WO2010131686A1 - スコロダイト型鉄砒素化合物粒子および製造方法並びに砒素含有固形物 - Google Patents
スコロダイト型鉄砒素化合物粒子および製造方法並びに砒素含有固形物 Download PDFInfo
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- WO2010131686A1 WO2010131686A1 PCT/JP2010/058064 JP2010058064W WO2010131686A1 WO 2010131686 A1 WO2010131686 A1 WO 2010131686A1 JP 2010058064 W JP2010058064 W JP 2010058064W WO 2010131686 A1 WO2010131686 A1 WO 2010131686A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to scorodite-type iron arsenic compound particles treated so that arsenic is hardly eluted, a method for producing the same, and an arsenic-containing solid material containing the scorodite-type iron arsenic compound particles.
- the arsenic compound recovered as a precipitate is stored or discarded, but it is important that the compound has little arsenic elution.
- Scorodite FeAsO 4 .2H 2 O
- Patent Document 2 The present applicant has succeeded in developing a wet process for synthesizing a scorodite-type iron arsenic compound having good crystallinity with good filterability.
- This iron arsenic compound contains arsenic at a very high quality of about 30% by mass, and the arsenic is immobilized in the compound and is not easily eluted.
- JP 54-106590 A Japanese Patent No. 4185541 JP 2008-222525 A JP 2008-150658 A JP 2008-150659 A
- an aggregate (powder) of scorodite crystal particles having an average particle diameter of about 1 to 50 ⁇ m can be obtained. These particles have good crystallinity, and when the aggregate of the obtained scorodite-type iron arsenic compound particles is thoroughly washed, the elution amount of arsenic in the elution test according to Ministry of the Environment Notification No. 13 is the standard (elution concentration 0) .3 mg / L or less).
- the scorodite-type iron arsenic compound is stable in an environment where the pH is about 4 to 6, but the stability is impaired in the pH range outside the range, and the elution amount of arsenic increases.
- Patent Document 3 discloses a technique for obtaining an arsenic-containing solid material in which a scorodite-type iron arsenic compound and an iron oxide compound are physically mixed.
- This method has an advantage that the amount of arsenic elution can be easily reduced by mixing the scorodite type iron arsenic compound with the iron oxide compound.
- the method is simple because of physical mixing, but the scorodite-type iron arsenic compound and the iron oxide compound may be non-uniformly mixed. Depending on the external environment, there is a risk of non-uniformity during storage, in which case the arsenic elution amount reduction effect tends to be insufficient.
- the present invention uses scorodite-type iron arsenic compound particles with good filterability as a standard in the dissolution test (initial pH 5.8 to 6.3) in accordance with the laws of Japan (Japan) (Ministry of the Environment Notification No. 13).
- An object of the present invention is to provide a clear and excellent arsenic elution preventing effect even in an environment around pH 3 and pH 7.
- scorodite-type iron arsenic compound particles having an iron-rich layer with a Fe / As molar ratio of 1.24 or more in the particle surface layer portion.
- An arsenic-containing solid material comprising an aggregate of the surface-treated scorodite-type iron arsenic compound particles, or an arsenic-containing solid material comprising a mixture of the surface-treated scorodite-type iron arsenic compound particles and the solid material not containing arsenic is arsenic. Excellent anti-elution effect, suitable for disposal, deposition or storage.
- the “scorodite type iron arsenic compound” is a compound in which an X-ray diffraction pattern corresponding to a crystal of scorodite (FeAsO 4 .2H 2 O) is observed.
- the arsenic elution amount in the elution test according to Ministry of the Environment Notification No. 13 is suppressed to 0.3 mg / L or less at least in a washed state. It has the immobilization ability.
- the particles of the scorodite-type iron arsenic compound with good crystallinity have a polyhedral form having a ridge.
- the average particle size of the powder composed of the particles is, for example, 10 to 50 ⁇ m. The average particle diameter can be determined by a laser diffraction particle size distribution measuring device.
- the scorodite-type iron arsenide compound particles of the present invention have an iron-rich layer on the surface of the scorodite-type iron arsenide compound particles having such good crystallinity, and thereby, excellent arsenic elution in a wider pH range. Demonstrate resistance (arsenic resistance).
- a treatment and B treatment are disclosed in the present invention.
- [B treatment] A method of forming an iron-rich layer on the surface of the scorodite-type iron arsenic compound particles by bringing the surface of the particles into contact with an aqueous solution containing iron ions.
- the iron-rich layer is preferably formed in an iron ion-containing aqueous solution in a state where the liquid has an interface with the oxygen-containing gas.
- an iron (III) sulfate aqueous solution or an iron (II) sulfate aqueous solution can be suitably employed.
- the B treatment is a step of subjecting the particles of “scorodite type iron arsenic compound having good crystallinity” to a surface treatment.
- the present invention it is possible to obtain scorodite-type iron arsenic compound particles that have a higher arsenic elution prevention effect than before.
- the slurry containing the iron arsenic compound particles has good filterability and is suitable for industrial production.
- the arsenic-containing solid material comprising an aggregate of the iron arsenic compound particles of the present invention, or the arsenic-containing solid material obtained by mixing the iron arsenic compound particles and a substance not containing arsenic is considered to have a pH fluctuation range considered in an actual deposition environment. In this case, the effect of preventing arsenic elution is maintained well, and it is extremely effective for the construction of an arsenic treatment process.
- Process drawing which showed an example of the arsenic processing process which manufactures the scorodite type iron arsenic compound particle
- Process drawing which showed an example of the arsenic processing process which manufactures the scorodite type iron arsenic compound particle
- 4 is an SEM photograph of scorodite-type iron arsenic compound particles obtained in Example 11.
- FIG. 3 is an SEM photograph of scorodite-type iron arsenic compound particles obtained in Comparative Example 1.
- FIG. 3 is an SEM photograph of scorodite-type iron arsenic compound crystal particles (particles serving as a base before forming an iron-rich layer on a surface layer portion) obtained in Comparative Example 2.
- FIG. 2 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 1.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 2.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 3.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 4.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 4.
- FIG. 6 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 5.
- FIG. 6 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 6.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 7.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 8.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 9.
- FIG. 9 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 9.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 10.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 11.
- FIG. 4 is an SEM photograph of scorodite-type iron arsenic compound crystal particles having an iron-rich layer on the surface obtained in Example 11.
- the inventors have found that when the Fe / As molar ratio of the surface layer portion of the scorodite-type iron arsenic compound particles having good crystallinity is 1.24 or more, the aggregate (powder) of the particles is And exhibiting a high arsenic elution preventing effect stably to such an extent that almost no arsenic elution is observed in the elution test according to Ministry of the Environment Notification No. 13, and a pH fluctuation range (pH 3) assumed in an actual deposition environment In 7), it was found that elution of arsenic can be suppressed.
- Scorodite (FeAsO 4 .2H 2 O) has a stoichiometric Fe / As molar ratio of 1, but according to the analysis of the actually synthesized scorodite crystal, the Fe / As molar ratio of the crystal is 1. It fluctuates somewhat around 0, and the Fe / As molar ratio may be about 1.2. However, the average composition of such particles as a whole does not necessarily match the Fe / As molar ratio of the particle surface layer. According to the investigation by the inventors, even in an example in which the Fe / As molar ratio in the average composition of the whole particle fluctuated as high as 1.20, for example, the Fe / As molar ratio of the particle surface layer portion was below 1.24.
- Such particles of the scorodite-type iron arsenic compound having an iron-rich layer on the surface can be obtained, for example, through a process A or B process described later.
- the Fe / As molar ratio of the surface layer portion can be determined by ESCA (X-ray photoelectron spectroscopy).
- the scorodite-type iron arsenic compound particles of the present invention which have improved arsenic-resistant elution performance by having an iron-rich layer on the surface, are physically or chemically iron oxide compounds (iron oxide or iron oxyhydroxide) on the surface. It is thought that it is adsorbed. Iron oxide (Fe 2 O 3 ) was detected on the surface of the surface-treated scorodite-type iron arsenic compound particles obtained in Examples described later. According to the study by the inventors, when an iron-rich layer is formed on the particle surface so that the Fe / As molar ratio obtained by ESCA (X-ray photoelectron spectroscopy) is 1.24 or more, excellent arsenic Elution suppression effect is obtained.
- ESCA X-ray photoelectron spectroscopy
- the average Fe / As molar ratio in the surface layer part at least up to 5 nm in depth from the outermost surface of the particles is 1.24 or more.
- the critical value of Fe / As molar ratio of 1.24 is significant. The reason why the scorodite-type iron arsenic compound particles having such an iron-rich layer on the surface are excellent in arsenic elution suppression performance has not been sufficiently elucidated at present.
- the arsenic-resistant elution performance tends to be stabilized at a better level.
- the Fe / As molar ratio of the iron-rich layer is 10.0 or more, it has been confirmed that the arsenic elution resistance is extremely excellent in the entire pH range of 3 to 7 (see Examples 1 and 7 described later). That is, the lower the As concentration of the particle surface layer portion is, the more advantageous it is in obtaining stable arsenic-resistant elution performance.
- Fe / As molar ratio is 1.24 or more
- Fe / As molar ratio is 1.24 or more
- FIG. 1 and FIG. 2 show an example of an arsenic treatment process in which the scorodite-type iron arsenic compound of the present invention is produced using A treatment and B treatment, respectively, and is used for disposal, deposition or storage.
- the scorodite-type iron arsenic compound can be obtained by using the technique disclosed in Patent Document 2 or the like, but any means capable of synthesizing scorodite-type iron arsenic compound particles having good crystallinity and good filterability. Various methods can be employed.
- the A treatment further synthesizes scorodite-type iron arsenic compound particles having an iron-rich layer on the surface thereof at a stage before the end of the reaction in the synthesis process (FIG. 1).
- the surface is subjected to “surface treatment” by bringing the particles into contact with an aqueous solution containing iron ions, and a scorodite type iron arsenic compound having an iron-rich layer on the surface.
- Particles are obtained (FIG. 2).
- the aggregate (powder) of particles obtained by these methods has high arsenic quality and remarkably suppressed arsenic elution, and is suitable for disposal, deposition, and storage. Below, each process is demonstrated.
- the steps of “preparation of arsenic-containing solution” and “synthesis of scorodite iron arsenic compound” are examples, and the step of preparing a scorodite-type iron arsenic compound having good crystallinity and good filterability. If there are, various processes can be adopted.
- An arsenic-containing solution (a solution in which arsenic is dissolved) is prepared as a raw material solution for synthesizing a scorodite-type iron arsenic compound.
- the arsenic-containing solution can be prepared using a technique for leaching arsenic from an arsenic-containing substance generated in a smelting process or the like.
- the method for example, the method disclosed by the present applicant in Patent Documents 4 and 5 can be suitably employed.
- oxygen gas is added to a slurry in which the sulfide is suspended in water and stirring is performed. Then, the arsenic leaching reaction is allowed to proceed, and after the reaction, the slurry is solid-liquid separated and the subsequent solution is recovered to obtain an arsenic-containing solution.
- the oxygen partial pressure in the gas phase portion in contact with the slurry liquid surface is set to 0.6 MPa or less. It can also be implemented in open systems that are open to the atmosphere.
- an arsenic-containing sulfide may be mixed with water whose alkali hydroxide concentration is limited to 0 to 1 mol / L to form a slurry.
- the arsenic leaching reaction is desirably performed at 60 ° C. or higher, and can be performed in an open tank system as long as it is 100 ° C. or lower. It is desirable that the oxidation-reduction potential (ORP, Ag / AgCl electrode) of the slurry after the reaction is 200 mV or more.
- an oxidizing agent such as oxygen gas is added to the slurry in which the copper arsenic compound-containing substance is suspended in water and stirred, and in the presence of simple sulfur or
- An arsenic-containing solution is obtained by allowing the arsenic leaching reaction to proceed in the presence of S 2 ⁇ ions, and after the reaction, the slurry is subjected to solid-liquid separation and the subsequent liquid is recovered.
- Elemental sulfur referred to as elemental sulfur
- zinc sulfide (ZnS) can be used as the S 2 -ion supply material.
- Such an arsenic leaching reaction is accompanied by copper sulfide.
- the supply amount of sulfur is desirably 1 equivalent or more with respect to the amount of copper in the copper arsenic compound-containing material.
- the arsenic-containing solution thus obtained is usually mainly composed of trivalent arsenic.
- a technique of adding an oxidizing agent such as MnO 2 or PbO 2 together with a mineral acid (for example, sulfuric acid) can be suitably employed.
- a pentavalent arsenic-containing solution can also be obtained by a process of oxidizing and leaching arsenic from an arsenic-containing substance using a strong alkaline solution, replacing with calcium, washing, and redissolving with sulfuric acid.
- the process of leaching arsenic into water as described above is more suitable when processing a large amount industrially.
- the reaction temperature is desirably 60 to 100 ° C, more preferably 80 to 100 ° C.
- the reaction can proceed under atmospheric pressure.
- the slurry containing the iron arsenic compound crystals synthesized in this manner is called “iron arsenic reaction slurry”. This iron arsenic reaction slurry contains scorodite type iron arsenic compound particles having good crystallinity as a solid component, and has good filterability.
- a processing a method of promoting oxidation at the stage before the completion of the reaction and synthesizing scorodite-type iron arsenic compound particles having an iron-rich layer on the surface directly in the reaction vessel is called “A treatment”.
- a treatment a method of promoting oxidation at the stage before the completion of the reaction and synthesizing scorodite-type iron arsenic compound particles having an iron-rich layer on the surface directly in the reaction vessel.
- the following synthesis methods can be employed. First, as described above, the precipitation reaction of the scorodite-type iron arsenic compound crystal proceeds at a pH of 2 or lower while supplying an oxygen-containing gas to an aqueous solution containing pentavalent arsenic ions and divalent iron ions.
- a oxidizing agent for treatment A an oxidizing agent (referred to as “A oxidizing agent for treatment A”) is further added to the liquid, and its high oxidizing power. The reaction is terminated in a state where is maintained.
- the oxidizing agent for treatment A include hydrogen peroxide water, ozone, manganese dioxide, and potassium permanganate. Further, an oxygen-containing gas may be added in an amount that can form an iron-rich layer. These may be used in combination.
- the timing for adding the oxidizing agent for treatment A is after the crystals of the scorodite-type iron arsenic compound are sufficiently formed. If the oxidizing agent for treatment A is added from the beginning, the oxidizing power is too strong and it becomes difficult to produce a scorodite type iron arsenic compound with good crystallinity.
- the iron arsenic reaction slurry thus subjected to the A treatment contains a scorodite-type iron arsenic compound having an iron-rich layer having a Fe / As molar ratio of 1.24 or more (eg, 1.24 to 1.50) on the surface. Crystal particles are present.
- the average particle size of the solid content (powder composed of scorodite-type iron arsenic compound particles having an Fe-rich layer) recovered by washing and solid-liquid separation of this slurry is, for example, 10 to 50 ⁇ m.
- the average particle diameter can be determined by a laser diffraction particle size distribution measuring device. Such particles are suitable for disposal, deposition or storage. Thorough cleaning is desirable before disposal, deposition or storage.
- the washed scorodite-type iron arsenic compound particles of the present invention obtained through the treatment A have an iron-rich layer having an Fe / As molar ratio of 1.24 or more (eg, 1.24 to 1.50) on the surface layer portion. Have.
- the solid content (powder) recovered by washing and solid-liquid separation of the iron arsenic reaction slurry obtained by the synthesis method described above is composed of particles of a scorodite-type iron arsenic compound with good crystallinity.
- the average particle diameter is, for example, 10 to 50 ⁇ m. Even if it has not undergone the treatment A, in many cases, these particles pass the standard in the dissolution test based on Ministry of the Environment Notification No.13. However, the arsenic-resistant elution performance at pH 3 or around pH 7 is not sufficient. Therefore, it is subjected to B treatment (surface treatment) as follows to form an iron-rich layer on the particle surface.
- the surface treatment is performed by bringing the scorodite-type iron arsenic compound particles having good crystallinity into contact with iron ions in an aqueous solution.
- this reaction is sometimes referred to as “contact reaction”.
- the iron ion may be trivalent or divalent.
- the iron ion source for example, iron (III) sulfate or iron (II) sulfate is suitable.
- the contact reaction can proceed by mixing an aggregate of scorodite-type iron arsenic compound particles (solid content after washing) with an iron ion-containing aqueous solution and stirring the solution. For example, the following conditions may be maintained during the contact.
- the pH is 2-9, preferably 2.5-8.
- the temperature is 0 to 95 ° C., preferably 15 to 85 ° C., more preferably 30 to 60 ° C.
- the iron ion concentration is set to 0.01 to 30% by mass.
- the optimum time can be found when the contact time (the time of stirring under the above conditions (1) to (3)) is in the range of 1 to 300 minutes.
- the scorodite-type iron arsenic compound particles of the present invention obtained by the B treatment have an iron-rich layer having a Fe / As molar ratio of 1.24 or more (for example, 1.24 to 15.00) on the surface layer portion thereof. .
- the scorodite-type iron arsenic compound particles and the aqueous solution may be brought into contact in an iron ion-containing aqueous solution in which the liquid has an interface with the oxygen-containing gas.
- the oxygen-containing gas air or oxygen gas can be used.
- an iron-rich layer can be formed by stirring the liquid under the atmosphere.
- the pH adjuster it is preferable to use a weak alkaline substance such as sodium hydrogen carbonate or a strong alkali such as caustic soda.
- the liquid after the contact reaction is separated into solid and liquid to recover the solid content. Further washing can be performed as necessary.
- the average particle diameter of the aggregate of the scorodite-type iron arsenic compound particles of the present invention is for example, it is 10 to 50 ⁇ m.
- the average particle diameter can be determined by a laser diffraction particle size distribution measuring device. Such particles can be directly discarded, deposited or stored. Moreover, you may discard as a mixture with the other solid substance which does not contain arsenic. In the case of obtaining a dried product, for example, it may be dried in the atmosphere of about 40 to 105 ° C. and then crushed as necessary.
- the X-ray diffraction pattern of the obtained dry solid was measured.
- this dry solid was a scorodite-type iron arsenic compound (the same applies in the following examples).
- the surface of the above dry solid (scorodite type iron arsenic compound powder) was analyzed by ESCA (X-ray photoelectron spectroscopic analysis; manufactured by ULVAC-PHI Co., Ltd., PHI 5800 ESCA System), and the Fe / As molar ratio of the surface layer portion. Asked.
- the measurement conditions were a monochrome Al anode source as an X-ray source, 150 W, an analysis area of 800 ⁇ m ⁇ , and a take-off angle of 45 °.
- the quantitative value of this measurement is calculated from the abundance ratio of Fe atoms and As atoms from the spectrum peak, and the detection lower limit is 0.1 at.%. Under this condition, information from the particle surface of the sample powder to a depth of several nm can be obtained.
- the particle size distribution of the above scorodite type iron arsenic compound powder was measured by a laser diffraction type particle size distribution measuring device (HORIBA, LA-300), and the average particle size was obtained by arithmetic mean.
- the particles constituting the powder were observed by SEM, and the particles exhibiting a polyhedral shape having ridges were evaluated as ⁇ (crystallinity: good), and the others were evaluated as x (crystallinity: poor).
- An SEM photograph of the powder particles obtained in this example is illustrated in FIG.
- the dried solid was subjected to a dissolution test.
- the test method was a method based on Ministry of the Environment Notification No. 13 and a method using a solution of each pH.
- a method in which the filtrate is analyzed after solid-liquid separation after shaking for a period of time.
- the arsenic elution amount by this test is required to be 0.3 mg / L or less.
- Table 1 the composition (mass analysis result) of the entire scorodite-type iron arsenic compound powder is also shown for reference (the same applies to the following examples).
- the scorodite-type iron arsenic compound powder obtained in this example did not have good crystallinity (see FIG. 4), and the Fe / As molar ratio of the particle surface layer portion was as low as 1.18.
- the arsenic-resistant elution performance of this powder was remarkably inferior to those of the examples described later.
- the concentration of arsenic (pentavalent) in the reaction vessel was 50.0 g / L
- the concentration of iron (divalent) was 55.9 g / L
- the Fe / As molar ratio in the liquid was about 1.5. It is.
- a two-stage disk turbine and four baffle plates were set and stirred. During this stirring, oxygen gas having a purity of 99% was blown into the liquid at a rate of 3.0 L / min. While continuing the stirring, the liquid temperature was maintained at 95 ° C., and oxygen blowing was continued for 7 hours to advance the precipitation reaction (iron arsenic reaction).
- FIG. 5 illustrates an SEM photograph of the powder particles obtained in this example. It can be seen that the scorodite-type iron arsenic compound particles obtained in this example exhibit a polyhedral form having ridges, and are particles having good crystallinity. In the dissolution test compliant with Ministry of the Environment Notification No. 13, good results were obtained, and the arsenic resistance performance was significantly improved compared to that of Comparative Example 1 (comprising particles having poor crystallinity) (Table 1). . However, the Fe / As molar ratio of the surface layer portion was as low as 1.20, and the arsenic-resistant elution performance at pH 3 and pH 7 was insufficient.
- Example 1 Using the dry solid (powder) of the scorodite-type iron arsenic compound obtained by the same method as in Comparative Example 2, the scorodite-type iron arsenic compound particles were subjected to B treatment (surface treatment) by the following procedure. After putting 3 L (liter) of water into the reaction vessel, the temperature of the water was raised to 40 ° C. while stirring, and 38.9 g of iron (III) sulfate n hydrate (Fe content 70%) was dissolved in water. Further, a few drops of dilute sulfuric acid was added to adjust the pH to 2.0. The iron ion concentration of this solution is 2.5 g / L.
- the slurry after the contact reaction was subjected to solid-liquid separation with a suction filter, and the solid content was recovered.
- This solid content (wet cake) was repulped with pure water and washed to separate the solid and liquid three times, and the solid content after washing was collected to obtain an aggregate of surface-treated scorodite-type iron arsenic compound particles. This was dried at 60 ° C. for 180 minutes to obtain a dry solid.
- the slurry after the contact reaction was subjected to solid-liquid separation with a suction filter, and the solid content was recovered.
- This solid content (wet cake) was repulped with pure water and subjected to solid-liquid separation three times, and the solid content after washing was recovered. This was dried at 60 ° C. for 180 minutes to obtain a powder composed of surface-treated scorodite-type iron arsenic compound particles.
- the obtained scorodite-type iron arsenic compound powder (surface-treated) was subjected to surface analysis by ESCA, particle size distribution measurement, SEM observation of particles and dissolution test in the same manner as in Comparative Example 1.
- FIG. 6 illustrates an SEM photograph of the powder particles obtained in this example.
- the Fe / As molar ratio of the surface layer portion of the scorodite-type iron arsenic compound particles obtained in this example is as high as 13.79, and good results were obtained in the dissolution test in accordance with Ministry of the Environment Notification No. 13, and at pH 3 and pH 7.
- the arsenic-resistant elution performance was significantly improved.
- Example 2 The experiment was performed under the same conditions as in Example 1 except that the amount of iron (III) sulfate n hydrate (Fe content 70%) was changed to 8.0 g.
- FIG. 7 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had a surface layer portion with a high Fe / As molar ratio of 9.74, and exhibited excellent arsenic resistance to elution as in Example 1.
- Example 3 The experiment was performed under the same conditions as in Example 1 except that the amount of iron (III) sulfate n hydrate (Fe content 70%) was changed to 1.56 g.
- FIG. 8 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of 2.12 in the surface layer portion, and exhibited excellent arsenic resistance.
- Example 4 The experiment was performed under the same conditions as in Example 1 except that the amount of iron (III) sulfate n hydrate (Fe content 70%) was changed to 0.52 g.
- FIG. 9 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of 1.46 in the surface layer portion, and exhibited excellent arsenic resistance.
- Example 5 The same experiment as in Example 1 was performed except that the liquid temperature during the contact reaction was changed from 40 ° C to 80 ° C.
- FIG. 10 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of the surface layer of 6.23 and exhibited excellent arsenic resistance.
- Example 6 The experiment was performed under the same conditions as in Example 1 except that the liquid temperature during the contact reaction was changed from 40 ° C to 95 ° C.
- FIG. 11 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of 3.27 in the surface layer portion, and exhibited excellent arsenic resistance.
- Example 7 The experiment was performed under the same conditions as in Example 1 except that the pH was adjusted to 7 with sodium bicarbonate.
- FIG. 12 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of the surface layer of 11.33, and exhibited excellent arsenic resistance.
- Example 8 The experiment was performed under the same conditions as in Example 1 except that iron (II) sulfate was used instead of iron (III) sulfate and sodium hydroxide was used instead of sodium hydrogen carbonate.
- the iron ion concentration and pH in the liquid were also the same as in Example 1.
- FIG. 13 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of 2.36 in the surface layer portion, and exhibited excellent arsenic resistance.
- Example 9 As described below, the synthesis of scorodite-type iron arsenic compound particles having an iron-rich layer in the surface layer portion by the treatment A was attempted.
- the iron arsenic reaction was allowed to proceed under the same conditions as in Comparative Example 2.
- a powder (dry solid) composed of scorodite-type iron arsenic compound particles was obtained as the same procedure as Comparative Example 2.
- FIG. 14 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example have a Fe / As molar ratio of 1.35 in the surface layer portion, and can be used for disposal, deposition or storage without undergoing B treatment (surface treatment). Arsenic elution performance with good level was exhibited.
- FIG. 15 illustrates an SEM photograph of the powder particles obtained in this example.
- the scorodite-type iron arsenic compound particles obtained in this example had a Fe / As molar ratio of 1.30 in the surface layer portion, and exhibited good arsenic resistance.
- the scorodite-type iron arsenic compound particles obtained in this example had an Fe / As molar ratio of 1.24 in the surface layer portion, and exhibited good arsenic resistance.
Abstract
Description
5価の砒素イオンと2価の鉄イオンを含む水溶液に酸素含有ガスを供給しながらpH2以下にてスコロダイト型鉄砒素化合物結晶を析出させる反応過程において、反応終了前のまだ液中に未反応の砒素イオンと鉄イオンが存在している時点で、更に酸化剤を前記の酸素含有ガスより酸化力の強い酸化剤を液中に加えることにより、既に析出しているスコロダイト型鉄砒素化合物粒子の表面にFe/Asモル比が1.24以上の鉄リッチ層を形成させること手法。
スコロダイト型鉄砒素化合物粒子の表面を、鉄イオン含有水溶液と接触させることによって、当該粒子の表面に鉄リッチ層を形成させる手法。
特に、上記鉄リッチ層の形成を、液が酸素含有ガスと界面を有する状態の鉄イオン含有水溶液中において行うことが好ましい。前記鉄イオン含有水溶液としては硫酸鉄(III)水溶液または硫酸鉄(II)水溶液が好適に採用できる。
B処理は「結晶性の良いスコロダイト型鉄砒素化合物」の粒子に表面処理を施す工程である。
以下に、各工程について説明する。ここで、「砒素含有溶液の作成」と「スコロダイト鉄砒素化合物の合成」の工程は例示であり、結晶性が良好で、かつ、濾過性が良好であるスコロダイト型鉄砒素化合物が用意できる工程であれば種々の工程が採用可能である。
スコロダイト型鉄砒素化合物を合成するための原料液として、砒素含有溶液(砒素が溶解している液)を用意する。砒素含有溶液は製錬工程などで発生する砒素含有物質から砒素を浸出させる手法を利用して作成することができる。その方法として、例えば本出願人が特許文献4、5などに開示した手法が好適に採用できる。例えば、As2S3やCuSの組成式で表される硫化物を主体とした砒素含有物質を使用する場合には、その硫化物が水中に懸濁しているスラリーに酸素ガスを添加するとともに撹拌しながら砒素の浸出反応を進行させ、反応後、スラリーを固液分離して后液を回収することによって砒素含有溶液が得られる。浸出反応を進行させる際には、スラリー液面に接する気相部における酸素分圧を0.6MPa以下とする。大気開放のオープン系でも実施可能である。前記浸出反応に供するスラリーを構成する水は、水酸化アルカリを添加していない水が使用できるが、水酸化アルカリが多少存在していても砒素の高い浸出率を実現する上で差し支えない。具体的には、水酸化アルカリ濃度が0~1mol/Lに制限された水に砒素含有硫化物を混合してスラリーとすればよい。砒素の浸出反応は60℃以上で行うことが望ましく、100℃以下であればオープンタンク系でも実施できる。反応後のスラリーの酸化還元電位(ORP、Ag/AgCl電極)が200mV以上となるようにすることが望ましい。
5価の砒素含有溶液からスコロダイト結晶を主体とする鉄砒素化合物を合成する方法としては例えば本出願人が特許文献2に開示した手法が好適に採用できる。すなわち、5価の砒素イオンと2価の鉄イオンを含む水溶液に酸化剤を添加して液を撹拌しながらpH2以下において鉄砒素化合物の沈殿析出反応(本明細書ではこれを「鉄砒素反応」と呼ぶ)を進行させる。酸化剤としては酸素含有ガスが好適に採用される。例えば、空気、純酸素ガスなどが挙げられる。酸素含有ガスは、反応進行中、継続的に供給することが望ましい。その供給形態としては液中に吹き込む方法、反応容器の気相部に連続的に導入する方法などがある。反応温度は60~100℃とすることが望ましく、80~100℃の範囲がより好ましい。大気圧下で反応を進行させることができる。後述のB処理に供する場合は、反応終了まで酸化剤として酸素含有ガスを供給し、液のpHが0~1.2の範囲で結晶の析出を終了させることが好ましい。このようにして合成した鉄砒素化合物の結晶を含むスラリーを「鉄砒素反応スラリー」と呼ぶ。この鉄砒素反応スラリーは結晶性が良好なスコロダイト型鉄砒素化合物の粒子を固体成分として含有しており、濾過性が良好である。
上記の合成過程において反応終了前の段階で酸化を促進させ、反応容器中で直接、表面に鉄リッチ層を有するスコロダイト型鉄砒素化合物粒子を合成する手法を「A処理」と呼ぶ。具体的には以下のような合成方法が採用できる。
まず、上記のように5価の砒素イオンと2価の鉄イオンを含む水溶液に酸素含有ガスを供給しながらpH2以下にてスコロダイト型鉄砒素化合物結晶の析出反応を進行させる。そして、反応終了前に、まだ液中に未反応の砒素イオンと鉄イオンが存在している時点で、更に酸化剤(「A処理用酸化剤」という)を液中に加え、その高い酸化力が維持されている状態で反応を終了させる。
A処理を経て得られた洗浄後の本発明のスコロダイト型鉄砒素化合物粒子は、その表層部にFe/Asモル比が1.24以上(例えば1.24~1.50)の鉄リッチ層を有している。
上述の合成方法によって得られた鉄砒素反応スラリーを洗浄、固液分離することによって回収された固形分(粉末)は、結晶性の良いスコロダイト型鉄砒素化合物の粒子で構成されている。その平均粒子径は例えば10~50μmである。A処理を経ていなくても、この粒子は多くの場合、環境省告示13号に準拠した溶出試験での基準をクリアするものである。しかし、pH3あるいはpH7付近での耐砒素溶出性能は十分ではない。そこで、以下のようにB処理(表面処理)に供し、粒子表面に鉄リッチ層を形成させる。
(1)pHを2~9、好ましくは2.5~8とする。
(2)温度を0~95℃、好ましくは15~85℃、さらに好ましくは30~60℃とする。
(3)鉄イオン濃度を0.01~30質量%とする。
接触時間(上記(1)~(3)の条件下で撹拌している時間)は1~300分の範囲で最適時間を見出すことができる。
B処理によって得られた本発明のスコロダイト型鉄砒素化合物粒子は、その表層部にFe/Asモル比が1.24以上(例えば1.24~15.00)の鉄リッチ層を有している。
容量5L(リットル)のチタン製密閉容器(反応槽)にAs濃度50.0g/L、Fe濃度55.90g/L(Fe/As比=1.5)の水溶液3.5Lを入れ、容器内の雰囲気を不活性ガス雰囲気として、1段の平パドルを800rpmにして撹拌しながら昇温させた。容器内の温度が100℃以上になった時点で一旦不活性ガスを脱気し、引き続き、最終的な設定温度175℃まで昇温させた。
〔環境省告示13号準拠の溶出試験〕
蒸留水を用いたpH=5.8~6.3の水を用意し、スコロダイト型鉄砒素化合物粉末と水を1対10の質量割合で混合してスラリーとし、このスラリーを振とう機で6時間振とうさせた後、固液分離して、濾液を分析する方法。
この試験による砒素溶出量が0.3mg/L以下であることが要求される。
乾燥固形物スコロダイト型鉄砒素化合物粉末と蒸留水を1対10の質量割合で混合してスラリーとし、このスラリーをpH=3、またはpH=7に維持しながら振とう機で6時間振とうさせた後、それぞれ固液分離して、濾液を分析する方法。
この試験による砒素溶出量が0.5mg/L以下であれば、堆積現場の実環境において優れた耐砒素溶出性能を呈すると評価される。
本例で得られたスコロダイト型鉄砒素化合物粉末は結晶性が良好でなく(図4参照)、粒子表層部のFe/Asモル比も1.18と低かった。この粉末の耐砒素溶出性能は、後述各例のものと比べ著しく劣っていた。
試薬の砒素含有溶液(和光純薬工業株式会社製、H3AsO4含有量62%)を用いてスコロダイト型鉄砒素化合物の合成を行った。砒素含有溶液5Lを反応容器に入れ、撹拌しながら砒素含有溶液の温度を80℃まで昇温させた。80℃に昇温後、濃硫酸(和光純薬工業株式会社製、H2SO4含有量98%)を用いてpHを1.15に調整し、その後95℃まで昇温させ、試薬の硫酸鉄(II)七水和物(和光純薬工業社製、FeSO4・7H2O)を添加した。この時の反応容器中の砒素(5価)の濃度は50.0g/L、鉄(2価)の濃度は55.9g/Lであり、液中のFe/Asモル比は約1.5である。この鉄砒素含有液を5分間保持した後、2段のディスクタービン、邪魔板4枚をセットして撹拌した。この撹拌時には大気開放下において純度99%の酸素ガスを液中に3.0L/分で吹込んだ。撹拌を継続しながら、液温を95℃に保持し、酸素吹き込みを7時間継続することによって析出反応(鉄砒素反応)を進行させた。その後、スラリーの温度が70℃に低下したのち、吸引濾過器を用いて固液分離し、固形分を回収した。この固形分(ウエットケーキ)を純水でリパルプしてパルプ濃度200g/Lとし、2段のディスクタービン、邪魔板4枚をセットした状態で撹拌することにより20分のリパルプ洗浄を3回行い、その後、吸引濾過を行い、固形分を回収した。この固形分を60℃で18時間乾燥させ、スコロダイト型鉄砒素化合物で構成される粉末を得た。
本例で得られたスコロダイト型鉄砒素化合物粒子は稜を有する多面体形態を呈するものであり、結晶性の良い粒子であることがわかる。環境省告示13号準拠の溶出試験では良好な結果が得られ、比較例1のもの(結晶性が良好でない粒子からなるもの)と比べ耐砒素溶出性能は格段に向上している(表1)。しかし、表層部のFe/Asモル比は1.20と低く、pH3、pH7での耐砒素溶出性能が不十分であった。
比較例2と同じ手法で得たスコロダイト型鉄砒素化合物の乾燥固形物(粉末)を用いて、以下の手順でスコロダイト型鉄砒素化合物粒子にB処理(表面処理)を施した。
水3L(リットル)を反応容器に入れた後、撹拌しながら水の温度を40℃まで昇温させ、硫酸鉄(III)n水和物(Fe含有量70%)38.9gを水中に溶解させ、さらに希硫酸を数滴添加して、pHを2.0とした。この液の鉄イオン濃度は2.5g/Lである。得られた鉄イオン含有水溶液を大気開放下で20分間保持後、上記スコロダイト型鉄砒素化合物の乾燥固形物を561.8g添加し、5分間保持した後、炭酸水素ナトリウムを溶液pHが4になるように10分間かけて添加した。pH調整完了後、温度を40℃に維持し、撹拌を継続させた状態で1時間保持することにより、スコロダイト型鉄砒素化合物粉末の粒子の表面と当該鉄イオン含有水溶液を接触させた(接触反応)。接触反応終了時点の液pHは約3.5であった。
接触反応後のスラリーを吸引濾過器により固液分離し、固形分を回収した。この固形分(ウエットケーキ)を純水でリパルプして固液分離する洗浄を3回行い、洗浄後の固形分を回収した。これを60℃で180分間乾燥させ、表面処理されたスコロダイト型鉄砒素化合物粒子で構成される粉末を得た。
硫酸鉄(III)n水和物(Fe含有量70%)の添加量を8.0gに変更した以外は実施例1と同様の条件で実験を行った。図7に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が9.74と高く、実施例1と同様、優れた耐砒素溶出性能を呈した。
硫酸鉄(III)n水和物(Fe含有量70%)の添加量を1.56gに変更した以外は実施例1と同様の条件で実験を行った。図8に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が2.12であり、優れた耐砒素溶出性能を呈した。
硫酸鉄(III)n水和物(Fe含有量70%)の添加量を0.52gに変更した以外は実施例1と同様の条件で実験を行った。図9に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が1.46であり、優れた耐砒素溶出性能を呈した。
接触反応時の液温を40℃から80℃に変更した以外は実施例1と同様の実験を行った。図10に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が6.23であり、優れた耐砒素溶出性能を呈した。
接触反応時の液温を40℃から95℃に変更した以外は実施例1と同様の条件で実験を行った。図11に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が3.27であり、優れた耐砒素溶出性能を呈した。
炭酸水素ナトリウムによりpHを7に調整したこと以外は実施例1と同様の条件で実験を行った。図12に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が11.33であり、優れた耐砒素溶出性能を呈した。
硫酸鉄(III)に代えて硫酸鉄(II)を使用し、炭酸水素ナトリウムに代えて水酸化ナトリウムを使用したことを除き、実施例1と同様の条件で実験を行った。液中の鉄イオン濃度およびpHも実施例1と同じとした。図13に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が2.36であり、優れた耐砒素溶出性能を呈した。
以下のようにして、A処理により表層部に鉄リッチ層を持つスコロダイト型鉄砒素化合物粒子の合成を試みた。
比較例2と同様の条件で鉄砒素反応を進行させた。ただし、比較例2では酸素吹き込みを7時間継続して反応を終了させたが、本例では酸素吹き込みを7時間継続した時点で、A処理用酸化剤として過酸化水素水(35%)155.6g(H2O2/Fe=0.4)を添加し、その後60分間保持して反応を終了させた。液温、撹拌、酸素の吹き込みは反応終了まで引き続き同条件を維持した。反応終了後は比較例2と同じ手順として、スコロダイト型鉄砒素化合物粒子で構成される粉末(乾燥固形物)を得た。
過酸化水素水の添加量を77.8g(H2O2/Fe=0.2)としたこと以外は実施例9と同様の条件で実験を行った。図15に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が1.30であり、良好な耐砒素溶出性能を呈した。
過酸化水素水の添加量を38.9g(H2O2/Fe=0.1)としたこと以外は実施例9と同様の条件で実験を行った。図3、図15に本例によって得られた粉末粒子のSEM写真を例示する。本例で得られたスコロダイト型鉄砒素化合物粒子は表層部のFe/Asモル比が1.24であり、良好な耐砒素溶出性能を呈した。
Claims (8)
- 粒子表層部にFe/Asモル比が1.24以上の鉄リッチ層を持つスコロダイト型鉄砒素化合物粒子。
- 請求項1に記載のスコロダイト型鉄砒素化合物粒子の集合物からなる砒素含有固形物。
- 請求項1に記載のスコロダイト型鉄砒素化合物粒子と、砒素を含有しない固体物質との混合物からなる砒素含有固形物。
- 5価の砒素イオンと2価の鉄イオンを含む水溶液に酸素含有ガスを供給しながらpH2以下にてスコロダイト型鉄砒素化合物結晶を析出させる反応過程において、反応終了前のまだ液中に未反応の砒素イオンと鉄イオンが存在している時点で、更に酸化剤を液中に加えることにより、既に析出しているスコロダイト型鉄砒素化合物粒子の表面にFe/Asモル比が1.24以上の鉄リッチ層を形成させることを特徴とする請求項1に記載のスコロダイト型鉄砒素化合物粒子の製造方法。
- 前記の更に加える酸化剤が過酸化水素水、オゾン、二酸化マンガン、過マンガン酸カリウム、酸素含有ガスの1種以上である請求項4に記載のスコロダイト型鉄砒素化合物粒子の製造方法。
- スコロダイト型鉄砒素化合物粒子の表面を、鉄イオン含有水溶液と接触させることによって、当該粒子の表面にFe/Asモル比が1.24以上の鉄リッチ層を形成させる請求項1に記載のスコロダイト型鉄砒素化合物粒子の製造方法。
- 上記鉄リッチ層の形成を、液が酸素含有ガスと界面を有する状態の鉄イオン含有水溶液中において行う請求項6に記載のスコロダイト型鉄砒素化合物粒子の製造方法。
- 前記鉄イオン含有水溶液は硫酸鉄(III)水溶液または硫酸鉄(II)水溶液である請求項6または7に記載のスコロダイト型鉄砒素化合物粒子の製造方法。
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EP10774943A EP2431331A1 (en) | 2009-05-13 | 2010-05-12 | Scorodite-type iron-arsenic compound particles, production method, and arsenic-containing solid |
AU2010248410A AU2010248410A1 (en) | 2009-05-13 | 2010-05-12 | Scorodite-type iron-arsenic compound particles, production method, and arsenic-containing solid |
CA 2758394 CA2758394A1 (en) | 2009-05-13 | 2010-05-12 | Scorodite-type iron-arsenic compound particles, production method thereof, and arsenic-containing solid |
CN2010800209924A CN102421708A (zh) | 2009-05-13 | 2010-05-12 | 臭葱石型铁砷化合物粒子及制造方法以及含砷固态物 |
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JP2011184266A (ja) * | 2010-03-10 | 2011-09-22 | Dowa Metals & Mining Co Ltd | ヒ酸鉄粒子の処理方法 |
JP6102590B2 (ja) * | 2013-07-10 | 2017-03-29 | 住友金属鉱山株式会社 | スコロダイトの製造方法 |
AR100110A1 (es) | 2014-01-31 | 2016-09-14 | Goldcorp Inc | Proceso para la separación y recuperación de sulfuros de metales de una mena o concentrado de sulfuros mixtos |
CN106082352B (zh) * | 2016-06-03 | 2018-07-20 | 中南大学 | 一种FeAsO4/Fe2O3复合材料及其制备方法和应用 |
CN106830091B (zh) * | 2016-12-21 | 2018-06-19 | 中南大学 | 一种从含砷溶液中沉淀得到高浸出稳定性臭葱石的方法 |
CN108164030A (zh) * | 2017-12-27 | 2018-06-15 | 中国科学院过程工程研究所 | 一种含砷溶液中砷的固定化方法 |
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US11220437B2 (en) * | 2018-12-24 | 2022-01-11 | Ecometales Limited | Procedure for obtaining scorodite with a high arsenic content from acidic solutions with high content of sulfuric acid |
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JP2009018978A (ja) * | 2007-07-13 | 2009-01-29 | Dowa Metals & Mining Co Ltd | 砒素の処理方法 |
JP2009018291A (ja) * | 2007-07-13 | 2009-01-29 | Dowa Metals & Mining Co Ltd | 種晶を添加する砒素の処理方法 |
JP2009050769A (ja) * | 2007-08-24 | 2009-03-12 | Dowa Metals & Mining Co Ltd | 砒素含有溶液の処理方法 |
JP2009084124A (ja) * | 2007-10-02 | 2009-04-23 | Dowa Metals & Mining Co Ltd | 鉄砒素化合物の製造方法 |
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JP5114049B2 (ja) | 2006-12-15 | 2013-01-09 | Dowaメタルマイン株式会社 | 銅砒素化合物からの砒素液の製法 |
JP5114048B2 (ja) | 2006-12-15 | 2013-01-09 | Dowaメタルマイン株式会社 | 砒素液の製法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2009018978A (ja) * | 2007-07-13 | 2009-01-29 | Dowa Metals & Mining Co Ltd | 砒素の処理方法 |
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