CN1798704A - Treating material for polluted water, method for production thereof and use thereof - Google Patents
Treating material for polluted water, method for production thereof and use thereof Download PDFInfo
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- CN1798704A CN1798704A CN 200480014973 CN200480014973A CN1798704A CN 1798704 A CN1798704 A CN 1798704A CN 200480014973 CN200480014973 CN 200480014973 CN 200480014973 A CN200480014973 A CN 200480014973A CN 1798704 A CN1798704 A CN 1798704A
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Abstract
A treating material for treating a polluted water containing, as a hazardous substance, arsenic, lead, cadmium, antimony, uranium, phosphorus, fluorine or the like, which comprises an oxygen-containing iron compound carried on a material containing a silicic acid based fiber or a silicate based fiber; a method for producing the treating material which comprises contacting and reacting a silicate based fiber, such as rock wool, with an iron-containing acidic water; and a method for treating the polluted water witch comprises contacting the treating material with the polluted water. The treating material has a fine structure wherein the above oxygen-containing iron compound is attached in a sheath form on the surface of a fiber reduced in an alkali component and increased in a silicic acid component as compared to, for example, rock wool. The oxygen-containing iron compounds include schwertmannite, ferrihydrite, akaganeite, amorphous hydrous iron oxide and fired ferric sulfate.
Description
Technical field
The present invention relates to a kind of being used for removes the processing material of objectionable impurities and uses this processing material to remove the method for objectionable impurities from the sewage that contains objectionable impuritiess such as heavy metal.
Technical background
The method of removing of objectionable impurities is extensive use of the method for the powder or the slurry that add slaked lime therein in the waste water.For example, known have a following treatment process: will contain after arsenic-vitriolic waste water once neutralizes by lime carbonate, slaked lime etc., thereby oxide treatment once in and water make after the arsenic oxidation, utilize slaked lime, lime carbonate etc. to carry out the secondary neutralizing treatment.Although this method reagent cost is low, it is strong that arsenic is removed ability, but in waste water, contain under the situation of excessive sulfate ion and iron ion, iron ion is separated out as the colloid of ironic hydroxide along with the rising of pH value, in addition, slaked lime or lime carbonate and sulfate ion react, and generate the gypsum of insoluble and the unreacted reactant of the slaked lime that uses as neutralization materials forms the mud shape of the high and difficult dehydration property of water content together and precipitates.This mud has problem owing to contain objectionable impurities in it is handled.
The granular cured article of mineral binder bonds such as mineral fibre such as the WO02-079100 communique discloses a kind of acid waste water and handled material, this material use aminanthine and slag cement.But, the processing material that contains excessive iron ionic acid waste water is only disclosed, the wastewater treatment that contains objectionable impuritiess such as arsenic, phosphoric acid is not mentioned.
In addition, known certain containing oxygen iron compound adsorbs arsenical ion.For example, the spy opens and discloses following method in the 2003-112162 communique: any iron cpd in the contaminated soil that contains arsenic or heavy metal in the moisture iron sulfate mineral (シ ユ ベ Le ト マ Na イ ト schwertmannlte) of interpolation chemosynthesis, pyrrhosiderite, jarosite, the ferrihydrite, make its arsenic-adsorbing or heavy metal, make it form stable state, the soil of purifying contaminated thus.The spy opens and discloses following method in the 2003-112163 communique: add the nutrient solution of iron-oxidizing bacterium in contaminated soil, make it generate the iron cpd of moisture iron sulfate mineral etc., make its arsenic-adsorbing etc. equally.But above-mentioned document is disclosed all to be only to the purification of contaminated soil, does not mention the processing to the waste water that contains objectionable impuritiess such as arsenic.
The oxygen acid of arsenic, phosphorus, selenium etc. is removed in known described moisture iron sulfate mineral absorption.At this, moisture iron sulfate mineral (シ ユ ベ Le ト マ Na イ ト schwertmannite) have consists of Fe
8O
8(OH)
8-2X(SO
4)
XIn addition, described absorption is removed and is meant except so-called absorption, also utilizes metal or ion and moisture iron sulfate mineral to exchange, and removes these poisonous metals or ion.
In addition, reported following content among geology impurity, the mat woven of fine bamboo strips 107 volume mat woven of fine bamboo strips No. 10 (October calendar year 2001), the p659-665: when having iron-oxidizing bacterium or sulfur-oxidizing bacteria in the acid wastewater in mine, generate on the water surface oil slick sample by membranaceous buoyant material (microbial film), be defined as moisture iron sulfate mineral.
Summary of the invention
The object of the present invention is to provide a kind of processing material and manufacture method efficiently thereof, it can be efficiently and carries out routine maintenance ground easily and handle the sewage that contains objectionable impuritiess such as arsenic, lead, cadmium, phosphorus, having good stability of resultant of reaction, objectionable impurities is few because of the stripping again of time variation or acidification, and does not need too much aftertreatment.Other purpose is to provide a kind of novel manufacture method with the moisture iron sulfate mineral processing material that is effective constituent.
In addition, also be to provide a kind of method of removing of objectionable impurities, it reaches the former water purification of tap water that contains micro-above-mentioned objectionable impurities also effective to the processing of ore deposit waste water, trade effluent, agricultural effluent, livestock industry waste water, aquatic products processing waste water, rivers and creeks water etc.
The present invention relates to a kind of processing material that is used to handle the sewage that contains objectionable impuritiess such as arsenic, it is characterized in that constituting by the containing oxygen iron compound that load on the material that contains the inorganic fibre that is selected from silicic acid matter fiber or phyllosilicate fiber.
Processing material of the present invention contains and has the containing oxygen iron compound of removing the objectionable impurities ability.This containing oxygen iron compound contains the material that load on the inorganic fibre in containing the material of inorganic fibre.Preferred negative is loaded on the inorganic fibre, and the containing oxygen iron compound is to carry out load around the sheath shape encirclement inorganic fibre.
The containing oxygen iron compound comprises that ferric oxide, hydrous ferric oxide etc. contain the compound of iron and oxygen.Can enumerate for example moisture iron sulfate mineral, ferrihydrite, kaganeite, pyrrhosiderite, lepidocrocite, rhombohedral iron ore, magnetite, maghemite, jarosite, moisture iron sulfate mineral sinter, the ferrihydrite sinter, the kaganeite sinter, the pyrrhosiderite sinter, amorphous hydrous ferric oxide sinter, the ferric sulfate sinter, the ferrous sulfate sinter, the iron(ic) chloride sinter, the iron protochloride sinter, the iron nitrate sinter, one or more of Iron nitrate sinter etc.At the containing oxygen iron compound is under the situation of sinter, preferably obtains about 30 minutes～2 hours by sintering under 150～800 ℃ of temperature, in the air.
And the containing oxygen iron compound is with FeOxZy or FeOxZynH
2O (Z is more than one atom or group, and x is the number greater than 0, and y is the number more than 0) expression.This containing oxygen iron compound can be the aggregate of various iron cpds, and can contain the containing oxygen iron compound that useful aforementioned formula represents is main component.Preferred moisture iron sulfate mineral, its content are more than the 30 weight % of containing oxygen iron compound, preferably contain more than the 50 weight %.
The material that contains inorganic fibre of load containing oxygen iron compound can use inorganic fibre separately, also can be the mixture of inorganic fibre and inorganic powder body or inorganic or organic binder bond.
Inorganic fibre uses silicic acid matter fiber or phyllosilicate inorganic fibre.What comprise the silica fiber representative in silicic acid matter inorganic fibre is the inorganic fibre of main component with silicon-dioxide.The silicate that comprises metals such as basic metal, alkaline-earth metal or aluminium (following above-mentioned metal is called the alkali composition) in the phyllosilicate inorganic fibre is the inorganic fibre of main component.Preferred inorganic fibre comprises with the acidic aqueous solution that contains iron ion handles the phyllosilicate inorganic fibre, removes at least a portion in the lixiviating composition, preferably removes more than 50%, more preferably more than 70%, makes the fiber of silicic acid component increase.The inorganic fibre that obtains except that the lixiviating composition is a porous matter, and surface-area is big, more volume ground load containing oxygen iron compound.
Concrete material as the phyllosilicate inorganic fibre, can enumerate aminanthine, nickel minerals slag wool, glass wool, ceramic fiber and as the broken thing of the calcium silicate board of building materials waste, just the broken thing of calcium silicate board that constitutes of tobermorite fiber, xonotlite fiber etc.What inorganic fibre preferably used is aminanthine, nickel minerals slag wool, glass wool.
The effective material that aminanthine is for example arranged or contain aminanthine.Aminanthine is except that without the aminanthine that uses, and also can be the recovery aminanthine etc. when containing the waste of aminanthine fireproof coating material (spraying aminanthine) of the above and cement of aminanthine 50 weight % and construction thereof.In addition, also can be with aminanthine and lime carbonate become the to grade waste of the aminanthine top ceiling that is principal constituent.Several shapes such as stratiform aminanthine, granular aminanthine are arranged, preferred granular aminanthine in aminanthine.Granular aminanthine is to utilize granulation machine or rotating screen etc. that the stratiform aminanthine is processed into the granulous material, and median size is about 1～50mm, about preferred 5～40mm.Can use in addition to add and reclaim aminanthine or tackiness agent, the granulous material is cut off or be broken into to the shaping aminanthine that is configured as tabular grade.This aminanthine is processed into granular product easily, water-permeable and good water-retaining property, the breeding of the suitable microorganism in its space etc.Preferably contain SiO
2: 30～50 weight %, Al
2O
3: 5～20 weight %, MgO+CaO:30～50 weight %, Na
2O+K
2O:0～10 weight % and other: the aminanthine of 0～10 weight %.
The material that contains inorganic fibre is under the situation that contains composition beyond the inorganic fibre, and preferred silicate is that inorganic powder body and tackiness agent are as described composition.Using silicate is under the situation of inorganic powder body, preferably than the material that the inorganic fibre silicate content lacks, basicity is high, and for example powder and the particle of the broken thing of cement, cement clinker, blast furnace slag, non-iron blast furnace slag, floating dust or concrete.In these materials, preferred high cement and the concrete of basicity.At silicate is that inorganic powder body still is under the situation of inorganic adhesive such as cement, does not need special tackiness agent, can use the organic binder bond of inorganic or resin system etc. under the situation beyond this.
Contain in the material of inorganic fibre, the contained ratio of inorganic fibre is the scope of 35～100 weight %, the scope of preferred 35～85 weight %.But the surface of inorganic fibre can major part be exposed.Using under the situation of inorganic fibre separately, inorganic fibre is preferably made textile-like with fiber, and it is interweaved.It is inorganic fibre and inorganic powder body mixture contain the material of inorganic fibre the time, both and the tackiness agent that adds as required, water etc. are mixed together, be configured as the granular use of Denging.
In addition, containing the material of inorganic fibre or making the voidage of the processing material of the present invention that its load containing oxygen iron compound obtains is more than 50%, and preferred more than 60%, bulk specific gravity is 0.1～1.5, preferred 0.1～0.5.
The method of load containing oxygen iron compound for example has following several in the material that contains inorganic fibre:
1) present method is to contain the material soaking of inorganic fibre in iron content sour water, utilize neutralization reaction and iron-oxidizing bacterium that the dissolving of alkali composition is separated out, in the fiber that the formation silica composition increases, show the containing oxygen iron compound of separating out saturation state to it.
2) present method is to prepare the slurry or the aqueous solution of the iron cpd that the containing oxygen iron compound is provided in advance, inorganic fibre etc. is immersed in this slurry or the aqueous solution, then sintering as required.
1) method is effective, in this case, when using with reactive low carbon fiber of acidic substance and silica fiber, then forms the few material of charge capacity of containing oxygen iron compound.
At first, to 1) carrying method describe, preferred its sulfate ion content of the iron content sour water that floods in containing the material of inorganic fibre is that 500～4000mg/l, ferrous ion content are 50～500mg/l, pH1.5～3.5.Preferred following method: with respect to this acidic solution 1000ml, add the material 1～100g that contains inorganic fibre, reacted in 1～100 hour by stirring at normal temperatures, forming the material while of containing inorganic fibre that silicic acid component increases, load containing oxygen iron compound.In this case, can carry out stirring reaction and reach 3～5 or 7～13 until the pH of acidic solution.At pH is 5～7 scope, and objectionable impurities is removed performance and reduced sometimes.
At this moment, the pH of the containing oxygen iron compound of the saturation state that generates when making and the difference of operation such as inflation are for being selected from the aggregate of one or more mineral in moisture iron sulfate mineral, ferrihydrite, kaganeite, pyrrhosiderite, lepidocrocite, rhombohedral iron ore, magnetite, maghemite, the jarosite.Wherein, consider active height of preferred surface and big ferrihydrite, moisture iron sulfate mineral, kaganeite, the pyrrhosiderite of specific surface area from the performance of removing objectionable impurities.
Acidic substance according to iron content sour water are different and different with the relation of the alkaline matter of the material that contains inorganic fibre, in treatment condition is that moisture ferriferous oxide generates moisture iron sulfate mineral, kaganeite, pyrrhosiderite, jarosite under the situation of acid (pH about 2～5).
Under acidic conditions, exist under ferrous situation,, preferably have iron-oxidizing bacterium in order to quicken the oxidation of iron.As the iron-oxidizing bacterium under the situation that iron-oxidizing bacterium is existed, can enumerate thiobacillus ferrooxidant (Thiobacillus ferooxidans), rust Jia Liweng Salmonella (Gallionella ferruginea), leptothrix ochracea (Leptothrix ochracea), hair tonic curly hair bacterium (Leptothrix trichogenes), Clonothrix species (Clonothrixsp.), Crenothrix species (Crenothrin sp.), Metallogenium species (Metallogeniumsp.), Ochrobium species (Ochrobium sp.) or Siderocapsa species (Siderocapsasp.) etc.Although different because of the kind of the iron content sour water that uses, for the strong oxidized water below the pH2, thiobacillus ferrooxidant is fit to, in addition preferred rust Jia Liweng Salmonella, hair tonic curly hair bacterium etc.
On the one hand, be under the situation of alkalescence in treatment condition, utilize not exist the atmospheric oxidation of iron-oxidizing bacterium to make the iron oxidation, generate ferrihydrite, lepidocrocite, rhombohedral iron ore, magnetite, maghemite as moisture ferriferous oxide.
Secondly, to 2) carrying method describe, amounts of insoluble iron compounds such as moisture iron sulfate mineral, ferrihydrite, kaganeite, pyrrhosiderite, amorphous hydrous ferric oxide, the acid ore deposit of iron content waste water neutralizing treatment throw out are made slurry, use water-soluble iron compounds such as ferric sulfate, ferrous sulfate, iron(ic) chloride, iron protochloride, iron nitrate and Iron nitrate as the aqueous solution.The concentration of the iron cpd in the slurry or the aqueous solution with iron be criterion calculation its be more than the 1000ppm (weight), more than the preferred 5000ppm.The usage quantity of iron cpd is its scope at 5～100 weight parts of criterion calculation with respect to material 100 weight parts that contain inorganic fibre with iron.
The containing oxygen iron compound of the saturation state that obtains as mentioned above can directly form processing material of the present invention as hydrate, perhaps also can by be dried, sintering, make processing material of the present invention.
In the latter case, the material that contains inorganic fibre of impregnation iron cpd is packed in the sintering oven, by 150～800 ℃ of temperature, preferred 250～650 ℃, for example sintering can be made processing material of the present invention about 30 minutes～2 hours.
Handle preferred 50～90 weight % of ratio of the material that contains inorganic fibre in the material, the scope of preferred 10～50 weight % of the ratio of containing oxygen iron compound.
The shape of processing material of the present invention is unqualified, and is preferably granular.The manufacture method of granular processing material can be performed as follows: use mixing machines such as ribbon blender, rotary pelleting machine in advance; making the material forming that contains inorganic fibre is that granulous material and iron content sour water reaction or contain is immersed in the containing oxygen iron compound, as required drying or sintering.When using granular aminanthine in the raw material, advantage is that omission is configured as the granulous operation.Under the situation of saccharoid, median size is about 0.5～100mm, preferred 1～50mm.
In addition, when the hydrate that does not need sintering circuit is directly made processing material of the present invention, the stratiform molding is arranged as other preferred shape.Just, preferred following material: it constitutes by make inorganic fibre form incorporate layer of fibers with the flexibility resin glue, makes it carry out wetting ability again and handles the material that obtains.The flexibility adhesive resin can use the powder that manifests thermoplastic resins such as close-burning vinyl chloride, polystyrene, polyolefin, polyester system, nylon system, acrylic acid series by heating, solution, emulsion etc. and thermal welding filamentary material.
It is integratedly made fibrolaminar method and can be: after inorganic fibre and flexibility resin glue were mixed, heating was shaped, and forms the laminar or felted of specific thicknesses.By in it is shaped or the shaping post-heating make its cohesive force that manifests resin glue, inorganic fibre is mutually combined.This fibrolaminar density is 30～300kg/m
3, preferred 60～250kg/m
3, fibrolaminar thickness is 1～30mm, preferred 2～20mm.
Processing material of the present invention is because be as carrier, so that it is a kind of voidage is very high, and the low processing material of bulk specific gravity with inorganic fibre such as aminanthine or inorganic powder body such as inorganic fibre and cement.In addition, even inorganic powder body exists, also because residual proterties such as space property as fiber, so water-permeable is very high, reactive good with objectionable impurities in the waste water, reaction back draining simultaneously is good, can carry out processed by just leaving standstill.And, show that coefficient of permeability is 1 * 10
-3More than the cm/s, preferred 1 * 10
-2The high water-permeability that cm/s is above.In addition, after using in wastewater treatment, do not carry out special dehydration operation and only it is picked up from water, just can make water ratio is below 90%, preferred below 80%.
The water that can use processing material of the present invention to handle is at least a sewage as objectionable impurities that contains in heavy metals such as arsenic, lead, cadmium, antimony, uranium and phosphorus, selenium or the fluorine.These can be used as water soluble ion or compound exists, and for example arsenic is with arsonium ion, and the form of arsenite ion, arsenic acid ion, arsenite, arsenate etc. exists.In addition, phosphorus or selenium majority exist with phosphoric acid or selenic acid.
When specifically exemplifying manageable water, except that polluted water such as ore deposit waste water, trade effluent, agricultural effluent, livestock products waste water, aquatic products processing waste water, rivers and creeks water, lakes and marhshes water, also can be used for the aftertreatment of reagent etc., and can be used to contain water pipe water, the phreatic purification of these objectionable impuritiess of trace.What be fit to use is to contain the water of arsenic as objectionable impurities, the trade effluent from the beverage water of lower concentration to high density.At this, under the situation that forms such as the arsonium ion that arsenic constitutes with tervalent arsenic, arsenite ion, arsenite exist, preferably utilize air etc. with its oxidation, become the arsenic of 5 valencys after, it is contacted with processing material of the present invention.
When using processing material processing of the present invention to contain the polluted water of objectionable impuritiess such as arsenic, effectively be provided with and be filled with the processing container of material,, make its contact to wherein flowing into polluted water.In addition, sewage also can be stored in container or the pond, is filled in the basket container handling material, puts into water and makes its contact.Reclaim used processing material, it is replaced with product innovation, in this case, it is effective putting into that container uses.And, also be favourable with a plurality of being used in combination of above-mentioned treatment process.
The temperature that contacts of handling material and sewage can be a normal temperature, the water quality that require according to the concentration of narmful substance that contains in loading level, water-flowing amount, the sewage, treating water duration of contact etc. changes, it is more than 15 minutes, and is preferred more than 1 hour, more preferably about 1～10 hour.Processing material water flowing physically exchanges at need, and perhaps the concentration of narmful substance in treating water is replaced interpolation before reaching prescribed value or predefined numerical value.
In addition, make up dexterously, can carry out a plurality of sewage disposals efficiently by manufacturing process and polluted water treatment process with processing material of the present invention.
At first, handle the Fe-laden acid wastewater with the phyllosilicate inorganic fibre, carry out the neutralization and the deferrization of waste water, make its generation load on moisture iron containing oxygen iron compound on the fibrous inorganic substance of silicic acid matter simultaneously, then, it as processing material of the present invention, is taken the wastewater treatment scene in order to remove arsenic, phosphorus etc., use there.
Aforesaid Fe-laden acid wastewater can be enumerated from the ore deposit waste water of the ferrous ion that contains iron sulphide oxidation generation of mine discharging.
Wherein, in initially treated Fe-laden acid wastewater, contain under the situation of oxygen acid of arsenic, phosphorus, selenium etc., generate and handle the containing oxygen iron compound that generates in the material, the SO that contains in the crystalline texture of for example moisture iron sulfate mineral
4Quilt is than SO
4The compound that thermodynamically stable arsenic acid, phosphoric acid, selenic acid etc. replace, in addition, the compound of the state of saturated mistakes such as the arsenic of the containing oxygen iron compound formation in the treatment agent, phosphorus, selenium, so form material, so can not use as processing material of the present invention to the adsorptive power difference of these objectionable impuritiess.Therefore, the present invention clearly is divided into the manufacturing process that handles material and uses operation.
Be used for the such Fe-laden acid wastewater of ore deposit waste water and handle resulting processing material, it is that the alkali composition that is used for the neutral fiber reduces, the material that silicic acid matter composition increases, and its be ferrous components with the containing oxygen iron compound attached to fiber surface, as treatment agent use of the present invention.
The processing material that obtains as mentioned above can carry out drying as required, carries the processing of other waste water that is used to contain hazardous substance or underground water etc.
Below, describe using the method that processing material processing of the present invention contains the acid ore deposit waste water of arsenic and iron at least.
This acidity ore deposit waste water is implemented following processing operation: dearsenification operation, 3 1) arsenic oxidation operation, 2)) iron oxidation operation, 4) deferrization operation and pH adjust operation.But, according to circumstances can carry out: i) omit the arsenic oxidation operation; Ii) part or all of arsenic oxidation operation and dearsenification operation carried out a) the arsenic oxidation dearsenification operation that dearsenification is carried out in the arsenic oxidation simultaneously; Perhaps iii) part or all of iron oxidation operation and deferrization operation carried out the b that deferrization is carried out in the iron oxidation simultaneously) iron oxidation deferrization operation.
In the arsenic oxidation operation, be that to change into arsenic acid be the such ion that contains 5 valency arsenic of title complex ion to the such ion-oxygen that contains 3 valency arsenic of ion with arsenus acid according to various reactions.
The dearsenification operation is an operation of utilizing processing material of the present invention that the ion that contains 5 valency arsenic that contains in the waste water is removed.In addition, when heavy metal classes such as lead, cadmium, antimony, uranium and phosphoric acid, selenic acid, fluorine etc. were contained in the waste water, it can be removed simultaneously with arsenic.
The iron oxidation operation is used for promoting that the divalent iron ion of the waste water after dearsenification is handled is oxidized to the iron ion of 3 valencys, promotes the deferrization in the subsequent processing.In order to promote the oxidation of the ferrous components in the water under the acidic conditions, can use molten increase and the iron-oxidizing bacterium of depositing oxygen in the waste water.
Iron-oxidizing bacterium is owing to mainly on the surface attached to the material that contains the phyllosilicate inorganic fibre that uses as the deferrization material in the deferrization operation, breed, with the iron ion oxidation in, separate out as the containing oxygen iron compound, so carry out deferrization simultaneously.In this case, iron oxidation operation and deferrization integrated process form iron oxidation deferrization operation.
The deferrization operation be will contain the phyllosilicate inorganic fibre material as the deferrization material, and use neutralizationization bacterium, the ferric ion in the iron content sour water is separated out, the formation insolubles as the containing oxygen iron compound.And containing oxygen iron compounds such as the moisture iron sulfate mineral that generate, pyrrhosiderite in a large amount of loads of the material that contains inorganic fibre that use under acidic conditions, therefore as the arsenic adsorbent material of dearsenification operation just treatment agent use.
PH from the effusive waste water of deferrization treatment process is preferably acidity because of above-mentioned reason, below the pH4.5, and preferred 3～4.4.
It is neutral operation before emitting the deferrization treating water that pH adjusts operation, and neutralization materials is used slaked lime, unslaked lime, lime carbonate, the broken thing of concrete etc.
Description of drawings
Fig. 1 is the SEM photo of the microtexture of the processing material that shows that embodiment 4 obtains, Fig. 2 is the SEM photo after the central part of Fig. 1 is amplified 100 times, and Fig. 3 shows the phosphorus concentration (UT-TP) of the lake water that embodiment 16 handled and the phosphorus concentration (T-TP) in the treating water and the relation of accumulating water-flowing amount (CTW).
Embodiment
Embodiment 1
The aminanthine (new daily use chemicals aminanthine Co., Ltd. system, S-Fiber granulated wool, median size 30mm), nickel minerals slag wool (Pacific Ocean metal Co., Ltd. system, granulated wool, median size 30mm), glass wool (no resin staple fibre), carbon fiber (pitch is staple fibre) or the silica fiber (tissue culture staple fibre) that use 75g respectively are as inorganic fibre.Use that reagent of sulfuric acid is ferrous, gypsum and sulfuric acid, it is added among the acidic solution 5L of pH2, total iron ion 340mg/l, calcium ion 250mg/l, sulfate ion 2000mg/l, make its reaction 28 days under the normal temperature.
Mensuration ferrous components this moment is to the adhesive rate of each inorganic fibre and the pH of reaction back solution.And for to observe the tack that ferrous components adheres to fiber surface, in solution, stirred 5 minutes, confirm the separate stage of fiber and resultant of reaction with range estimation.In addition, analyze with high performance type X-ray powder diffraction device attached to the ferrous components of fiber surface.
Embodiment 2
Contain the 15g biomaterial of iron-oxidizing bacterium-thiobacillus ferrooxidant except that adding again, carry out same experiment with embodiment 1.
Table 1 shows that ferrous components is to the adhesive rate of fiber and the pH of solution.In addition, RW is an aminanthine in the table 1, and NW is that nickel minerals slag wool, GW are that glass wool, CF are that carbon fiber, SF are that silica fiber, S+G are the moisture iron sulfate mineral of low-crystallinity and the mixture of pyrrhosiderite, and-expression resultant can not be measured less.
Table 1
| Embodiment 1 | Embodiment 2 | |||||||||
| Inorganic fibre | RW | NW | GW | CF | SF | RW | NW | GW | CF | SF |
| pH | 4.0 | 3.5 | 2.4 | 2.3 | 2.4 | 4.4 | 4.3 | 2.2 | 2.1 | 2.1 |
| Adhesive rate % | 57 | 82 | 33 | 5 | 9 | 87 | 100 | 40 | 29 | 30 |
| X-ray diffraction | S+G | S+G | S+G | - | - | S+G | S+G | S+G | S+G | S+G |
Embodiment 3
Use aminanthine (S-Fiber granulated wool, median size 30mm), slag cement (slag cement Co., Ltd. of Nippon Steel system, B kind slag cement), with ribbon mixer aminanthine 60 weight % and slag cement 40 weight % are mixed, obtain the particulate mixtures of median size 20mm, bulk specific gravity 0.15, voidage 94%.The chemical constitution of this particulate mixtures is SiO
2: Al 33.0%,
2O
3: 10.2%, CaO:47.8%, MgO:4.2%, Fe
2O
3: TiO 1.4%,
2: 0.5%, MnO:0.2%, SO
3: Ig.loss:1.2% 0.7%.
Use ferrous sulfate, gypsum and sulfuric acid in addition, preparation contains the acidic solution of the pH2.5 of sulfate ion 1080mg/l, total iron ion 137mg/l, calcium ion 250mg/l.
In the synthetic resins system pillar of diameter 10.4cm, fill particulate mixtures 100g and be thickness 6.8cm, bulk specific gravity 0.174, fed acidic solution 10 days with the ratio of 5L/ day.The ferrous components adhesive rate of every 1kg particulate mixtures is scaled 68.5g with metallic iron after the water flowing.In addition, the pH and the ferrous components concentration of discharging solution when assaying reaction finishes, the result is pH10.0, total iron ion 0.01mg/l.
Reacted particulate mixtures forms the processing material of load containing oxygen iron compound.This processing material is measured its water-permeable, and coefficient of permeability is 4.0 * 10 as a result
-1Cm/sec, water ratio are 76%.In addition, attached to the ferrous components on the fiber surface be the ferrihydrite of low-crystallinity.
Embodiment 4
Use Portland cement to replace slag cement, to feed the acidic solution 6 days that is added with iron-oxidizing bacterium Thiobacillus ferooxidans 5L/ day, in addition, other are identical with embodiment 3 again.The proterties of discharging solution was pH4.0, total iron ion 1.4mg/l, sulfate ion 1000mg/l, silicic acid 16mg/l, calcium ion 297mg/l when reaction finished.In addition, the ferrous components adhesion amount of every 1kg processing material is scaled 407g with metallic iron.The water-permeable coefficient of this processing material is 7.0 * 10
-2Cm/sec, water ratio are 78%.
Processing material with electron microscope observation load containing oxygen iron compound, the result is shown in Fig. 1 and 2, several microns warty resultant (schwertmannite) is connected around the aminanthine fiber, is deposited as the sheath shape, and this warty resultant is the aggregate of the acicular particles of submicron.In addition, the chemical constitution of the fiber that contains in the processing material comprises SiO
2: Al 98.3%,
2O
3: CaO:0.0% 0.8%,, aminanthine forms the porous silica fiber that keeps fiber shape.The chemical constitution of containing oxygen iron compound is Fe
2O
3: SiO 85.6%,
2: 2.8%, CaO:0.2%, SO
3: 11.0%, be the schwertmannite of low-crystallinity.
Embodiment 5～6
In the nitric acid acidic solution 1L of the pH3.6 that contains 3 valency arsonium ion 15mg/l, cadmium ion 15mg/l, lead ion 15mg/l, add the processing material 9g that obtains among the embodiment 3 or 4, reacted for 1 time at normal temperatures after, filter.Measure each ionic concn and pH in the filtered liquid.The results are shown in table 2.
Table 2
| Handle material | As | Cd | Pb | pH | |
| Embodiment 5 | Embodiment 3 | 3.7mg/l | 0.05mg/l | 0.01mg/l | 9.4 |
| Embodiment 6 | Embodiment 4 | 2.4mg/l | 0.75mg/l | 3.45mg/l | 3.0 |
Embodiment 7
The processing material that uses embodiment 4 to obtain, processing contains arsenic artificial wastewater (3 valency arsonium ion 50mg/l), and the result is under the condition of addition 5g/l, and the arsenic rate of removing is 45.2%, when handling phosphorous artificial wastewater (phosphatase 79 8mg/l), under the condition of addition 5g/l, the phosphorus rate of removing is 99.5%, when handling fluorine-containing artificial wastewater (fluorine 3.6mg/l), under the condition of addition 100g/l, the fluorine rate of removing is 40%
In addition, the processing material after the wastewater treatment is the sheath shape at the fibrous silicon-dioxide of fiber surface by moisture iron sulfate mineral and surrounds, owing to these moisture iron sulfate mineral of quilt such as arsenic are won over by any means, so stably exist.For this reason, the direct taking-up of material should be handled and aftertreatment can be carried out.
Embodiment 8
Use any 50 weight part and ACRYLIC EMULSION 2 weight parts in nickel minerals slag wool (granulated wool, median size 30mm) 50 weight parts, moisture iron sulfate mineral (S), magnetite (MG), pyrrhosiderite (G) or the ferrihydrite (FH) as moisture ferriferous oxide, mix with ribbon mixer, obtain the particulate mixtures of median size 20mm, bulk specific gravity 0.2, voidage 95%.
Here moisture iron sulfate mineral use the material of following generation: use ferrous sulfate, gypsum and sulfuric acid, in the acidic solution of the pH2.5 that contains sulfate ion 1080mg/l, total iron ion 137mg/l, calcium ion 250mg/l, add iron-oxidizing bacterium-thiobacillus ferrooxidant, the limit is blown into the air that 1L/ divides at normal temperatures, and stirred 7 days on the limit.In addition, magnetite, pyrrhosiderite, ferrihydrite use commercially available product (テ Star ゲ Application Co., Ltd. system).
Use this processing material, contain arsenic artificial wastewater (3 valency arsonium ion 50mg/l) or phosphorous artificial wastewater (phosphatase 79 8mg/l) with addition 10g/l processing, as shown in table 3, show good arsenic-removing rate, dephosphorization rate.In addition, the processing material after the wastewater treatment does not form the mud shape, directly takes out the processing material and can carry out aftertreatment.
Table 3
| S | MG | G | FH | |
| Arsenic-removing rate % | 30.8 | 29.4 | 46.8 | 23.6 |
| Dephosphorization rate % | 65.0 | 57.1 | 40.8 | 59.2 |
Embodiment 9
Use ribbon mixer that aminanthine (granulated wool, median size 30mm) 40 weight %, slag cement (B kind slag cement) 60 weight % are mixed, obtain the particulate mixtures of median size 20mm, bulk specific gravity 0.15, voidage 94%.In the synthetic resins system pillar of width 120cm, height 90cm, thickness 16cm, fill particulate mixtures 20kg and form thickness 60cm, bulk specific gravity 0.174.
Contain sulfate ion 875mg/l, total iron ion 124mg/l, calcium ion 226mg/l, feed the acid ore deposit waste water 10 days in the iron sulphide mine of the pH2.8 that iron-oxidizing bacterium-thiobacillus ferrooxidant lives with the ratio of 1L/ day.
Particulate mixtures after water flowing finishes forms the compound loaded processing material of containing oxygen iron.This ferrous components adhesion amount of this processing material per 20 is scaled about 6kg with metallic iron.In addition, the pH of discharging solution was 4.1 when reaction finished, and total iron ion is 0.09mg/l, and in addition, coefficient of permeability is 0.6 * 10
-2Cm/sec, water ratio are 78%.In addition, the bulk specific gravity of 100 ℃ of dry things is 0.18.The ferrous components that adheres to is the moisture iron sulfate mineral of low-crystallinity and the mixture of pyrrhosiderite.
Then, feed the waste water that contains arsonium ion 1.07mg/l, total iron ion 0.07mg/l, lead ion 0.003mg/l of the pH6.9 of 10L with the water-flowing amount of 0.5L/ day.Analyze treating water at this moment, pH3.9, arsonium ion 0.01mg/l, total iron ion 2.3mg/l, lead ion can't check as a result.And during water-permeable behind the assaying reaction, coefficient of permeability is 0.5 * 10
-2, the water ratio when reaction finishes is 77%.In addition, the bulk specific gravity of 100 ℃ of dry things is 0.19.
Embodiment 10
Mix aminanthine (granulated wool, median size 30mm) 60 weight parts and slag cement 40 weight parts mix with ribbon mixer, make the particulate mixtures of median size 20mm, bulk specific gravity 0.15, voidage 94%.
Then, using ferrous sulfate, ferric sulfate, iron protochloride to make ferrous components content is that 5 weight parts and particulate mixtures 5 weight parts mix, and this mixture is put into the magnetic crucible, adds the water of 5 weight parts, stirs and places 1 hour.
With its with the electric furnace of band crucible in oxidizing atmosphere 350 ℃ of following sintering of sintering temperature 1 hour, content is taken out in the cooling back, carries out coarse reduction with agate mortar, obtains handling materials A～C.
In the phosphoric acid solution (the about 100mg/l of concentration) of 1000ml, add each 1.25g with handling materials A～C, measure 30 fens dephosphorization rates after the stirring respectively, calculate the dephosphorizing capacity (PO that every 1g handles material
4-mg/g).In addition, in the liquor sodii arsenatis (concentration 15mg/l) of 1000ml, add and handle each 125g of materials A～C, stir and measure arsenic-removing rate respectively after 30 minutes, calculate the dearsenification ability (As-mg/g) that every 1g handles material.And, during with the painted investigation dephosphorization of the solution after filtering and the ferrous components during dearsenification have or not outflow (red water generates).The results are shown in table 4.
Table 4
| Handle material | A | B | C |
| Iron cpd | Ferrous sulfate | Ferric sulfate | Iron protochloride |
| Dearsenification ability mg/g | 30.1 | 40.2 | 37.9 |
| Dephosphorizing capacity mg/g | 38.2 | 51.0 | 48.0 |
| Ferrous components flows out | Do not have | Do not have | Do not have |
Embodiment 11
The aminanthine (RW) and the slag cement (BC) that use embodiment 10 to use are formed according to the cooperation of table 5 it are mixed with ferrous sulfate or ferric sulfate and water, stir in the magnetic crucible, place 1 hour.Then, with its with the electric furnace of band crucible in oxidizing atmosphere under 350 ℃ of sintering temperatures with its sintering 14, the time, content is taken out in the cooling back, carries out coarse reduction with agate mortar, obtains handling material D, E.The numeral weight part of table 5.
Table 5
| Handle material | D | E |
| Iron cpd | Ferrous sulfate 9.0 | Ferric sulfate 9.0 |
| RW | 5 | 0 |
| | 0 | 5 |
| Water | 5 | 5 |
In the phosphoric acid solution (the about 100mg/l of concentration) of 1000ml, add and handle material D1.25g, measure the dephosphorization rate that stirs after 30 minutes, calculate the dephosphorizing capacity (PO that every 1g handles material
4-mg/g).In addition, in the liquor sodii arsenatis (concentration 15mg/l) of 1000ml, add and handle material D1.25g, measure the arsenic-removing rate that stirs after 30 minutes, calculate the dearsenification ability (As-mg/g) that every 1g handles material.When reinvestigating dephosphorization and the ferrous components during dearsenification have or not outflow.Processing material F, G that a sintering processes material E and iron cpd (ferrous sulfate or ferric sulfate) are obtained also carry out same test.The results are shown in table 6.
Table 6
| Handle material | D | E | F | G |
| Dearsenification ability mg/g | 58.7 | 27.3 | 47.2 | 56.1 |
| Dephosphorizing capacity mg/g | 74.4 | 34.6 | 59.8 | 71.1 |
| Ferrous components flows out | Do not have | Do not have | Have | Have |
Embodiment 12
The aminanthine that uses embodiment 10 to use, use throw out (the acid ore deposit of iron content waste water neutralizing treatment throw out) 15 weight parts (metallic iron is 5 weight parts) and water in the acid ore deposit of the iron content waste water that the mixture of moisture iron sulfate mineral and pyrrhosiderite constitutes, forming mixing by the cooperation of table 7 makes the weight of each ferrous components content and aminanthine roughly the same, mixture is put into the magnetic crucible, stir and placed 1 hour.With this mixture with the electric furnace of band crucible in oxidizing atmosphere under the sintering temperature shown in the table 7 sintering 14, the time, content is taken out in the cooling back, uses the agate mortar coarse reduction, obtains handling material H～K.
Table 7
| Handle material | H | I | J | K |
| Throw out | 5 | 15 | 15 | 15 |
| RW | 5 | 5 | 5 | 0 |
| Water | 5 | 5 | 5 | 5 |
| | 100℃ | 150 | 700℃ | 350℃ |
In the phosphoric acid solution (the about 100mg/l of concentration) of 1000ml, add each 1.25g of treatment agent H～K, measure the dephosphorization rate separately that stirs after 30 minutes, calculate the dephosphorizing capacity (PO that every 1g handles material
4-mg/g).In addition, material 1.25g is respectively handled in interpolation in the liquor sodii arsenatis (concentration 15mg/l) of 1000ml, measures the arsenic-removing rate that stirs after 30 minutes, calculates the dearsenification ability (As-mg/g) that every 1g handles material.During again with the painted investigation dephosphorization of the solution after filtering and the ferrous components during dearsenification have or not outflow.The results are shown in table 8.
Table 8
| Handle material | H | I | J | K |
| Dearsenification ability mg/g | 39.1 | 34.9 | 10.3 | 28.2 |
| Dephosphorizing capacity mg/g | 49.6 | 44.3 | 13.0 | 35.7 |
| Ferrous components flows out | Do not have | Have | Do not have | Do not have |
In addition, embodiment 10～12 shows the example of removing arsenic, phosphorus, confirms can remove equally lead, cadmium, antimony, uranium, selenium, the fluorine of other objectionable impurities.
Embodiment 13
Former water uses and contains sulfate ion concentration 956mg/l, total iron concentration 116.4mg/l, total arsonium ion concentration 0.68mg/l, and 4.8 acidity are 768mgCaCO
3/ l, 8.3 acidity are 830mgCaCO
3/ l, acid ore deposit waste water 1t/ day of the iron content of the pH2.7 that iron-oxidizing bacterium-thiobacillus ferrooxidant is lived, use the equipment that comprises arsenic oxidation operation, dearsenification operation, iron oxidation operation and deferrization operation, contain the ore deposit wastewater treatment of arsenic and iron.The particulate mixtures that uses embodiment 3 to obtain in the deferrization operation carries out the part neutralization when the containing oxygen iron compound is separated out.Iron cpd is separated out, and the material that the alkali composition reduces in the aminanthine uses in the dearsenification operation as treatment agent, and arsenic is removed in absorption.
The water quality of dearsenification treating water is pH2.8, sulfate ion concentration 956mg/l, total iron concentration 117.0mg/l, total arsonium ion concentration 0.014mg/l.The water quality of the dearsenification treating water having been carried out the deferrization treating water of deferrization processing is pH4.1, sulfate ion concentration 938mg/l, total iron concentration 0.09mg/l, total arsonium ion concentration 0.007mg/l, 4.8 acidity 2mgCaCO
3/ l, 8.3 acidity 117mgCaCO
3/ l.
In addition, in the artificial waste liquid shown in 8 (containing the solution of each metal), add the particulate mixtures that uses in the processing material that uses in the 9g/l dearsenification operation, the deferrization operation, the measurement result of each metal concentration after 1 hour is shown in table 9 as nitrate.The numeric representation metal concentration (mg/l) of table 9.
Table 9
| Fe | Mn | Cu | Zn | Pb | Cd | As(III) | As(V) | |
| Artificial waste liquid | 90.4 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Handle material | 92.59 | 15.44 | 15.90 | 15.11 | 3.45 | 0.75 | 2.42 | 0.01 |
| Particulate mixtures | 0.01 | 0.09 | 0.16 | 0.01 | ND. | 0.05 | 13.66 | 3.68 |
Embodiment 14
Fill the processing material 50g that embodiment 9 makes in the pillar of 75mm diameter, making its filling thickness is 50mm, with the logical diluted liquid fertilizer (Da mound chemistry of the 15ml/min system OkF2 of society) phosphoric acid concentration made is the former water 30 days of 0.1mg/l.
The beginning water flowing is measured the phosphoric acid concentration in the treating water after 1 day, after 15 days and after 30 days, and the result is below the 0.005mg/l.The volume of processing material at this moment is 220.8cm
3, the residence time is about 15 minutes.
Embodiment 15
The chemical constitution (weight %) of the processing material B that table 10 expression embodiment 10 makes.This processing material shows that it is that voidage is about 75% pumice shape, and coefficient of permeability is 1.4 * 10 ° of cm/sec.
Table 10
| CaO | MgO | SiO 2 | Al 2O 3 | Fe 2O 3 | TiO 2 | Na 2O | K 2O | MnO | SO 3 | Add up to |
| 13.2 | 1.8 | 14.7 | 4.3 | 25.9 | 0.2 | 0.1 | 0.1 | 0.1 | 39.5 | 99.9 |
In order to control the dephosphorization performance of this processing material with respect to the low phosphorus acid solution, dilution OKF2 makes phosphoric acid concentration and is 0.1 and the former water of 1.0mg/l.Add in this former water 200ml and handle material 0.2g, normal temperature stirs after 15 minutes down, filters, and measures the phosphoric acid concentration in the filtrate.When former water 0.1mg/l, the phosphoric acid concentration of filtrate is below the 0.005mg/l, and when former water 1mg/l, the phosphoric acid concentration of filtrate is 0.01mg/l.
Embodiment 16
In the pillar of 150mm diameter, fill the processing material 100g that embodiment 9 makes, making its filling thickness is 50mm, with the logical continuously dustiness of the speed of 60ml/min is moderate lake water, measure the phosphorus concentration (UT-TP) of former water this moment and the phosphorus concentration (T-TP) in the treating water, the results are shown in Fig. 3. transverse axis represents to accumulate water-flowing amount (CTW) among Fig. 3, and the longitudinal axis represents to add up to phosphorus concentration (TP).The volume of processing material at this moment is 883.1cm
3, superficial velocity is the 0.34cm/ branch, the residence time is about 15 minutes.
Among the embodiment 14～16, the phosphorus of the lower concentration that processing material of the present invention contains with respect to lakes and marhshes water etc. also has steady and continuous ground dephosphorization function.
Processing material of the present invention can utilize efficient and easy various polluted water and the pipeline removed of easy treatment process with the objectionable impurities that contains in the former water with safeguarding, also keeps water permeability after the use, can use for a long time.Handle having good stability of resultant, objectionable impurities changes in time or acidification is dissolved and separated out fewly, and aftertreatment is easy.
Claims (15)
1, a kind of sewage treating material, it is used for handling the sewage that contains at least a objectionable impurities that is selected from arsenic, lead, cadmium, antimony, uranium, phosphorus, selenium and fluorine, it is characterized in that it is made of the containing oxygen iron compound that loads on the material that contains the inorganic fibre that is selected from silicic acid matter fiber or phyllosilicate fiber.
2, processing material as claimed in claim 1, wherein inorganic fibre is the phyllosilicate fiber with acid-respons, a part at least wherein and acid-respons, silicic acid component increases.
3, processing material as claimed in claim 2, the phyllosilicate fiber that wherein has acid-respons are to be selected from least a in aminanthine, nickel minerals slag wool and the glass wool.
4, processing material as claimed in claim 1, the material that wherein contains inorganic fibre are that inorganic fibre and inorganic powder material, inorganic or organic binder bond mix or incorporate material.
5, processing material as claimed in claim 1 or 2, wherein load forms the containing oxygen iron compound by inorganic fibre being surrounded as the sheath shape.
6, processing material as claimed in claim 1, wherein the containing oxygen iron compound is to be selected from least a in moisture iron sulfate mineral or its sinter, ferrihydrite or its sinter, kaganeite or its sinter, pyrrhosiderite or its sinter, lepidocrocite, rhombohedral iron ore, magnetite, maghemite, jarosite, amorphous hydrous ferric oxide sinter, ferric sulfate sinter, ferrous sulfate sinter, iron(ic) chloride sinter, iron protochloride sinter, iron nitrate sinter and the Iron nitrate sinter.
7, processing material as claimed in claim 1, wherein voidage is more than 50%, bulk specific gravity is 0.1～1.5.
8, processing material as claimed in claim 1, wherein objectionable impurities is an arsenic, arsenic exists as water miscible arsenic compound or by the ionic form of its generation.
9, a kind of manufacture method of handling material, it is a method of making processing material as claimed in claim 1, it is characterized in that, contains the material of inorganic fibre with the water treatment of iron content acidity, obtains loading on the containing oxygen iron compound on the inorganic fibre.
10, the manufacture method of processing material as claimed in claim 9, wherein iron content sour water is iron content sulfuric acid water or Fe-laden acid wastewater, with the material processing iron content sour water that contains inorganic fibre, make its neutralization and generate the containing oxygen iron compound, obtain being carried on the containing oxygen iron compound of inorganic fibre.
11, when wherein using the water treatment of iron content acidity, also there is iron-oxidizing bacterium in the manufacture method of processing material as claimed in claim 9.
12, a kind of manufacture method of handling material, it is a method of making processing material as claimed in claim 1, its material soaking that will contain inorganic fibre is in containing the aqueous solution or slurries that is selected from iron cpd at least a in moisture iron sulfate mineral, ferrihydrite, kaganeite, pyrrhosiderite, amorphous hydrous ferric oxide, ferric sulfate, ferrous sulfate, iron protochloride, iron(ic) chloride, iron nitrate and the Iron nitrate, sintering does being shaped as fibrous containing oxygen iron compound afterwards.
13, a kind of treatment process of sewage is characterized in that, at least a sewage as objectionable impurities contacts in making the described processing material of claim 1 and containing arsenic, lead, cadmium, antimony, uranium, phosphorus, selenium and fluorine.
14, the treatment process of sewage as claimed in claim 13, it carries out oxide treatment to containing 3 valency arsenic as the sewage of objectionable impurities, and 3 valency arsenic are become after the 5 valency arsenic, makes it and handles material and contact.
15, a kind of treatment process of sewage, it is characterized in that, it has the material that contains silicate matter fiber of acid-respons with the acid water treatment of iron content, make its at least a portion and acid-respons, thereby make the processing material that is carried on the containing oxygen iron compound formation on silicic acid matter fiber or the phyllosilicate fiber that silicic acid component increases, the processing material delivery that will obtain afterwards is to the sewage-farm, at this above-mentioned processing material is contacted with above-mentioned sewage, wherein above-mentioned sewage contains and is selected from objectionable impurities at least a in arsenic, lead, cadmium, antimony, uranium, phosphorus, selenium and the fluorine.
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| JP2003161028A JP4355522B2 (en) | 2003-06-05 | 2003-06-05 | Material for treating hazardous substances in wastewater and method for producing the same |
| JP161028/2003 | 2003-06-05 | ||
| JP294929/2003 | 2003-08-19 | ||
| JP305122/2003 | 2003-08-28 |
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| CN104525144A (en) * | 2014-12-30 | 2015-04-22 | 中南大学 | Aluminum sulfate modified iron-based biological material for heavy metal adsorption and preparing and application method thereof |
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| CN117438124A (en) * | 2023-12-22 | 2024-01-23 | 中核第四研究设计工程有限公司 | Method for long-term stable treatment of uranium-containing waste residues |
| CN117438124B (en) * | 2023-12-22 | 2024-04-09 | 中核第四研究设计工程有限公司 | Method for long-term stable treatment of uranium-containing waste residues |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004358396A (en) | 2004-12-24 |
| JP4355522B2 (en) | 2009-11-04 |
| CN100355668C (en) | 2007-12-19 |
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