied with the oxygenant feedway of above-mentioned reactor;

Regulate the setting device of hydrogen ion concentration in the described reactor;

Retrieving arrangement with the resultant fluid recovery that generates in the described reactor.

Described waste treatment apparatus, it is characterized in that, above-mentioned waste is an organic waste, and above-mentioned reactor is the reactor that above-mentioned organic waste is decomposed, and described waste supplying device is an organic waste feedway of described organic waste being supplied with described reactor.

Described waste treatment apparatus is characterized in that, above-mentioned setting device is mixed back supply response device with mineral acid and medium, to become predetermined hydrogen ion concentration.

Described waste treatment apparatus is characterized in that, above-mentioned setting device has:

Mineral acid is supplied with the sour feedway of described reactor;

The hydrogen ion concentration instrumentation device of hydrogen ion concentration in the described reactor of instrumentation;

According to from the signal of described hydrogen ion concentration instrumentation device, the mineral acid of calculated amount is supplied with control device in the described reactor from described sour feedway.

Described waste treatment apparatus is characterized in that, above-mentioned setting device is regulated described hydrogen ion concentration according to the kind of described organic waste and the feed rate of described oxygenant.

Described waste treatment apparatus is characterized in that, in above-mentioned organic waste feedway, medium feedway, oxygenant feedway, is respectively equipped with the pressurizing device and the primary heater unit that are used to pressurize with preheating organic waste, medium, oxygenant; In above-mentioned retrieving arrangement, be provided with the fluid pressure and refrigerative reliever and the refrigerating unit that are used to make described reactor generation.

Described waste treatment apparatus is characterized in that, above-mentioned recycling and processing device has gas-liquid separation device, gas treatment equipment and fluid treatment appts.

Described waste treatment apparatus is characterized in that, the aforesaid liquid treatment unit, have make liquid contact with extraction agent, extract and recovering liquid in the extraction recycling and processing device of mineral ion.

Described waste treatment apparatus is characterized in that, adopts the thinner of carbonic acid gas as the said extracted agent.

Described waste treatment apparatus, it is characterized in that, above-mentioned waste is an inorganic waste, above-mentioned reactor is the reactor that the contained inorganics of above-mentioned inorganic waste is decomposed, and above-mentioned waste supplying device is an inorganic waste feedway of above-mentioned inorganic waste being supplied with described reactor.

Described waste treatment apparatus is characterized in that, above-mentioned setting device is mixed back supply response device with mineral acid and medium with predetermined hydrogen ion concentration.

Described waste treatment apparatus is characterized in that, above-mentioned setting device is regulated hydrogen ion concentration according to the kind of described inorganic waste and the feed rate of described oxygenant.

With mineral acid supply with described reactor sour feedway,

The hydrogen ion concentration instrumentation device of the interior hydrogen ion concentration of the described reactor of instrumentation,

According to from the signal of described hydrogen ion concentration instrumentation device, the mineral acid of calculated amount is supplied with control device in the described reactor from sour feedway.

In the medium of supercritical state, make the contained whole or most of organism of organic waste carry out lower molecular weightization, follow the reactor that at subcritical state resultant is mixed and makes oxidation with oxygenant;

Described medium are supplied with the medium feedway of described reactor;

Oxygenant is supplied with the oxygenant feedway of described reactor;

Be used to be recovered in the resultant fluidic retrieving arrangement that described reactor generates.

The 1st refuse processing method of the present invention is characterized in that, has lower molecular weight chemical industry preface and oxidation operation; In the lower molecular weight operation, the mixture of organic waste and medium is kept the scheduled time in supercritical state, make whole or most of organism contained in the organic waste carry out lower molecular weightization; In oxidation operation, the resultant that generates in described lower molecular weight operation is mixed with oxygenant, and keep the scheduled time to carry out oxidation at subcritical state.

According to this method, in advance in supercritical state, when oxygenant does not exist, make organism carry out lower molecular weightization, under the undercritical conditions that inorganics is difficult to separate out, add the oxygenant decomposing organic matter then, so, decomposing organic matter effectively, and prevent separating out of inorganics.

Organic waste there is no particular determination, and paper, cloth waste, activated carbon, pitch, various resins etc. are for example arranged.Organic waste also can contain more than 2 kinds of nitrate, vitriol, muriate, phosphoric acid salt or silicate or they.

The insoluble substance person who contains sand, gravel, cobble etc. is also arranged in the organic waste.

In addition, there are polyethylene, propylene, PET resin, various ion exchange resin etc. not to contain inorganic additive or organo-metallic salt addn person in the resin, vinyl-chloride-containing, silicon, fibre reinforced plastics inorganic additive or organo-metallic salt addn persons such as (FRP) are also arranged.

Inorganic additive has stablizer, the CaCO of lead salt, Sn salt etc. ₃Or SiO ₂Such weighting agent, Al ₂(OH) ₃, Sb ₂O ₃, MgO etc. fire retardant, conduction with or strengthen the carbon etc. of usefulness.The organo-metallic salt addn for example has lead stearate.

When containing a large amount of inclusiones, inorganic additive or organo-metallic salt addn in the organic waste, separate out, preferably reduce the amount of primary treatment in order to prevent inorganics.

The 2nd refuse processing method of the present invention is characterized in that, has lower molecular weight chemical industry preface, separation circuit and oxidation operation; In the lower molecular weight operation, the mixture of organic waste and medium is kept the scheduled time in supercritical state, make whole or most of organism contained in the organic waste carry out lower molecular weightization; In separation circuit, separate contained insoluble inclusion in the organic waste; In oxidation operation, the resultant that generates in described lower molecular weight operation is mixed with oxygenant, and keep the scheduled time to carry out oxidation at subcritical state.

According to this method, even organic waste contains insoluble inclusion, inorganic additive or the organo-metallic salt addn of volume, after the processing of supercritical state, after removing these inclusiones etc., add oxygenant at subcritical state and make oxidation operation, so, decomposing organic matter effectively, and prevent to separate out at the inorganics of subcritical state.Needn't reduce the amount of primary treatment.

In these refuse processing methods, the hydrogen ion concentration of medium is 10 with respect to the above-mentioned medium of 1kg preferably ^-4More than the mole.Because improve the solubleness of inorganics, can reduce separating out of inorganics more.

The 3rd refuse processing method of the present invention, be that the mixture of organic waste and medium is kept the scheduled time in supercritical state, organism contained in the organic waste is decomposed, it is characterized in that, the hydrogen ion concentration of above-mentioned medium is, is 10 with respect to the above-mentioned medium of 1kg ^-4More than the mole.

According to this method, because the hydrogen ion concentration of medium is to be 10 with respect to the above-mentioned medium of 1kg ^-4More than the mole, so can prevent separating out of inorganics.

Medium also can contain oxygenant.

Process object can be with the 1st or the 2nd refuse processing method in same organic waste, in addition, organic waste also can contain oxide compound.According to this refuse processing method, can handle these materials effectively.

The 4th refuse processing method of the present invention, be that the mixture of inorganic waste and medium is kept the scheduled time in supercritical state, inorganics contained in the inorganic waste is decomposed, it is characterized in that, the hydrogen ion concentration of above-mentioned medium is, is 10 with respect to the above-mentioned medium of 1kg ^-4More than the mole.

In the medium of supercritical state, inorganics is decomposed effectively.Hydrogen ion concentration is 10 in the medium of every 1kg ^-4More than the mole, so according to this refuse processing method, the inorganics after the decomposition is not separated out, and can be present in the fluid.

Process object preferably only contains the waste of inorganics, for example, also can handle the cured body that contains the α waste.Inorganic waste also can contain nitric acid and/or nitrate.But, be not limited thereto, also can be containing some organic wastes as process object.

Medium also can contain oxygenant.

In the refuse processing method of the present invention, overcritical chemical industry preface of medium and mixed processes can be set also:, make medium become supercritical state in the overcritical chemical industry preface of medium; At mixed processes, the medium of supercritical state and the mixture of organic waste or inorganic waste have been become.With the medium of organic waste or inorganic waste supply supercritical state, can carry out offal treatment expeditiously continuously continuously.

Certainly, also can medium with after organic waste or inorganic waste mix, to the mixture heating up that obtains, pressurization and become supercritical state.

Medium can adopt water, carbonic acid gas or hydrocarbon or their mixtures more than 2 kinds.

Usually, in the medium of supercritical state, at normal temperatures and pressures, the material of gas or liquid all can be equably with any mixed.In addition, in the medium of supercritical state, compare, be expected to obtain high material translational speed with the situation that adopts liquid vehicle.Therefore, supercritical state medium of the present invention can adopt water, carbonic acid gas, the hydrocarbon with above-mentioned characteristic according to process object.

By they are mixed, can change the stagnation point of medium.

Oxygenant can adopt more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they; The consumption of these oxygenants preferably makes organic waste or more than 1 times of the required stoichiometry of inorganic waste complete oxidation.Preferably use stoichiometric 1.2～10 times.

When regulating hydrogen ion concentration, preferably use mineral acid.Preferably use sulfuric acid, hydrochloric acid etc.Be not suitable for adopting pyrolysated acid under high heat resemble nitric acid.

The 1st waste treatment apparatus of the present invention is characterized in that, has:

Organic waste feedway with organic waste supply response device;

Medium feedway with medium supply response device;

Make the oxidation reactor of the resultant of reactor generation in the subcritical state oxidation;

Oxygenant is supplied with the oxygenant feedway of oxidation reactor;

Be used to be recovered in the resultant fluidic retrieving arrangement that oxidation reactor generates.

The 2nd waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, make the contained whole or most of organism of organic waste carry out lower molecular weightization, follow the reactor that at subcritical state resultant is mixed and makes its oxidizing reaction with oxygenant;

Organic waste feedway with organic waste supply response device;

Medium feedway with medium supply response device;

Oxygenant feedway with oxygenant supply response device;

Be used to be recovered in the resultant fluidic retrieving arrangement that reactor generates.

The 3rd waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, the reactor that the contained organism of organic waste is decomposed;

With the organic waste feedway of organic waste supply response device,

With the medium feedway of medium supply response device,

The setting device of the interior hydrogen ion concentration of conditioned reaction device,

Retrieving arrangement with the resultant fluid recovery that generates in the reactor.

The 4th waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, make the contained whole or most of organism of organic waste carry out lower molecular weightization, then resultant be mixed the reactor that makes its oxidation with oxygenant at subcritical state;

With the organic waste feedway of organic waste supply response device,

With the medium feedway of medium supply response device,

With the oxygenant feedway of oxygenant supply response device,

The 5th waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, make the contained whole or most of organism of organic waste carry out lower molecular weightization reactor,

With the organic waste feedway of organic waste supply response device,

With the medium feedway of medium supply response device,

Make resultant that reactor generates the oxidation reactor of subcritical state oxidation,

With oxygenant supply with oxidation reactor the oxygenant feedway,

The 6th waste treatment apparatus of the present invention is characterized in that, has:

In the medium of supercritical state, the reactor that the contained inorganics of inorganic waste is decomposed;

With the inorganic waste feedway of inorganic waste supply response device,

With the medium feedway of medium supply response device,

The 1st, 2,3,4,5 waste treatment apparatus of the present invention also can have the neutral salt adding set, and this adding set is used for adding neutral salt at the medium of supply response device.

In the above-mentioned reactor, the device to content irradiation ultraviolet radiation or radioactive rays can be set also.

In the aforesaid liquid treatment unit, also can be provided for the neutralising arrangement of the acid in the neutralising fluid.

In the 3rd, 4,5,6 waste treatment apparatus of the present invention, above-mentioned setting device is mixed back supply response device with mineral acid and medium with predetermined hydrogen ion concentration.

Above-mentioned setting device can have: with the hydrogen ion concentration instrumentation device of hydrogen ion concentration in the sour feedway of mineral acid supply response device, the instrumentation reactor, according to from the signal of hydrogen ion concentration instrumentation device with the mineral acid of the calculated amount control device in the sour feedway supply response device.

Above-mentioned mineral acid preferably adopts at least one side in sulfuric acid or the hydrochloric acid.

Above-mentioned reactor is provided with the agent gas feedway of supplying with oxygenant, and above-mentioned setting device is regulated hydrogen ion concentration according to the kind and the oxygenant feed rate of organic waste or inorganic waste.Can handle various wastes effectively.

Waste treatment apparatus of the present invention can have the tripping device that separates contained insoluble inclusion in organic waste or the inorganic waste in above-mentioned reactor.

Preferably be provided with the device that is used for the media state in the detection reaction device.Like this, whether the medium that can correctly grasp in the reactor are supercritical state, with optimal state processing waste.For example, if the device of instrumentation reactor temperature and pressure is set, just can detect the state of medium.Also can be the direct temperature and pressure in the assaying reaction device, but measure the temperature and pressure of the mixture of medium before the supply response device and waste.

In above-mentioned organic waste or inorganic waste feedway, medium feedway, be provided for respectively pressurizeing and the pressurizing device and the primary heater unit of preheating organic waste or inorganic waste, medium; In above-mentioned retrieving arrangement, be provided with the fluid pressure and refrigerative reliever and the refrigerating unit that are used to make the reactor generation.When having sour feedway or oxygenant feedway, the pressurizing device and the primary heater unit of pressurization and pre-hot acid or oxygenant can be set also.Make such structure, supply with, reclaim, handle waste etc. serially, improve processing efficiency.

Above-mentioned oxygenant can adopt more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they; The consumption of these oxygenants preferably makes organic waste or more than 1 times of the required stoichiometry of inorganic waste complete oxidation.Preferably use stoichiometry 1.2～10 times.

The device of at least a portion of topped organic waste or inorganic waste feedway preferably is set.For example, preferably at least a portion of organic waste or inorganic waste feedway is arranged in spherical case or the guard shield.

Above-mentioned topped device preferably has explosion-proof.

Above-mentioned retrieving arrangement preferably has gas-liquid separation device, gas treatment equipment, fluid treatment appts.

The above-mentioned gas treatment unit preferably has strainer and washer; Strainer is used for removing solids, radioactive substance or the objectionable impurities of gas; Washer is used for reclaiming the radioactive substance or the objectionable impurities of gas.

Wherein at least a of the solution that is used for washer, the water that preferably adopts water, contains the alkaline solution of sodium hydride or contain reductive agent.

The aforesaid liquid treatment unit preferably has the device of taking liquid to analyze.

The aforesaid liquid treatment unit preferably has the whipping appts that stirred liq is used.

The aforesaid liquid treatment unit preferably has the refrigerating unit that cooling liqs is used.

The aforesaid liquid treatment unit preferably has the device of the mineral ion coagulative precipitation that makes in the liquid.

The aforesaid liquid treatment unit preferably has the device of the frozen composition in the separating liquid.

The aforesaid liquid treatment unit preferably has the ion exchange unit of removing liquid intermediate ion composition.

The aforesaid liquid treatment unit preferably has makes liquid contact, extract the extraction recycling and processing device of mineral ion in the recovering liquid with extraction agent.

The said extracted agent, at least one side who preferably adopts neutral organophosphorus compound or acid organo phosphorous compounds.

The thinner of said extracted agent preferably adopts carbonic acid gas.

The aforesaid liquid treatment unit preferably has the liquid of making or sludge exsiccant drying installation.

The aforesaid liquid treatment unit preferably has the liquid of making or sludge solidified solidification equipment.

Above-mentioned solidification equipment preferably makes the thing that mixes of liquid or sludge or their mixture and solidifying agent solidify in container.

Therefore,, utilize the medium of supercritical state, when handling organic waste or inorganic waste, can prevent effectively that inorganics from separating out according to the present invention, and, a large amount of wastes can be handled effectively.Can reduce the cost of erection and the running cost of device significantly.

Description of drawings

Fig. 1 is the procedure chart of the refuse processing method of the embodiment of the invention 1.

Fig. 2 is the refuse processing method procedure chart of conventional example.

Fig. 3 is the graphic representation that is illustrated in the plumbous oxide solubleness under overcritical, the undercritical conditions.

Fig. 4 is the curve that the ionic product of water of expression when temperature and pressure is changed changes.

Fig. 5 is the curve of the cerium deposition rate of expression when the oxygenant addition is changed.

Fig. 6 is the waste treatment apparatus synoptic diagram of expression embodiment 3.

Fig. 7 is the figure that expression is located at the separator of reactor lower part.

Fig. 8 is the critical curve of expression water and the stagnation point of hydrocarbon class mixture.

Fig. 9 is the waste treatment apparatus synoptic diagram of expression embodiment 4.

Figure 10 is the waste treatment apparatus synoptic diagram of expression embodiment 5.

Figure 11 is the waste treatment apparatus synoptic diagram of expression embodiment 6.

Figure 12 is the figure of the α nuclear species retrieving arrangement structure of expression embodiment 6.

Figure 13 is the waste treatment apparatus synoptic diagram of expression embodiment 7.

Figure 14 is the partial figure of waste treatment apparatus of expression embodiment 8.

Figure 15 is the state graph of water.

Figure 16 is the partial figure of waste treatment apparatus of expression embodiment 9.

Figure 17 is the partial figure of waste treatment apparatus of expression embodiment 10.

Figure 18 is the partial figure of waste treatment apparatus of expression embodiment 11.

Figure 19 is the partial figure of waste treatment apparatus of expression embodiment 12.

Figure 20 is the partial figure of waste treatment apparatus of expression embodiment 13.

Figure 21 is the partial figure of waste treatment apparatus of expression embodiment 14.

Figure 22 is the partial figure of waste treatment apparatus of expression embodiment 15.

Figure 23 is the partial figure of waste treatment apparatus of expression embodiment 16.

Figure 24 is the partial figure of waste treatment apparatus of expression embodiment 17.

Figure 25 is the partition ratio curve of expression 30%TBP-nitrose class radioactivity (ア Network チノイ De) element.

Figure 26 is the partition ratio curve of expression HDEHP-nitrose radioactivity (ア Network チノイ De) element.

Embodiment

Following with reference to accompanying drawing, describe embodiments of the invention in detail.

The following describes embodiment, in following embodiment or figure, same parts are annotated with same numeral, and its repeat specification is omitted.

(embodiment 1)

Fig. 1 represents the procedure chart of the embodiment of the invention 1.Fig. 2 is the procedure chart of conventional example.

As shown in Figure 2, in the existing method,, make water become supercritical state as medium in the overcritical chemical industry preface 1 of medium.At mixed processes 2, add the organic waste of sulfur-bearing hydrochlorate in the water of this supercritical state.At overcritical decomposition process 6, the mixture that obtains is being kept the scheduled time above under the High Temperature High Pressure of water stagnation point with oxygenant.The organic waste of sulfur-bearing hydrochlorate divides at the water oxygen of supercritical state to be separated.

The inorganicss such as vitriol (oxide compound etc.) that contain in the decomposition gas that generates and decomposed solution and the organic waste are sent to recovery process 5, accept the processing of nuisance recovery, curing etc.

And in the method for embodiment 1,, make water become supercritical state as medium in the overcritical chemical industry preface 1 of medium.At mixed processes 2, add the organic waste of sulfur-bearing hydrochlorate in the water of this supercritical state.

In addition, can the medium of supercritical state not mixed with organic waste yet, but earlier with medium with after organic waste mixes, heat again and heat this mixture, make medium become supercritical state.

In lower molecular weight operation 3, the mixture that obtains is kept the scheduled time in the water that does not have the oxygenant supercritical state, make the whole or most of organism lower molecular weightizations in the sulfur-bearing hydrochlorate organic waste.

Then, the resultant that generates in lower molecular weight chemical industry preface is mixed with oxygenant, keep the scheduled time at subcritical state at oxidation operation 4.

Contained inorganicss such as vitriol (ion) in the decomposition gas that generates and decomposed solution and the organic waste are sent to recovery process 5, accept the processing of nuisance recovery, curing etc.

In the existing method, though the organism in the oxygenolysis organic waste effectively, when containing organic/inorganic substance in organic waste, in supercritical state, with subcritical state relatively, the easier formation oxide compounds of inorganics etc. are also separated out.

With lead is the example explanation.Fig. 3 is the solubility curve (chemical science understands the 63rd annual meeting, engineering portion of Northeastern University, make pottery him " solubility test of the metal oxide in subcritical, the supercritical water ") of overcritical, the undercritical conditions of expression plumbous oxide down.Shown in this curve, at supercritical range more than 374 ℃, the solubleness of plumbous oxide is little, is 0.5 * 10 at 450 ℃ ^-3Mol/kg.But in subcritical region, solubleness rises about 10 times, is 0.5 * 10 ^-2Mol/kg.When coexisting with oxygen, then solubleness has the tendency that more reduces.

Therefore, if in prior art, handle the organic waste that contains inorganic additive or organo-metallic salt addn with supercritical state under the condition that oxygenant exists, then contained inorganics is separated out as oxide compound in inorganic additive or the organo-metallic salt addn.

In the present embodiment, in lower molecular weight chemical industry preface, owing to there is not oxygenant, inorganicss such as vitriol contained in the organic waste are not oxidized, therefore, can prevent separating out of inorganic oxide.

Then, add oxygenant at subcritical state and make its oxidation, decomposing organic matter effectively.

Before organism and oxygenant mixed oxidization, mix when being incorporated in supercritical state and making its reaction with water, then be present in the organism in conjunction with the little combination of energy, selectively be thermal decomposited or add water decomposition, can make high-molecular weight organism lower molecular weightization.Then, add oxygenant in the organism after the lower molecular weightization, make its reaction at subcritical state because organic molecular weight is little, fast with the speed of response of oxygen, oxidation at short notice.

Therefore, after supercritical state makes organic waste with scheduled time reaction, keep the scheduled time, can decompose organic waste effectively, and can prevent separating out of inorganics at subcritical state.

Among the embodiment 1, be to use hydrogen peroxide as oxygenant, but be not limited thereto.Also can use in oxygen, air, ozone or oxygen, air, hydrogen peroxide, the ozone more than 2 kinds.

Organism usually reacts with group (ラジカ Le) and decomposes.For organism, active group is hydroxyl (OH: to call the OH yl in the following text).The OH base has the redox potential shown in the I formula in 25 ℃ acidic solution, be the oxygenant stronger than ozone.

2.85V.vs.NHE …I

Therefore, for decomposing organic matter effectively, the generation of OH base is crucial.

In supercritical water, water and oxygen reaction generate OH base and the hydroperoxidation base (OOH) shown in the II formula.

…II

According to people's such as Baulch research, if the reaction velocity constant of II formula is 10 in 500 ℃ ^-10.5Then very slow during mol/s.(oxygen 0.00631mol, water 6.31mol), in addition, the hydroperoxidation base reacts as (III) formula, generates hydrogen peroxide and oxygen, and the IV formula is decomposed like that for another example, generates the OH base.

…III

…IV

Usually, group reaction each other is fast, and the decomposition reaction of hydrogen peroxide is easy during temperature more than 100 ℃, so the speed of response of III, IV formula is fast.

When in supercritical water, using the oxygen decomposing organic matter, because the speed of response of II formula is slow, so, add hydrogen peroxide, when directly generating the OH base, can cause organic decomposition reaction effectively.

Below be to decompose poly result with embodiment 1 method.

Polyethylene 10mg that is attached with the 2mg cerous sulfate and water 2ml, add in the reactor (5.6ml), with 400 ℃, 30MPa it was reacted 30 minutes.

After the reaction, get back to normal temperature and pressure and measure, the result is that the polyethylene that exists as solid has 99% above thermolysis at first, becomes the paraffinic and the chain alkene of c=1～30, is present in gas or the liquid.

Then, add hydrogen peroxidase 10 .3g and water 1.6g (becoming 3.6g altogether), with 350 ℃, 30MPa maintenance 60 minutes.After the reaction, get back to normal temperature and pressure, measure the organic body carbon amount in gas and the liquid, the result is the oxidized decomposition of the organism more than 99%.

After the reaction, get back to normal temperature and pressure, filter decomposed solution, with the cerium in ICP (InductivelyCoupled Plasma Spectroscopy) the mensuration filtrate.In addition, with acid dissolving filter paper, similarly measure cerium with ICP, the result is a sediment-free.Therefore, cerium all exists with ionic species, not as oxide precipitation.

As a comparative example, in prior art, under the condition that oxygenant exists, in supercritical water, polyethylene has been done decomposition.

The polyethylene 10mg that is attached with the 2mg cerous sulfate and water 2ml and hydrogen peroxidase 10 .3g, add in the reactor (5.6ml), with 400 ℃, 30MPa it was reacted 30 minutes.

The result is that the polyethylene more than 99% is oxidized, generates to have decomposed carbonic acid gas.There is the cerium of half to become oxide precipitation.

From as can be known above-mentioned, with the method for embodiment 1, do not separate out inorganics, can decompose organic waste effectively.

(embodiment 2)

In the method for embodiment 2, in the overcritical chemical industry preface 1 of existing medium shown in Figure 2, making hydrogen ion for the water of 1kg is 10 ^-4Mole adds mineral acid abovely, and this solution is become supercritical state, uses as overcritical medium in operation thereafter.

According to people's such as Smith research, the metallic element in the nitric acid waste adds water decomposition shown in the V formula under High Temperature High Pressure, and then, thermolysis shown in the VI formula finally becomes oxide compound.

Nitric acid in that the V formula generates produces oxygen after the thermolysis, so, form oxide compound easily.

Formula V

Formula VI

In order to prevent such water decomposition that adds, must add acid, the balance of formula V is moved to the left.

Hydrogen ion concentration in the water has substantial connection with the ionic product of water.The ionic product of the water when Fig. 4 represents the temperature and pressure variation changes.

For example, when pressure was 25MPa, the ionic product of water was maximum near 300 ℃, is 10 ^-11(mol/kg) ²Hydrogen ion concentration in the supercritical water when therefore, not coexisting with acid etc. is 3.3 * 10 ^-6Mol/kg.Under the condition of supercritical water more than 374 ℃, the ionic product of water is less than 10 ^-11(mol/kg) ², in the time of 600 ℃, be 10 ^-24(mol/kg) ²Therefore, the hydrogen ion concentration in the time of 600 ℃ is 10- ¹²Mol/kg, much smaller during than 300 ℃.

In the prior art, during with the supercritical water decomposing organic matter, adopt high temperature and than the condition (for example 600 ℃, 25MPa) of low pressure more.Therefore, only water is added in the organism that contains inorganics when making its reaction with high temperature, it is extremely low that the hydrogen ion concentration in the reactor becomes, and the balance of formula V is moved right, and inorganics is separated out as oxide compound.

In order to increase the ionic concn in the supercritical water, must increase ionic product.As shown in Figure 4, ionic product increases along with the rising of pressure, and the actual pressure that can use is as below the 50MPa.

For example, 350 ℃, during 50MPa, ionic product is 10 ^-12(mol/kg) ², than the ionic product under the normal temperature and pressure 10 ^-14(mol/kg) ² Big 100 times, hydrogen ion concentration is 10 ^-6Mol/kg.Like this,, the hydrogen ion concentration in the supercritical water is extremely increased, in the present embodiment, in supercritical water, add acid, can regulate hydrogen ion concentration, prevent separating out of inorganics by selecting temperature and pressure.

With the method for present embodiment, research is added acid, the condition that inorganics is not separated out in supercritical water.

Add 5 * 10 ^-5The sulfuric acid of mole, the hydrogen ion concentration that obtains water is 10 ^-4The medium of mol/kg.

The medium that obtain are mixed with cerous nitrate (cerium 1mg), after 30 minutes, get back to normal temperature and pressure, filter decomposed solution, measure cerium in the filtrate with ICP with 400 ℃, 25MPa reaction.In addition,, similarly measure cerium, confirm to have sediment-free with ICP with acid dissolving filter paper.The result is as shown in table 1.

In addition, as conventional example, represented to adopt the result of two kinds of medium.A kind of is not add sulfuric acid only with the result of water as medium.Another kind is the water adding 5 * 10 for 1kg ^-6The mole sulfuric acid, be that hydrogen ion concentration is 10 ^-5The result of the medium of mol/kg.

As shown in table 1, in the conventional example, cerium 100% becomes the cerium oxide precipitation, and has added 5 * 10 ^-5During mol sulfuric acid, deposition rate is 0%, and all the cerium amount remains in the liquid with dissolved state.In addition, added 5 * 10 ^-6During mol sulfuric acid, 70% cerium precipitation.

From the above, make hydrogen ion concentration become 10 ^-4When mol/kg ground adds acid, there is not the precipitation of cerium.

Table 1

The sulfuric acid amount of in 1kg water, adding	0 mole	5×10 ^-6 Mole	5×10 ^-5Mole
The sulfuric acid amount of in 1kg water, adding	0 mole	5×10 ^-6 Mole	5×10 ^-5Mole	The cerium deposition rate	100％	70％	0％
Remarks	Conventional example		The present invention	The cerium deposition rate	100％	70％	0％

When having oxygen in the inorganics, oxidized and become oxide compound.In the method for present embodiment, studied when having oxygenant in the medium, inorganics is separated out and the condition of energy decomposing organic matter.

Fig. 5 is illustrated in and adds water, sulfuric acid and oxygenant in the cerous nitrate (cerium 1mg), with 400 ℃, 30 minutes result of 25MPa reaction.Water for 1kg has added 5 * 10 ^-3The sulfuric acid of mole.The result who measures with ICP is that cerium precipitates along with the increase of oxygenant addition.When the oxygenant addition surpasses 600 times (hydrogen peroxidase 10 .3g) of stoichiometry (supposing that cerium becomes cerium dioxide), 97% cerium precipitation.

Therefore, when oxygenant exists,, must increase the addition of acid along with the increase of oxygenant addition.

Table 2 is illustrated in the oxygenant that adds 4 times of stoichiometry in the cerous nitrate (cerium 1mg), with 400 ℃, 30 minutes result of 25MPa reaction.Sulfuric acid is 5 * 10 with respect to the addition of water ^-2During mol/kg, the deposition rate of cerium is 0%.

Therefore, under the condition that oxygenant exists,, must add 5 * 10 with respect to the water of 1kg ^-2(hydrogen ion concentration is 10 to mol/kg sulfuric acid ^-1Mol/kg).

Table 2

The sulfuric acid amount of in 1kg water, adding	5×10 ^-4 Mole	5×10 ^-3 Mole	5×10 ^-2Mole
The sulfuric acid amount of in 1kg water, adding	5×10 ^-4 Mole	5×10 ^-3 Mole	5×10 ^-2Mole	The cerium deposition rate	98％	70％	0％

As mentioned above, when oxygenant exists, in the 1kg medium, make hydrogen ion concentration become 10 ^-1When mole ground adds acid, can not separate out inorganics ground decomposing organic matter.

In the method for present embodiment, the situation when having studied the inorganic salt that contain in the organic waste beyond the nitrate.

In nitrate, vitriol, muriate, phosphoric acid salt and the oxide compound (cerium 1mg) of cerium, 4 times have been added to the oxygenant of stoichiometry, as process object.In water, added 5 * 10 ^-2Mol/kg sulfuric acid was as medium, with 400 ℃, 30MPa reaction 30 minutes.

The result is as shown in table 3.

Under nitrate, vitriol, muriate and phosphatic situation, the result who measures with ICP is, the amount of the cerium that exists as ion in water is 100%, and the deposition rate of cerium is 0%.In addition, at first 50% of the oxide compound that exists with solid, be dissolved in the liquid, even there is a spot of oxide compound also to can be recycled in the liquid.

Table 3

The form of cerium	Nitrate	Vitriol	Muriate	The phosphoric acid salt oxide compound
The form of cerium	Nitrate	Vitriol	Muriate	The phosphoric acid salt oxide compound	The amount that is present in the cerium in the water	100％	100％	100％	100％ 50％

As mentioned above, according to the method for present embodiment,, also can make inorganics not separate out the ground decomposing organic matter even not only nitrate contains vitriol, muriate, phosphoric acid salt, oxide compound.

For example, when processing contains the organic waste of plutonium oxide, plutonium can be recovered in the liquid as ion, so, the organic waste (for example cloth waste, gloves) that is polluted by plutonium can be become to non-α waste (only containing the waste of not emitting the alpha-ray element), can lower processing cost.

In addition, in the method for present embodiment,, whether can not separate out inorganics ground processing organic waste and do research for adopting sulfuric acid, hydrochloric acid as the mineral acid of regulating the medium hydrogen ion concentration.

In cerous nitrate, add 4 times to the oxygenant of stoichiometry, in 1kg water, add 5 * 10 respectively ^-2The sulfuric acid of mol/kg, hydrochloric acid, nitric acid, with it as medium.With 400 ℃, 30MPa reaction 30 minutes, its result was as shown in table 4.

Result with ICP measures during with sulfuric acid, hydrochloric acid, does not find the precipitation of cerium, when still adding nitric acid, and 100% cerium precipitation.Because nitric acid thermolysis at high temperature, hydrogen ion concentration is in 1kg water 10 ^-4Below the mol, the solubleness of inorganics is low, therefore produces precipitation.

As mentioned above, when adopting sulfuric acid or hydrochloric acid, can not separate out inorganics ground and decompose organic waste as mineral acid.

Table 4

The kind of acid	Sulfuric acid	Hydrochloric acid	Nitric acid
The kind of acid	Sulfuric acid	Hydrochloric acid	Nitric acid	The cerium deposition rate	0％	0％	100％

(embodiment 3)

Fig. 6 is the synoptic diagram of expression present embodiment waste treatment apparatus.

The waste treatment apparatus of present embodiment has: the supercritical state of water handle organic waste reactor 11, with organic waste drop into reactor 11 organic waste feedway 12, will as the water feeder 13 of the water supply reactor 11 of medium, make the low-molecular-weight organic matter oxidation that generates at reactor 11 oxidation reactor 14, with oxygenant supply with oxidation reactor 14 oxygenant feedway 15, reclaim oxidation reactor 14 and the retrieving arrangement 30 of resultant.

Retrieving arrangement 30 has gas-liquid separator 33, gas treatment equipment 34, fluid treatment appts 40.

Fluid treatment appts 40 has the moisture eliminator 45 and the solidification device 46 of drying, solidified liquid sludge.

In the present embodiment, reactor 11 and oxidation reactor were arranged in 14 minutes, the two are connected, delivering to oxidation reactor 14 at the resultant of reactor 11 generations with pipe etc.But also can become the structure that a container is divided into 2 chambers with division plate etc.Also can a container be used as reactor 11 and oxidation reactor 14 by suitably regulating pressure and temperature.

Process object is not particularly limited.Can be the organic waste that contains resin etc., by polluted organic waste of radiation material etc., can handle various organic wastes.

Contain the organic waste of insoluble inclusiones such as sand, gravel in processing, when containing the organic waste of inorganic additives or organic metal salt additive resin etc., earlier after supercritical state makes the organism lower molecular weightization, carry out oxidation at subcritical state again, also can fully prevent separating out of inorganics.

In this case, preferably reduce the amount of the organic waste of primary treatment.In addition, as shown in Figure 7, can be provided with separator 18, utilize weight or inertia to remove the inorganics of separating out in supercritical state in the bottom of reactor 11.Like this, can prevent to separate out at the inorganics of subcritical state.

As shown in Figure 7, separator 18 can be located at the inside of reactor 11, also can be located between reactor 11 and the oxidation reactor 14.

In the present embodiment, be to adopt water, but be not limited to this, also can adopt carbonic acid gas, various hydrocarbon or their mixture as overcritical medium.

Fig. 8 is the critical curve of the stagnation point of expression water and hydrocarbon class mixture.Label 116 is critical curves of water-benzene class, label 117 is critical curves of heavy water-benzene class, label 118 is critical curves of water-toluene class, label 119 is critical curves of water-o-Xylol class, label 120 is critical curves of water-1,3,5-Three methyl Benzene class, label 121 is critical curves of water-cyclohexanes, label 122 is critical curves of water-ethane class, label 123 is critical curves of water-normal butane class, label 124 is critical curves of water-naphthalene class, label 125 is critical curves of water-biphenyl class, and label 126 is critical curves of water.The stagnation point of water is 374 ℃, 22MPa, in Fig. 8, for example in water-benzene class, with 2 kinds of compositions of specific mixed, stagnation point can be reduced to more than 300 ℃.Therefore, if the mixture that adopts water, carbonic acid gas, hydrocarbon as medium, then can keep supercritical state ground under the soft condition of more low temperature, low pressure, handle organic waste.

In the present embodiment, be to adopt hydrogen peroxide, but be not limited thereto, also can adopt the mixture more than 2 kinds of oxygen, air or ozone or oxygen, air, hydrogen peroxide or ozone as oxygenant.

When adopting hydrogen peroxide, decomposing organic matter effectively.

For complete decomposing organic matter, the addition of hydrogen peroxide preferably makes organism become more than 1 times of carbonic acid gas or water aequum.Be preferably 1.2～10 times.

When handling organic waste with this device, will be by water feeder 13 as the water supply reactor 11 of medium.In the water that becomes supercritical state, supply with organic waste at reactor 11, mix, keep the scheduled time in supercritical state with supercritical water with organic waste feedway 12.

Organic waste is in reactor 11, under the supercritical state of medium water, by lower molecular weightization.Resultant is moved on to oxidation reactor 14, behind the interpolation oxygenant, in the subcritical state oxidation.

The resultant that generates at oxidation reactor 14 is sent to retrieving arrangement 30, is separated into gas and liquid by gas-liquid separator 33, is sent to gas treatment equipment 34 and fluid treatment appts 40 respectively, reclaims objectionable impurities.

The solid phase or the liquid phase that decompose to generate after moisture eliminator 45 dryings, are sneaked into solidifying agent in solidification device 46, solidify in the processing vessel of releasing jar etc., become stable cured body.Like this, the security in the time of can guaranteeing to handle, it is also easy to manage.Solidifying agent preferably adopts grout.

By organic waste supplying device 12, water feeder 13, oxygenant feedway 15 are set, supply with organic waste, water, oxygenant to reactor 11 serially, in addition, take out resultant continuously by retrieving arrangement 30.Therefore, handle organic waste serially.

As mentioned above, according to the waste treatment apparatus of present embodiment, when utilizing supercritical state to handle organic waste, the inorganics that exists of can preventing is over separated out this problem.

Therefore, can avoid separating out the troubles such as reactor obturation that cause because of inorganics.But the working cost of reducing apparatus and maintenance cost.In addition, when inorganics is radioactive substance, can reduce harm to the operator.

When hydrogen peroxide is added as oxygenant, can generate the OH base at short notice, so a large amount of organism of disaggregating treatment at short notice.

Make inorganic salt not become oxide compound, and reclaim with the ion shape, the inorganics that exists as oxide compound also can be recovered in the liquid from the beginning, so, organic waste can be become lost body for even matter.

(embodiment 4)

Fig. 9 is the synoptic diagram of present embodiment waste treatment apparatus.

The waste treatment apparatus of embodiment 4 has: the reactor 11 of handling organic waste in the supercritical state of water, organic waste is dropped into the organic waste feedway 12 of reactor 11, will be as the water feeder 13 of the water supply reactor 11 of medium, the PH of the hydrogen ion concentration of water meter 23 in the assaying reaction device 11, sour feedway 16 with sour supply response device 11, control sour feedway 16 and with the controller 24 of the sour supply response device 11 of calculated amount according to the instrumentation value of PH meter 23, reclaim the retrieving arrangement 30 of reactor 11 resultants.

From the acid that sour feedway 16 is supplied with, be to adopt ionized mineral acid in medium water, still, be not suitable for using resembling pyrolysated acid when height is warm the nitric acid.Preferably adopt sulfuric acid or hydrochloric acid.

As described in embodiment 2, when the decomposition of organic waste, if the hydrogen ion concentration of water is 10 ^-4More than the mole/kg, then can suppress the inorganics of supercritical state and separate out.

But, consider different types of organic waste, its decomposition product is to the influence of the hydrogen ion concentration of water.

For example, the polymer container that polyethylene or polyvinyl chloride are done under the water existence condition, makes its reaction with 374 ℃, 22.1MPa, and polyethylene adds water decomposition, generates ethanol and organic acid etc., but polyvinyl chloride also generates hydrochloric acid except generating ethanol and organic acid.Cl content in the polyvinyl chloride is 56wt%, if add the polyvinyl chloride of 0.006g in the water of 1kg, then the hydrogen ion concentration in the reactor is 10 ^-4Mole/kg.

Therefore, when in 1kg water, adding the polyvinyl chloride of 0.006g, needn't add acid.But, because polyethylene does not generate acid, so, add acid, make that the hydrogen ion concentration in 1kg water is 10 ^-4Mole/kg.

In addition, when decomposing the mixed waste of the polyvinyl chloride that does not generate sour polyethylene and generate acid, understand its ratio of mixture, grasp from the amount of the acid of organism generation.

In the present embodiment, count hydrogen ion concentration in the 23 The real time measure reactors 11,, calculate by controller 24 that hydrogen ion concentration becomes 10 in every 1kg water according to this measured value with PH ^-4The amount of the above required acid of mole is controlled the sour supply response device 11 of sour feedway 16 with calculated amount.

According to this structure, with the organic waste kind irrespectively, all the hydrogen ion concentration in the reactor can be remained on appropriate state.

According to process object, supply with the acid of optimal dose, can reduce the amount of the acid of supply significantly.

In addition, since following, compare with conventional example, can adopt small-sized gas-liquid separator 33.

Carbonic acid gas is dissolved in water shown in the VII formula become carbonic acid, and carbonic acid is decomposed into the ion shown in VIII, the IX formula in water.

…VII

…VIII

…IX

For the balance that makes VII, VIII, IX formula is moved to the left, separating carbon dioxide and water must increase the hydrogen ion concentration in the liquid.When the sour separation constant of VIII formula is 20 ℃ 10 ^-3.6(mol/l).(HCO when hydrogen ion concentration is changed ₃ ^-)/(H ₂CO ₃) ratio as shown in table 5.

Because H ₂CO ₃With the carbon dioxide balance in the gas phase, the HCO in being dissolved in liquid ₃ ^-Ratio greater than H ₂CO ₃The time, the separation difficulty of water and carbonic acid gas.In the existing method, because the hydrogen ion concentration in the liquid is 10 ^-7About mole/Kg, so, the H in the liquid ₂CO ₃Ratio few, during separating carbon dioxide, must contact with the air of volume, just need bigger gas-liquid separator.

But among the present invention, because hydrogen ion concentration is 10 ^-4More than the mole/Kg, so, compare with conventional example, can adopt small-sized gas-liquid separator, can lower cost of equipment.In addition, needn't add air, reduce the treatment capacity of gas processing device, lower cost of equipment and working cost.

Table 5

Hydrogen ion concentration (mol/l)	[HCO ₃ ^-]/[H ₂CO ₃] ratio
Hydrogen ion concentration (mol/l)	[HCO ₃ ^-]/[H ₂CO ₃] ratio	10 ^-1	0.0025
10 ^-2	0.025	10 ^-1	0.0025
10 ^-2	0.025	10 ^-3	0.25
10 ^-4	2.5	10 ^-3	0.25
10 ^-4	2.5	10 ^-7(conventional example)	2500

In the present embodiment, be with the hydrogen ion degree of depth in the PH meter 23 direct assaying reaction devices 11, but in fact owing to be High Temperature High Pressure in the reactor, PH counts sometimes is provided with difficulty.

Also can calculate the amount that is added to the acid in the water, resupply reactor 11 after being mixed into the acid of aequum in the water according to the kind of processed waste and amount etc.Like this, even the hydrogen ion concentration of the medium in the not direct assaying reaction device also can be controlled hydrogen ion concentration, so, the PH meter needn't be set.

As mentioned above, in the organic waste decomposer of present embodiment, according to the feed rate that the kind of organic waste is regulated mineral acid, control becomes the most suitable hydrogen ion concentration state that prevents that inorganics from separating out, and also can easily handle mixing various organic waste.

The amount of the mineral acid in the handle assembly in the organic waste water converts with hydrogen ion, and control becomes in the 1kg water 10 ^-4More than the mole, facility investment that can be big prevents that effectively inorganics from separating out.In addition, gas-liquid separator also can miniaturization.

Make inorganic salt not become oxide compound, reclaim with the ion shape, the inorganics that exists as oxide compound also can be recovered in the liquid from the beginning, organic waste can be become the lost body for even matter.

(embodiment 5)

Figure 10 is the synoptic diagram of present embodiment waste treatment apparatus.

The waste treatment apparatus of present embodiment is in the waste treatment apparatus of embodiment 4, is provided with the oxygenant feedway 15 with oxygenant supply response device 11 usefulness.

In the waste treatment apparatus of present embodiment, in reactor 11, the supercritical state at water makes the organism lower molecular weightization earlier, reduces the pressure and temperature in the reactor 11 then, carries out organic oxidation at subcritical state.

Hydrogen ion concentration in the reactor 11 is, by the measured value of controller 24 according to PH meter 23, controls sour feedway 16, is adjusted to that hydrogen ion concentration is 10 in every 1kg water ^-4More than the mole.

Organic waste preferably contains volume inclusion, inorganic additives or organo-metallic salt additives.If contain the inorganic additives of volume etc. in the organic waste, reduce the amount of the organic waste of primary treatment, perhaps, the precipitate tripping device is set, after the processing in supercritical state, remove the inorganics of separating out, handle at subcritical state again.

As mentioned above, in the organic refuse treatment appts of present embodiment, make the organism lower molecular weightization, carry out oxygenolysis at subcritical state then, can prevent separating out of inorganics in supercritical state.

Because the processing of supercritical state and the processing of subcritical state are carried out in same reactor, so the expense of restraining device is operated also simple.

In addition, the hydrogen ion concentration of every 1kg water is adjusted to 10 ^-4More than the mole, can prevent more effectively that inorganics from separating out.

According to the oxidant content of the kind of organic waste and amount, use etc., the feed rate of regulating mineral acid can be controlled to be hydrogen ion concentration appropriate state, also can easily handle mixing various organic waste.

By adding oxygenant, a large amount of organism of disaggregating treatment at short notice.

(embodiment 6)

Figure 11 is the synoptic diagram of present embodiment waste treatment apparatus.

In the waste treatment apparatus of present embodiment, organic waste supplying device 12 is not set, but is provided with inorganic waste feedway 51 inorganic waste supply response device 11.In addition, in gas treatment equipment 34, have ammonia treatment device 52, in fluid treatment appts 40, have α nuclear species retrieving arrangement 53.In addition, all the other structures are identical with the waste treatment apparatus of embodiment 5.As shown in figure 12, α nuclear species retrieving arrangement 53 is made of the separator 44 of the solids in cyclator 43 and the separating liquid.

In addition, also inorganic waste feedway 51 can be set, and also supply with inorganic waste by organic waste feedway 12.Like this, can handle organic waste and inorganic waste, help reducing cost with same device.

As process object, preferably only contain the waste of inorganics.For example, also can handle the cured body that contains the α waste.But, be not limited thereto, also can will contain organic waste as process object.

Adopt this device to handle when containing the inorganic waste of such radioactive substance of α nuclear species or nitrate, will be by water feeder 13 as the water supply reactor 11 of medium.With inorganic waste feedway 51 inorganic waste is supplied with the water that has become supercritical state in reactor 11, mix, keep the scheduled time in supercritical state with supercritical water.

Hydrogen ion concentration in the reactor 11 is, by the measured value of controller 24 according to PH meter 23, controls sour feedway 16, is adjusted to that hydrogen ion concentration is more than the 10-4 mole in every 1kg water.

Inorganic waste in reactor 11, under the condition that oxygenant exists, oxygenolysis under the supercritical state of medium water.

In the present embodiment, because the hydrogen ion concentration of every 1kg water is adjusted to 10 ^-4More than the mole,, can be recycled in the liquid so radioactive substance (for example plutonium etc. α nuclear species) is not separated out.Contained nitric acid or nitrate are not separated out yet and are decomposed in the inorganic waste, are recovered in the gas as ammonia.

The resultant that generates is sent to retrieving arrangement 30, is separated into gas and liquid by gas-liquid separator 33, delivers to gas treatment equipment 34 and fluid treatment appts 40 respectively.

Contain ammonia gas in ammonia treatment device 52, be heated to more than 310 ℃ under the condition that the platinum catalyst exists, ammonia becomes nitrogen.

Contain the liquid of α nuclear species such as plutonium, in the cyclator 43 of α nuclear species retrieving arrangement 53, be added barium, generate the barium sulfate of insoluble.The α nuclear species of III valency and IV valency and barium sulfate coprecipitation.After the α nuclear species of V valency and VI valency is reduced agent and is reduced to III valency and IV valency, with the barium sulfate coprecipitation.When containing caesium, strontium etc., by adsorbents adsorb postprecipitations such as zeolite, cobaltous ferrocyanide, metatitanic acids.

When liquid contains ammonia, add sodium hydroxide, make the pH value of liquid become 9 after, ammonia is replaced as vapor phase, from liquid, remove.

Reclaim after also can containing the neobalgin that precipitates the α nuclear species, become the vitrification body with separator 44 separation.Also can become solidified cement body.

Except barium, also can add iron, PH is become more than 4, make the ironic hydroxide coprecipitation of α nuclear species and generation, make ironic hydroxide become solidified cement body.Also can make the microcosmic salt coprecipitation of itself and lanthanum.

Removed the liquid of α nuclear species, after moisture eliminator 45 dryings, in solidification device 46, mixed, in the processing vessel of releasing jar etc., solidified, become the cured body of non-α waste with solidifying agent.Solidifying agent can adopt grout.

As mentioned above, in the waste treatment apparatus of present embodiment, be that every 1kg water is 10 by the medium hydrogen ion concentration of regulating supercritical state ^-4Mole can prevent that the inorganics of radioactive substance or nitrate etc. from separating out.Therefore, can avoid separating out the troubles such as reactor obturation that cause because of inorganics.Working cost and maintenance cost that can not only reducing apparatus also can reduce radioactive material confrontation operator's harm.

According to present embodiment,, do not contain nitrate in the cured body of the α waste after the first supercritical processing because nitrate ion is decomposed into most of nitrogen.Therefore, cured body is embedded in the underground ammonia that also do not produce of reducing atmosphere, can prevents nuclear substance strippings from cured body such as plutonium.

In addition, the cured body that the liquid of having removed the α nuclear species and sludge have been solidified, right and wrong α waste, so, can in shallow stratum, handle, like this, depleted is handled easily.And, reduce the deep stratum of waste and handle, can reduce processing costs.

For example, obtain the cured body of radioactive waste, from this cured body, reclaim the α nuclear species of plutonium etc., become the vitrification body, can reduce the amount of α waste significantly with usual method.

In the present embodiment, be to make α nuclear species precipitate and separate reclaim it, but be not limited to the α nuclear species, also can make the mineral ion cohesion of the metal that is dissolved in the liquid phase etc., carry out precipitation process.

In addition, in

embodiment

3 or 4 the treatment unit, also the device that makes these mineral ion coagulative precipitations can be set.

(embodiment 7)

The waste treatment apparatus of present embodiment, as shown in figure 13, be in the waste treatment apparatus of embodiment 3, in organic waste feedway 12, water feeder 13, oxygenant feedway 15, well heater 25a～c and pressurizer 26a～c are set respectively, in retrieving arrangement 30, pressure reducer 31 and water cooler 32 are set.

In the waste device of embodiment 4 or embodiment 5, in organic waste feedway 12, water feeder 13, oxygenant feedway 15, sour feedway 16, also same well heater and pressurizer can be set, in retrieving arrangement 30, also same pressure reducer and water cooler can be set.

In the waste treatment apparatus of embodiment 6, in inorganic waste feedway 51, water feeder 13, oxygenant feedway 15, sour feedway 16, also same well heater and pressurizer can be set, in retrieving arrangement 30, also same pressure reducer and water cooler can be set.

Well heater 25a～c heats organic waste, medium, oxygenant respectively, pressurizer 26a～c pressurize respectively organic waste, medium, oxygenant.Make such structure, can be continuously organic waste, water, oxygenant supply response device 11, and, do not reduce temperature of reaction and pressure ground and handle organic waste continuously.

The decomposition product that generates at oxidation reactor 14 is sent to retrieving arrangement 30, is depressurized device 31 and water cooler 32 decompression coolings.Make such structure, extract the resultant fluid from oxidation reactor 14 serially, and then carry out the fluidic gas-liquid separation effectively by gas-liquid separator 33.

Oxygen is added to when decomposing in the organism, and carbon becomes carbonic acid gas, and hydrogen becomes water.Under the condition of supercritical water, mix arbitrarily as the water of medium and the carbonic acid gas of decomposition generation, be not easy to separate.But,, when becoming normal temperature and pressure, can divide dried up and major part carbonic acid gas to the fluid that decompose the to generate cooling of reducing pressure.

Like this, according to present embodiment, compare with batch treatment, processing speed is fast, can reduce working cost significantly.In addition, the gas-liquid separation of gas-liquid separation device 33 can be carried out effectively.

(embodiment 8)

The waste treatment apparatus of present embodiment as shown in figure 14, is in the waste treatment apparatus of embodiment 3, is provided with temperature sensor 21 and pressure transmitter 22 in reactor 11.

In

embodiment

4,5,6 or 7 the waste treatment apparatus, also can make same structure.

Figure 15 represents the state graph of water.The state of water depends on temperature and pressure, so, whether be supercritical state or subcritical state in the reactor 11, just can hold by monitoring the temperature and pressure in the reactor.

With the temperature and pressure that temperature sensor 21 and pressure transmitter 22 monitor in the reactor 11, whether the medium that can accurately grasp in the reactor 11 are supercritical state, like this, and can be with optimal state processing waste.

Not only reactor 11, be preferably in same temperature sensor and pressure transmitter also are set in the oxidation reactor 14, and whether like this, can grasp in the oxidation reactor 14 is subcritical state.

As the waste treatment apparatus of embodiment 7, have in the device of well heater 25a～c and pressurizer 26a～c, also can before the supply response device, measure the temperature and pressure of the waste that is heated or pressurizes, medium etc.Even temperature and pressure in the not direct assaying reaction device also can be grasped the state in the reactor.

(embodiment 9)

The waste treatment apparatus of embodiment 9 as shown in figure 16, is in the waste treatment apparatus of embodiment 3, and at least a portion of reactor 11 and organic waste feedway 12 is arranged in the loft drier (グロ-Block ボ Star Network ス) 27.

In

embodiment

4,5,6,7 or 8 the waste treatment apparatus, also can make same structure.

When handling, must be able to not make radioactive substance or objectionable impurities leak into the outside by radioactive substance or the polluted organic waste of objectionable impurities.The waste treatment apparatus of embodiment 3, major part is handled in the system of sealing, but the part of organic waste feedway 12 becomes open system in order to accept organic waste.Therefore, when handling, the organic waste feedway 12 that becomes open system is arranged in the parts such as guard shield (Off-De) or loft drier, can antipollutionly spreads by radioactive substance or the polluted organic waste of objectionable impurities.

In addition, topped parts such as loft drier or guard shield preferably can be explosion-proof.Because of the decomposition of organic waste produce explosion hazard volatile organic matter or, when adhering to the volatile organic matter that explosion hazard is arranged on the organic waste, also can handle.

According to present embodiment, because the part of treatment unit is arranged in the spherical case, and whole device is arranged on topped parts internal-phase ratio, can make the equipment scale miniaturization.

(embodiment 10)

Present embodiment is in the waste treatment apparatus of embodiment 3 as shown in figure 17, is provided with neutral salt feedway 29, and this neutral salt feedway 29 is used for adding neutral salt to medium water.

In

embodiment

4,5,7,8 or 9 the waste treatment apparatus, also can make same structure.

Usually, the salt M of insoluble _nL _mSolubleness Ks, with the amount of living shown in the X formula.

M ^m++L ^n-→M _nL _m，Ks＝a1 ^m·a ²ⁿ …X

A1:M ^M+The amount of living, a2:L ^N-The amount of living

The amount of living a is with living coefficient of discharge γ and concentration C shown in the XI formula.

a＝γ·C …XI

When temperature and pressure is one regularly, the amount of living a be that necessarily Ks has certain value.In thin solution, γ=1, the amount of living a equates with concentration C.But, when ionic strength increases, γ＜1, concentration C increases as a result, is dissolved in the M in the solution ^M+And L ^N-Increase, solubleness has the tendency of increase.

Therefore, when adding neutral salt, the solubleness of indissoluble salt increases, and can suppress precipitation.

This neutral salt can adopt sodium-chlor, Repone K, calcium chloride, magnesium chloride, sodium sulfate, vitriolate of tartar etc.

According to present embodiment,, can more effectively suppress inorganics and separate out owing to add neutral salt.

(embodiment 11)

The waste treatment apparatus of present embodiment as shown in figure 18, is in the waste treatment apparatus of embodiment 3, has the radiation exposure device 28 to the content irradiation radioactive rays of reactor 11.

Also can make same structure in

embodiment

4,5,7,8,9 or 10 the waste treatment apparatus.

Also can not use the radiation exposure device, and use the UV irradiation equipment of irradiation ultraviolet radiation.

During Xiang Shuizhong irradiation radioactive rays, shown in the XII formula, generate the OH base.

…XII

The OH base becomes strong oxidizer shown in the I formula, so, also can decomposing organic matter even do not add oxygenant.

In addition, under the condition that oxygenant exists, if irradiation ultraviolet radiation and radioactive rays then more can quicken this reaction.For example, during the irradiation radioactive rays, oxygen generates group, finally generates hydrogen peroxide.Hydrogen peroxide as the reaction of XIII formula ground, generates the OH base under the condition that radioactive rays exist, but decomposing organic matter.

…XIII

Ozone reacts with ultraviolet ray shown in the XIIII formula, generates hydroperoxy-.Hydrogen peroxide reacts shown in the XIII formula with ultraviolet ray again, generates the OH base.

…XIIII

For another example shown in the XV formula, hydrogen atom and oxygen reaction in that the VII formula generates generate the hydroperoxidation base, shown in the XVI formula and ozone reaction, generate the OH base for another example.

…XV

…XVI

Therefore,, can generate the OH base effectively by the irradiation radioactive rays, thus decomposing organic matter more effectively.

When processing contains the waste of radioactive substance, needn't just can easily form radiation field from the external irradiation radioactive rays, so, can not obtain above-mentioned effect even have the radiation exposure device yet.

(embodiment 12)

The waste treatment apparatus of present embodiment, as shown in figure 19, be in the waste treatment apparatus of embodiment 3, gas treatment equipment 34 has strainer 35 and washer 36, strainer 35 is used for removing the solids or the objectionable constituent of gas, and washer 36 is used to reclaim objectionable constituent.

Also can make same structure in

embodiment

4,5,6,7,8,9,10 or 11 the waste treatment apparatus.

For example, when the waste of having handled by the radio contamination of processing plant again, the such volatile element of technetium or ruthenium carries out the transition in the gas phase.

Ruthenium carries out the transition in the gas phase as ruthenium tetroxide, but reduction becomes ruthenium dioxide when organism exists.Ruthenium dioxide is solid at normal temperatures, so, can remove with the strainer of removing solids.

Technetium carries out the transition in the gas phase as seven technetium oxides or the acid of mistake technetium, but shown in XVII, XVIII formula, when contacting with water, is dissolved in the water with ionic forms.

…XVII

…XVIII

Therefore, when being provided with washer, technetium can be recovered in the liquid.

In order more effectively to reclaim the element of technetium etc., in washer, except making water, preferably use the water that contains the alkaline solution of sodium hydroxide or contain reductive agent.

When technetium contacts with water, shown in XVII, XVIII formula, with anionic form dissolving.This negatively charged ion and sodium ion reaction generate salt, so, the form of technetium with salt can be recovered in the solution.

…XVIIII

When reductive agent existed, technetium was reduced, and became from mistake technetium acid (VII valency) to be titanium dioxide technetium (IV valency).For the water of normal temperature and pressure, the solubleness of titanium dioxide technetium is little, so technetium can be recovered in the water with solid form.

As mentioned above,, can remove the solid or the volatility harmful element that in gas phase, move by spittle companion according to present embodiment, even contaminated by radioactive substances waste also can safe handling.

(embodiment 13)

The waste treatment apparatus of embodiment 13 as shown in figure 20, is in the waste treatment apparatus of embodiment 3, and fluid treatment appts 40 has the agitator 41 of stirred liq and takes that liquid analyzes takes analytical equipment 42.

In

embodiment

4,5,6,7,8,9,10,11 or 12 the waste treatment apparatus, also can make same structure.

Deliver to the liquid of fluid treatment appts 40 from gas-liquid separation device 33, after being stirred device 41 and stirring, it is even that liquid phase becomes.With taking analytical equipment 42 to take the part of uniform liquid, and analyze, then can understand the composition of liquid phase.In solidification device 46, can select storage, handle the most suitable solidification equipment.In addition, the content of the cured body after the solidification treatment is very clear, so the management when storage, processing is easy.

Even contain outstanding turbid solid substance in the liquid, also available agitator 41 stirs, and is cured processing in solidification device 46 easily.

Do not take analytical equipment 42 if be not provided with, then do not know the content of cured body, will be in management with measuring its content someway.But in the mensuration of cured body content, it is difficult taking representational sample, so low precision has problems on waste management.

(embodiment 14)

The waste treatment apparatus of present embodiment as shown in figure 21, is in the waste treatment apparatus of embodiment 3, and fluid treatment appts 40 has neutralizing treatment device 50, and this neutralizing treatment device 50 is used for acid, the alkali that neutralizing treatment liquid contains.

In

embodiment

4,5,7,8,9,10,11,12 or 13 the waste treatment apparatus, also can make same structure.

For example, when processing contained the solid radiation waste of technetium, technetium became seven technetium oxides and carries out the transition in the gas phase.

But, from oxidation reactor 14 decomposition product is recovered to retrieving arrangement 30 after, when adding the such alkali of sodium hydroxide, shown in the XVIIII formula, can make trace remain in the technetium stabilization in liquid phase in the liquid after the gas-liquid separation with neutralizing treatment device 50.

Therefore, according to present embodiment, contained objectionable impurities stabilizations such as radioactive substance in the liquid, solidification treatment easily in solidification device.

(embodiment 15)

The waste treatment apparatus of embodiment 15 as shown in figure 22, is in the waste treatment apparatus of embodiment 3, is provided with the water cooler 47 that the cooling liquid phase is used in the fluid treatment appts 40.

In

embodiment

4,5,6,7,8,9,10,11,12,13 or 14 the waste treatment apparatus, also can make same structure.

When handling radioactive waste, because the radioactive substance in the fluid treatment appts 40 sends heat, liquid can not cool off and seethe with excitement, and may enlarge the pollution of radioactive substance.During with water cooler 47 cooling liqss, can avoid this danger, make radioactive substance in liquid phase, keep stable.

(embodiment 16)

The waste treatment apparatus of present embodiment as shown in figure 23, is in the waste treatment apparatus of embodiment 3, is provided with ion exchange tower 48 in the fluid treatment appts 40.

In

embodiment

4,5,6,7,8,9,10,11,12,13,14 or 15 the waste treatment apparatus, also can make same structure.

For example, when the waste of having handled by the radio contamination of processing plant again, though the such volatile element of technetium or ruthenium carries out the transition in the gas phase, but its part remains in the liquid phase, technetium became technetium acid and existed in solution, and the complex compound that ruthenium becomes chloride ion or nitrate ion exists in solution.

Because crossing technetium acid is negatively charged ion, available anionite-exchange resin is removed.Ruthenium is a positively charged ion, and available Zeo-karb is removed.

Therefore,, can remove the such harmful ion composition of contained radioactive substance in the solution of decomposition product, rest solution can be discharged outside the system, lower the processing costs of waste according to present embodiment.

In addition, removed the harmful ion composition in the liquid in this wise after, supply to the waste liquid of solidification device from the liquid treatment line, its liquid phase and solid phase are even, become homogeneous.As long as sneak into solidifying agent in this waste liquid, just can form the cured body of homogeneous, this stable cured body is stored, handled to available simple process.

(embodiment 17)

The waste treatment apparatus of present embodiment, as shown in figure 24, be in the waste treatment apparatus of embodiment 3, be provided with in the fluid treatment appts 40 and extract retrieving arrangement 49, this extraction retrieving arrangement 49 is used to make liquid to contact with extraction agent, and the harmful mineral ion in the water is recovered in the extraction agent.

In

embodiment

4,5,7,8,9,10,11,12,13,14 or 15 the waste treatment apparatus, also can make same structure.

For example, from the radioactive waste that processing plant produces again, contain the nuclear fuel material of uranium, plutonium etc.Directly solidify if will contain the organic waste of these elements, then become the α waste, increase the cured body processing costs.Therefore, must from waste, remove these elements.

As extraction agent, can adopt the acid organo phosphorous compounds of the basic phosphoric acid of neutral organophosphorus compound or two (HDEHP) etc. of tricresyl phosphate butyl (hereinafter referred to as TBP) etc.

Figure 25 represents the partition ratio of TBP-nitrose radioactivity (ア Network チノイ De) element of 30vol%.When concentration of nitric acid was 3mol/ liter (リ Star ト Le), the partition ratio of uranium, plutonium, neptunium was more than 10, and the partition ratio of thorium is more than 3.

With after extracting retrieving arrangement 49 and will being recovered to liquid acid concentration adjustment to 3 gram mol/ in the fluid treatment appts and rising, it is contacted with TBP, radioelement such as plutonium can be recovered among the TBP.In addition, the TBP that contains radioelement such as plutonium is contacted with diluted acid, the radioelement of plutonium etc. can be recovered in the diluted acid.

Figure 26 has represented to adopt the partition ratio of the radioelement of HDEHP.Even concentration of nitric acid is 10 ^-1Below mol/ rose, the partition ratio of plutonium, uranium, americium also more than 100, can be recycled among the HDEHP.In addition, make when acid contacts with HDEHP about the 1mol/ liter that contains hydrazine reductive agents such as (ヒ De ラジ Application), the VI valency of plutonium or uranium is reduced, and becomes the III valency, is recovered in the acid.

If use HDEHP, be 10 then in acid concentration ^-1About mol/ rises, recyclable radioelement, so, compare with neutral organophosphorus compounds such as using TBP, can reduce the amount of adding the acid in the Separation and Recovery device to, lower working cost.

The thinner of extraction agents such as above-mentioned TBP or HDEHP preferably adopts supercritical co.Because the amount of the organic solvent after capable of reducing using lowers secondary offal treatment expense significantly.

The proportion of TBP at normal temperatures and pressures and water with, be 1g/ml, with n-dodecane (ノ Le マ Le De デカ Application) when adding among the TBP as thinner, but separate easily organic phase and water.After being recovered to the radioactive substance of plutonium etc. among the TBP, because TBP or n-dodecane after using have radioactivity, so, must handle as the radioactivity organic waste.

Usually, owing to mixed, so the treatment capacity of n-dodecane is more than 2 times of TBP with TBP30vol%, n-dodecane 70vol%.Therefore, if do not need to handle n-dodecane, processing costs can be reduced to 1/3rd.

Under 31 ℃, condition more than the 7.4MPa, carbonic acid gas becomes supercritical state, mix arbitrarily with organism, so, when TBP is contacted with supercritical carbon dioxide, can be from decomposed solution the radioelement of plutonium etc. be recovered among the TBP.At normal temperatures and pressures, carbonic acid gas becomes gas after the use, can separate with TBP easily, so, do not need the processing of carbonic acid gas.

Therefore, when adopting supercritical carbon dioxide, can reduce processing costs significantly as thinner.

As mentioned above,, the harmful mineral ion in the liquid is recovered in the extraction agent, can reduces the processing costs of cured body according to present embodiment.

In addition, removed the harmful ion composition in the liquid in this wise after, supply to the waste liquid of solidification device from fluid treatment appts, its liquid phase and solid phase are even, become homogeneous.As long as sneak into solidifying agent in this waste liquid, just can form the cured body of homogeneous, this stable cured body is stored, handled to available simple process.

Claims

1. a refuse processing method is characterized in that, has lower molecular weight chemical industry preface and oxidation operation; In lower molecular weight chemical industry preface,, make whole or most of organism contained in the organic waste carry out lower molecular weightization with the mixture maintenance scheduled time of organic waste with the medium that are in supercritical state that do not have oxygenant; In oxidation operation, the resultant that generates in described lower molecular weight chemical industry preface is mixed with oxygenant, and in being in the described medium of subcritical state, keep the scheduled time to carry out oxidation.

2. refuse processing method as claimed in claim 1 is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the medium of supercritical state and the mixture of organic waste have been become.

3. refuse processing method as claimed in claim 1 is characterized in that, above-mentioned organic waste contains more than 2 kinds of nitrate, vitriol, muriate, phosphoric acid salt or silicate or they.

4. refuse processing method as claimed in claim 1 is characterized in that, above-mentioned medium are water, carbonic acid gas or hydrocarbon or their mixtures more than 2 kinds.

5. refuse processing method as claimed in claim 1 is characterized in that, above-mentioned oxygenant is to use more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they; The consumption of these oxygenants is to make more than 1 times of the required stoichiometry of organic waste complete oxidation.

6. refuse processing method as claimed in claim 1 is characterized in that, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the above-mentioned overcritical medium of 1kg ^-4More than the mole.

7. refuse processing method as claimed in claim 1 is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned critical medium, and the hydrogen ion concentration of above-mentioned overcritical medium is that the overcritical medium above-mentioned with respect to 1kg are adjusted into 10 ^-4More than the mole.

8. refuse processing method as claimed in claim 1 is characterized in that, also has separation circuit, after lower molecular weight chemical industry preface, before the oxidation operation, separates contained insoluble inclusion in the organic waste.

9. refuse processing method as claimed in claim 8 is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the described medium of supercritical state and the mixture of described organic waste have been become.

10. refuse processing method as claimed in claim 8 is characterized in that, above-mentioned organic waste contains more than 2 kinds of nitrate, vitriol, muriate, phosphoric acid salt or silicate or they.

11. refuse processing method as claimed in claim 8 is characterized in that, above-mentioned medium are water, carbonic acid gas or hydrocarbon or their mixtures more than 2 kinds.

12. refuse processing method as claimed in claim 8 is characterized in that, above-mentioned oxygenant is to use more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they; The consumption of these oxygenants is to make more than 1 times of the required stoichiometry of organic waste complete oxidation.

13. refuse processing method as claimed in claim 8 is characterized in that, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

14. refuse processing method as claimed in claim 8 is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned critical medium, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

15. refuse processing method is characterized in that according to claim 1, it is characterized in that, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the above-mentioned medium of 1kg ^-1More than the mole.

16. refuse processing method as claimed in claim 15 is characterized in that, described waste is an organic waste, and organism contained in the described organic waste is decomposed.

17. method for organic waste disposal as claimed in claim 16 is characterized in that, has overcritical chemical industry preface of medium and mixed processes; In the overcritical chemical industry preface of medium, make described medium become supercritical state; At mixed processes, the described medium of supercritical state and the mixture of described organic waste have been become.

18. refuse processing method as claimed in claim 16 is characterized in that, above-mentioned organic waste contains more than 2 kinds of nitrate, vitriol, muriate, phosphoric acid salt or silicate or they.

19. refuse processing method as claimed in claim 16 is characterized in that, above-mentioned medium are water, carbonic acid gas or hydrocarbon or their mixtures more than 2 kinds.

20. refuse processing method as claimed in claim 16 is characterized in that, above-mentioned overcritical medium contain oxygenant.

21. refuse processing method as claimed in claim 16, it is characterized in that, above-mentioned overcritical medium contain more than 2 kinds of oxygen, air, hydrogen peroxide or ozone or they, and amount is to make more than 1 times of the required stoichiometry of described organic waste oxidation fully.

22. refuse processing method as claimed in claim 16 is characterized in that, adds at least one side of sulfuric acid or hydrochloric acid in above-mentioned critical medium, the hydrogen ion concentration of above-mentioned overcritical medium is, is 10 with respect to the described overcritical medium of 1kg ^-4More than the mole.

23. a waste treatment apparatus is characterized in that having:

In the medium of the supercritical state that does not have oxygenant, make the contained whole or most of organism of organic waste carry out the reactor of lower molecular weightization;

Described medium are supplied with the medium feedway of described reactor;

24. waste treatment apparatus as claimed in claim 23 is characterized in that, has: the setting device of regulating hydrogen ion concentration in the described reactor.

25. waste treatment apparatus as claimed in claim 23 is characterized in that, above-mentioned reactor has the tripping device that separates contained insoluble inclusion in the described organic waste.

26. waste treatment apparatus as claimed in claim 23, it is characterized in that, in above-mentioned organic waste feedway, described medium feedway, described oxygenant feedway, be respectively equipped with the pressurizing device and the primary heater unit that are used to pressurize with the organic gurry of preheating, medium, oxygenant;

27. waste treatment apparatus as claimed in claim 23 is characterized in that, has the device that detects the media state in the described reactor.

28. waste treatment apparatus as claimed in claim 23 is characterized in that, above-mentioned reactor has the device of internal dress thing irradiation ultraviolet radiation or radioactive rays.

29. waste treatment apparatus as claimed in claim 23 is characterized in that, above-mentioned recycling and processing device has gas-liquid separation device, gas treatment equipment, fluid treatment appts.

30. waste treatment apparatus as claimed in claim 29 is characterized in that, the above-mentioned gas treatment unit has strainer and washer; Described strainer is used for removing solids, radioactive substance or the objectionable impurities of gas; Described washer is used for reclaiming the radioactive substance or the objectionable impurities of gas.

31. waste treatment apparatus as claimed in claim 29 is characterized in that, the aforesaid liquid treatment unit has the device of the mineral ion coagulative precipitation that makes in the liquid.

32. waste treatment apparatus as claimed in claim 29 is characterized in that, the aforesaid liquid treatment unit has the device of the solids in the separating liquid.

33. waste treatment apparatus as claimed in claim 29 is characterized in that, the aforesaid liquid treatment unit has the ion exchange unit of removing liquid intermediate ion composition.

34. waste treatment apparatus as claimed in claim 29 is characterized in that, the aforesaid liquid treatment unit has the liquid of making and contacts with extraction agent, with the extraction recycling and processing device of mineral ion in extraction and the recovering liquid.

35. waste treatment apparatus as claimed in claim 34 is characterized in that, adopts the thinner of carbonic acid gas as described extraction agent.

36. waste treatment apparatus as claimed in claim 29 is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment.

37. waste treatment apparatus as claimed in claim 36 is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment and makes liquid or sludge exsiccant drying installation.

38. waste treatment apparatus as claimed in claim 36 is characterized in that, above-mentioned solidification equipment solidifies the batch mixing thing of liquid or sludge or their mixture and solidifying agent in container.

39. a waste treatment apparatus is characterized in that, has:

In the medium of supercritical state, the reactor that waste is decomposed;

Waste supplying device with the described reactor of described waste supplying;

Described medium are supplied with the medium feedway of described reactor;

Oxygenant is supplied with the oxygenant feedway of above-mentioned reactor;

Being adjusted to hydrogen ion concentration in the described reactor with respect to the described overcritical medium of 1kg is 10 ^-4The setting device that mole is above;

40. waste treatment apparatus as claimed in claim 39, it is characterized in that, above-mentioned waste is an organic waste, above-mentioned reactor is the reactor that above-mentioned organic waste is decomposed, and described waste supplying device is an organic waste feedway of described organic waste being supplied with described reactor.

41. waste treatment apparatus as claimed in claim 40 is characterized in that, above-mentioned setting device is mixed back supply response device with mineral acid and medium, to become predetermined hydrogen ion concentration.

42. waste treatment apparatus as claimed in claim 40 is characterized in that, above-mentioned setting device has:

Mineral acid is supplied with the sour feedway of described reactor;

43. waste treatment apparatus as claimed in claim 42 is characterized in that, above-mentioned setting device is regulated described hydrogen ion concentration according to the kind of described organic waste and the feed rate of described oxygenant.

44. waste treatment apparatus as claimed in claim 42, it is characterized in that, in above-mentioned organic waste feedway, medium feedway, oxygenant feedway, be respectively equipped with the pressurizing device and the primary heater unit that are used to pressurize with preheating organic waste, medium, oxygenant; In above-mentioned retrieving arrangement, be provided with the fluid pressure and refrigerative reliever and the refrigerating unit that are used to make described reactor generation.

45. waste treatment apparatus as claimed in claim 39 is characterized in that, above-mentioned reactor has the device of internal dress thing irradiation ultraviolet radiation or radioactive rays.

46. waste treatment apparatus as claimed in claim 39 is characterized in that, above-mentioned recycling and processing device has gas-liquid separation device, gas treatment equipment and fluid treatment appts.

47. waste treatment apparatus as claimed in claim 46 is characterized in that, the above-mentioned gas treatment unit has strainer and washer; Described strainer is used for removing solids, radioactive substance or the objectionable impurities of gas; Described washer is used for reclaiming the radioactive substance or the objectionable impurities of gas.

48. waste treatment apparatus as claimed in claim 46 is characterized in that, the aforesaid liquid treatment unit has the device of the mineral ion coagulative precipitation that makes in the liquid.

49. waste treatment apparatus as claimed in claim 46 is characterized in that, the aforesaid liquid treatment unit has the device of the solids in the separating liquid.

50. waste treatment apparatus as claimed in claim 46 is characterized in that, the aforesaid liquid treatment unit has the ion exchange unit of removing liquid intermediate ion composition.

51. waste treatment apparatus as claimed in claim 46 is characterized in that, the aforesaid liquid treatment unit, have make liquid contact with extraction agent, extract and recovering liquid in the extraction recycling and processing device of mineral ion.

52. waste treatment apparatus as claimed in claim 46 is characterized in that, adopts the thinner of carbonic acid gas as the said extracted agent.

53. waste treatment apparatus as claimed in claim 46 is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment.

54. waste treatment apparatus as claimed in claim 39, it is characterized in that, above-mentioned waste is an inorganic waste, above-mentioned reactor is the reactor that the contained inorganics of above-mentioned inorganic waste is decomposed, and above-mentioned waste supplying device is an inorganic waste feedway of above-mentioned inorganic waste being supplied with described reactor.

55. waste treatment apparatus as claimed in claim 54 is characterized in that, above-mentioned setting device is mixed back supply response device with mineral acid and medium with predetermined hydrogen ion concentration.

56. waste treatment apparatus as claimed in claim 54 is characterized in that, above-mentioned setting device is regulated hydrogen ion concentration according to the kind of described inorganic waste and the feed rate of described oxygenant.

57. waste treatment apparatus as claimed in claim 54 is characterized in that, above-mentioned setting device has:

With mineral acid supply with described reactor sour feedway,

58. waste treatment apparatus as claimed in claim 54 is characterized in that, above-mentioned recycling and processing device has gas-liquid separation device, gas treatment equipment and fluid treatment appts.

59. waste treatment apparatus as claimed in claim 58 is characterized in that, the above-mentioned gas treatment unit has strainer and washer; Described strainer is used for removing solids, radioactive substance or the objectionable impurities of gas; Described washer is used for reclaiming the radioactive substance or the objectionable impurities of gas.

60. waste treatment apparatus as claimed in claim 58 is characterized in that, the aforesaid liquid treatment unit has the device of the mineral ion coagulative precipitation that makes in the liquid.

61. waste treatment apparatus as claimed in claim 58 is characterized in that, the aforesaid liquid treatment unit has the device of the solids in the separating liquid.

62. waste treatment apparatus as claimed in claim 58 is characterized in that, the aforesaid liquid treatment unit has the liquid of making or sludge solidified solidification equipment.

63. a waste treatment apparatus is characterized in that having:

In the medium of the supercritical state that does not have oxygenant, make the contained whole or most of organism of organic waste carry out lower molecular weightization, follow the reactor that at subcritical state resultant is mixed and makes oxidation with oxygenant;

Described medium are supplied with the medium feedway of described reactor;

Oxygenant is supplied with the oxygenant feedway of described reactor;

64. as the described waste treatment apparatus of claim 63, it is characterized in that, have: the setting device of regulating hydrogen ion concentration in the described reactor.