TWI535664B - Molybdenum-contained wastewater treatment method and molybdenum recovery method - Google Patents

Description

Molybdenum containing wastewater treatment and molybdenum recovery method

The invention relates to a method for treating and recovering molybdenum containing molybdenum wastewater; in particular to a method for treating molybdenum-containing wastewater using a selective adsorbent for molybdenum; more particularly, a method for recovering high-purity molybdenum after treatment with molybdenum-containing wastewater.

A method of treating molybdenum recovery, for example, a patent application of Process for separating and recovering valuable metals, which discloses a method for separating and recovering precious metals. The method for separating and recovering precious metals is only used to separate a raw material containing vanadium oxide and molybdenum oxide by a leaching step to obtain vanadium oxide (vanadium). Oxide] and a solution of a molybdenum oxide compound.

Another conventional treatment method for the recovery of molybdenum, for example, U.S. Patent Publication No. 20100115988, the disclosure of which is incorporated herein by reference. The molybdate-containing waste liquid stream treatment method is only used to treat an aqueous solution containing sodium carbonate and/or sodium bicarbonate and sodium molybdate, which utilizes condensation crystallization. Method (freeze crystallising) treating the aqueous solution at a eutectic freezing point to obtain pure sodium carbonate and/or sodium hydrogencarbonate, and obtaining water An aqueous product solution containing dissolved sodium molybdate.

Another conventional treatment method for the recovery of molybdenum, for example, US Patent Publication No. 20130108526, Method for materials recovery from catalysts comprising iron, cerium, molybdenum and potassium, discloses a method for recovering iron, bismuth, molybdenum and molybdenum from a catalyst. A method of potassium species, wherein the method is only used to treat the catalyst as an aqueous leachant to remove molybdenum and potassium from the catalyst.

However, the aforementioned methods of treating molybdenum in wastewater treatment are not disclosed in the aforementioned U.S. Patent Publication Nos. 20040213717, 20100115988 and 20130108526. Therefore, the treatment method of conventional molybdenum recovery necessarily has a further need for how to recover molybdenum from wastewater treatment. The above-mentioned patents and patent applications are merely for the purpose of the technical background of the present invention and are not intended to limit the scope of the present invention.

Another conventional recyclable magnetic adsorbent and a method for producing the same, for example, the patent application of the magnetic adsorbent of the cookware of the Republic of China Patent No. 201139287 and the preparation method of the adsorbent, which discloses a magnetic adsorbate Preparation. The method for preparing the adsorbent comprises (a) a preparation step, (b) a blending step, (c) a heating and agitating step, (d) a stirring and drying step, and (e) an adsorption layer forming step. The adsorbent is coated with a carrier by an outer shell, and the adsorbent layer has a covalently bonded amine functional group, so that the adsorbent can be quickly recovered by using an external magnetic field after the reaction is completed. .

Another conventional iron oxide adsorbent and a method for producing the same are, for example, the patent of the granulated iron oxide adsorbent of the Republic of China Patent No. I223607, which discloses a granular iron oxide adsorbent and a method for producing the same. The method for preparing the granular iron oxide adsorbent comprises: mixing a citrate solution with a ferric salt solution to obtain a mixed solution; controlling a pH condition of the mixed solution to form a colloidal solution; and the colloid Solution holding The mixture is stirred and mixed to produce a nucleation effect; after sufficient growth, a settling colloid is formed; and the settling colloid is further washed and dried to obtain a granular adsorption. Agent. The particulate adsorbent has the property of sufficient mechanical strength.

However, the aforementioned US Patent Publication No. 201139287 and the Republic of China Patent No. I223607 do not disclose an adsorbent suitable for recovering molybdenum from waste water. Therefore, conventional recyclable magnetic adsorbents or iron oxide adsorbents and methods for their manufacture necessarily require further provision of adsorbents suitable for the recovery of molybdenum from wastewater. The above-mentioned patents and patent applications are merely for the purpose of the technical background of the present invention and are not intended to limit the scope of the present invention.

In view of the above, in order to meet the above technical problems and needs, the present invention provides a method for treating and recovering molybdenum containing molybdenum, which comprises adding a selective adsorbent of molybdenum to wastewater, and generating a molybdenum adsorbent which has been used, and then A treated wastewater is discharged, and the molybdenum sorbent is desorbed with a desorbing agent to obtain a selective adsorbent for recovering molybdenum ions and a regenerated molybdenum, which is processed relative to conventional molybdenum recovery Or the adsorbent has the effect of treating the molybdenum-containing wastewater and separately removing the molybdenum ions and molybdenum from the wastewater.

The main object of the preferred embodiment of the present invention is to provide a method for treating molybdenum-containing wastewater, which comprises adding a selective adsorbent of molybdenum to waste water, and generating a used molybdenum adsorbent, and discharging a treated wastewater to To achieve the purpose of providing molybdenum wastewater treatment.

In order to achieve the above object, a method for treating a molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises: adding a selective adsorbent of molybdenum to a wastewater containing molybdenum; mixing the wastewater with a selective adsorbent of molybdenum so as to be Molybdenum ions are adsorbed by the selective adsorbent of the molybdenum in the wastewater; The wastewater is separated from the selective adsorbent of molybdenum to obtain a used molybdenum adsorbent and a treated wastewater; and the treated wastewater is discharged, and the used molybdenum adsorbent is left behind.

In a preferred embodiment of the invention, the wastewater is mixed with a selective adsorbent of molybdenum for a predetermined period of time.

In a preferred embodiment of the present invention, the mixed water of the wastewater and the selective adsorbent of molybdenum is subjected to static precipitation for a predetermined period of time.

The selective adsorbent for molybdenum according to a preferred embodiment of the present invention is an adsorbent having a nanometer-sized particle size.

The preferred embodiment of the invention has been formed using a molybdenum adsorbent as a saturated molybdenum adsorbent.

Another object of the preferred embodiment of the present invention is to provide a method for recovering molybdenum containing molybdenum wastewater, which comprises adding a molybdenum selective adsorbent to the wastewater, and generating a used molybdenum adsorbent, and then treating the treated wastewater. Discharging, and using the molybdenum adsorbent to desorb molybdenum ions with a molybdenum desorbing agent to obtain a selective adsorbent for recovering molybdenum ions and a regenerated molybdenum to achieve separate recovery of molybdenum ions and molybdenum from wastewater The purpose of the selective adsorbent.

In order to achieve the above object, a method for recovering molybdenum in a molybdenum-containing wastewater treatment according to a preferred embodiment of the present invention comprises: adding a molybdenum desorbing agent to a used molybdenum adsorbent; and using the molybdenum adsorbent and the molybdenum desorbing agent Mixing to remove molybdenum ions from the used molybdenum adsorbent to form a selective adsorbent comprising a molybdenum ion solution and a regenerated molybdenum; separating the molybdenum ion-containing solution from the selective adsorbent of the regenerated molybdenum; The molybdenum-containing ion solution is discharged and collected, and a selective adsorbent for the regenerated molybdenum is left.

The molybdenum desorbent of the preferred embodiment of the invention is selected from the group consisting of an alkaline solution.

The molybdenum desorbing agent of the preferred embodiment of the invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide or any combination thereof.

In a preferred embodiment of the invention, the molybdenum adsorbent has been stirred and mixed with the molybdenum desorbing agent for a predetermined period of time.

In a preferred embodiment of the present invention, the molybdenum ion-containing solution and the selective adsorbent for regenerating molybdenum are subjected to static precipitation for a predetermined period of time.

Another object of the preferred embodiment of the present invention is to provide a selective adsorbent for molybdenum and a method for producing the same, which utilizes at least one divalent cation to synthetically incorporate a ferrite lattice to form a doped ferrite a lattice body, and the divalent cation changes the characteristics of the doped ferrite lattice to achieve selective adsorption of molybdenum ions.

In order to achieve the above object, a selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises: a ferrite lattice body comprising ferrous ions and oxygen ions, the ferrous ions and oxygen ions combined to form the ferrite lattice And at least one divalent cation which is synthetically incorporated into the ferrite lattice to form a doped ferrite lattice; wherein the divalent cation changes the characteristics of the doped ferrite lattice, The doped ferrite lattice thus selectively adsorbs molybdenum ions.

In a preferred embodiment of the invention, the divalent cation is selected from the group consisting of nickel ions, copper ions, cobalt ions, titanium ions, barium ions, calcium ions, magnesium ions, zinc ions, manganese ions, or any combination thereof.

In the preferred embodiment of the present invention, the molybdenum selective adsorbent is a gravity type adsorbent or a magnetic type adsorbent.

In the preferred embodiment of the present invention, the molybdenum selective adsorbent is a slurry type adsorbent or a dry powder type adsorbent.

The selective adsorbent for molybdenum according to a preferred embodiment of the present invention is Nano-sized adsorbent.

In order to achieve the above object, a method for producing a selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises: preparing a ferrous ion-containing solution and at least one divalent cation-containing solution; and the ferrous ion-containing solution and divalent cation-containing solution The solution is mixed to obtain a mixed solution; the mixed solution is adjusted to a pH value of 7 to 14 to obtain a pH-adjusted solution; the adjusted pH solution is heated to a predetermined temperature and continues Heating for a predetermined time; supplying a reactive gas to the adjusted pH solution while heating the adjusted pH solution; and when the solid crude product of the doped ferrite lattice is obtained, the doping is performed The solid crude product of the ferrite lattice is separated.

In a preferred embodiment of the invention, the solid crude product of the doped ferrite lattice is conditioned with an acidic solution.

In a preferred embodiment of the invention, the ferrous ion-containing solution is selected from the group consisting of ferrous sulfate or ferrous chloride, and the divalent cation-containing solution is selected from the group consisting of nickel nitrate, nickel sulfate, nickel chloride or other sources of nickel.

In the preferred embodiment of the invention, the heated pH of the solution is from 50 ° C to 100 ° C.

The reaction gas of the preferred embodiment of the invention is selected from the group consisting of oxygen or air.

10‧‧‧Selective adsorbent for molybdenum

10'‧‧‧Used Molybdenum Adsorbent

10"‧‧‧Selective adsorbent for regenerated molybdenum

20‧‧‧pH value meter

Fig. 1 is a schematic view showing the flow of a method for treating molybdenum-containing wastewater according to a preferred embodiment of the present invention.

Figure 2: Recovery of molybdenum from treatment of molybdenum-containing wastewater in accordance with a preferred embodiment of the present invention Before, the schematic diagram of the cleaning method using a molybdenum selective adsorbent.

Fig. 3 is a flow chart showing the process for recovering molybdenum in the treatment of molybdenum-containing wastewater according to a preferred embodiment of the present invention.

Fig. 4 is a flow chart showing a method for producing a selective adsorbent for molybdenum according to a preferred embodiment of the present invention.

Fig. 5 is a graph showing the surface electrical change (zero potential point shift) of the selective adsorbent of molybdenum in the preferred embodiment of the present invention after nickel incorporation.

Fig. 6 is a schematic view showing the magnetic properties of a selective adsorbent of molybdenum according to a preferred embodiment of the present invention [taking a nickel-iron system as an example].

In order to fully understand the present invention, the preferred embodiments of the present invention are described in detail below, and are not intended to limit the invention.

The molybdenum-containing wastewater treatment mode, method and system thereof according to the preferred embodiment of the present invention are suitable for combination application to various wastewater treatment facilities; in addition, the molybdenum recovery mode, method and system for treating molybdenum-containing wastewater in accordance with a preferred embodiment of the present invention are suitable for combination It is applied to the recovery (regeneration or desorption) of various wastewater treatments. It is especially suitable for wastewater treatment in the photovoltaic industry, metal recycling industry and metallurgical chain industry, but it is not limited to this invention.

The molybdenum-containing wastewater treatment of the preferred embodiment of the present invention is also suitable for use in various wastewater treatment facilities, and the molybdenum selective adsorbent is made into various adsorbent products, such as powder or ingot. Or other forms of products; in addition, the selective adsorbent manufacturing mode, method and production system of the preferred embodiment of the present invention are suitable for use in various related adsorbent manufacturing apparatuses, but are not intended to limit the present invention.

In general, molybdenum characteristics are different from those of most heavy metals, and in molybdenum-containing wastewater, molybdenum is present in the form of several oxo-acid anion groups (generally collectively referred to as molybdate ions), particularly with changes in concentration and pH. Therefore, in the process of wastewater treatment, since it is easily interfered by anions such as phosphate and sulfate, the conventional ion exchange method or coagulation sedimentation method is not suitable for the effective treatment of wastewater to remove molybdenum ions. In fact, the selective adsorbent of molybdenum according to the preferred embodiment of the present invention is a highly selective adsorbent and is not interfered by anions such as phosphate or sulfate, so that it can be suitably used for the effective treatment of wastewater to remove molybdenum ions.

The technical term of the present invention uses iron ions in the yttrium iron oxide crystal lattice to contain divalent and trivalent iron ions, all of which are present in the ferrite lattice, and the technical term of the present invention is also used in the bismuth containing molybdate ion solution. In the solution containing molybdate ion, the technical term of the present invention further adopts a solid crude product of cerium and a solid crude product containing cerium-doped ferrite lattice, which is described first.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a process for treating a molybdenum-containing wastewater according to a preferred embodiment of the present invention, which comprises four illustrative steps which are merely exemplified for use in a single wastewater storage facility (e.g., a wastewater tank). Referring to FIG. 1, a method for treating a molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises the steps of: first, a selective adsorbent 10 of molybdenum in an appropriate amount (for example, an adsorbent of a suitable weight) and an appropriate manner [for example] : Automatic, semi-automatic or manual injection method] added to the appropriate amount of molybdenum-containing wastewater (for example: the amount of appropriate wastewater volume). For example, the volume of wastewater is about 50 L, and the selective adsorbent 10 of the molybdenum is about 50 g.

Referring to FIG. 1 again, the method for treating molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises the steps of: subsequently, mixing the molybdenum-containing wastewater with the selective adsorbent 10 of molybdenum for use in the molybdenum-containing wastewater. The molybdenum selective adsorbent 10 selectively adsorbs molybdate ions. At this time, the selective adsorbent 10 of the molybdenum is continuously selectively adsorbed by the molybdate ion without being interfered by sulfate ions, phosphate ions, nitrate ions, acetate ions, chloride ions or other anions. For example, the wastewater is mixed with the molybdenum selective adsorbent 10 by a stirrer for a predetermined time (for example, continuous stirring for 60 minutes). For example, the molybdenum The wastewater is preferably adjusted to a pH in the range of 1 to 7, preferably at a pH of 3, and is measured using a pH meter 20.

Referring to FIG. 1 again, the method for treating molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises the steps of: subsequently separating the wastewater from the selective adsorbent 10 of molybdenum to obtain a molybdenum adsorbent 10' [As shown in Figure 2] and a treated wastewater. After continuous selective adsorption of molybdate ions, the molybdenum adsorbent that has been used may form a saturated molybdenum adsorbent. For example, the mixed water of the wastewater and the selective adsorbent 10 of molybdenum is subjected to static precipitation separation for a predetermined time (for example, the stirring is stopped and allowed to stand for 30 minutes), and the used molybdenum is gradually produced from the treated wastewater. Precipitation of the adsorbent.

Referring to FIG. 1 again, the method for treating molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises the steps of: subsequently discharging the treated wastewater, which meets the requirements of China's regulations, and the concentration of molybdenum in the industrial discharge water must be treated to 0.6 mg/ The molybdenum adsorbent 10' which has been used below L and leaves a precipitate, as shown in the lowermost layer of Fig. 1 and Fig. 2 is shown. For example, the treated wastewater is discharged and collected into a predetermined collection tank (not shown).

2 is a schematic flow chart showing a cleaning method using a molybdenum selective adsorbent prior to recovering molybdenum in a molybdenum-containing wastewater treatment according to a preferred embodiment of the present invention, which comprises four schematic steps corresponding to those included in FIG. Subsequent treatment of molybdenum wastewater treatment methods. Referring to Fig. 2, a method for cleaning a selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises the steps of: first, adding a cleaning liquid to the used molybdenum adsorbent 10'. For example, the cleaning solution is selected to be used in an amount of 0.5 L, and the cleaning solution is prepared by nitric acid and has a pH of 3.

Referring to FIG. 2 again, the method for cleaning a selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises the steps of: subsequently, mixing the used molybdenum adsorbent 10' with a cleaning solution, so as to be in the cleaning solution. The surface of the molybdenum adsorbent 10' that has been used is cleaned. For example, the molybdenum has been used The auxiliary agent 10' is washed with a washing liquid by a stirrer for a predetermined time (for example, continuous stirring for 5 minutes). For example, the molybdenum adsorbent 10' and the cleaning solution have been preferably adjusted to have a pH in the range of 1 to 7, preferably selected as pH 3, and measured using the pH meter 20 .

Referring to Fig. 2 again, the method for cleaning a selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises the step of: subsequently separating the used molybdenum adsorbent 10' from the cleaning liquid. For example, the molybdenum adsorbent 10' has been subjected to static precipitation separation with a cleaning liquid for a predetermined time (for example, stirring is stopped and allowed to stand for 30 minutes), and the used molybdenum adsorbent 10 is gradually produced from the cleaning liquid. 'The precipitation down.

Referring to FIG. 2 again, the cleaning method of the selective adsorbent for molybdenum according to the preferred embodiment of the present invention comprises the steps of: subsequently discharging the cleaning solution, and leaving the used molybdenum adsorption after the completion of the cleaning. Agent 10' is shown as the lowermost material in Figure 2. For example, the cleaning solution is combined into the molybdenum-containing wastewater to be treated or collected into a predetermined collection tank (not shown).

3 is a schematic flow chart showing a method for recovering molybdenum in a molybdenum-containing wastewater treatment according to a preferred embodiment of the present invention, which comprises four schematic steps corresponding to the molybdenum-containing wastewater treatment method of FIG. 1 or the selectivity of FIG. Subsequent treatment of the cleaning method of the adsorbent. Referring to FIG. 3, the molybdenum recovery method for treating molybdenum-containing wastewater according to a preferred embodiment of the present invention comprises the steps of: first, applying a molybdenum desorbing agent in an appropriate amount (for example, an appropriate amount of molybdenum desorbing agent) and an appropriate manner. [Example: automatic, semi-automatic or manual injection] is added to the already used molybdenum adsorbent 10'. For example, the molybdenum desorbing agent is selected from an alkaline solution, an acidic solution or a salt, and the molybdenum desorbing agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, and hydrogen. Ammonium hydroxide or any combination thereof. For example, 1 L of pure water and sodium hydroxide are prepared to form the alkaline solution having a pH of 13.

Referring to FIG. 3 again, the method for recovering molybdenum containing molybdenum wastewater treated according to a preferred embodiment of the present invention comprises the steps of: subsequently, mixing the used molybdenum adsorbent 10' with a molybdenum desorbing agent to remove molybdenum ions. Detaching the molybdenum adsorbent 10' used to form a molybdate-containing ion solution (or a solution rich in molybdate ions) and a selective adsorbent for regenerating molybdenum 10". For example, the molybdenum adsorbent has been used. 10' and the molybdenum desorbing agent are stirred and mixed by a mixer for a predetermined time (for example, continuous stirring for 60 minutes), and the molybdenum desorbing agent is preferably adjusted to a pH value of 7 to 14, and the optimum choice is pH. The value is 13 and the measurement is performed using the pH meter 20.

Referring to FIG. 3 again, the method for recovering molybdenum containing molybdenum wastewater treated according to a preferred embodiment of the present invention comprises the steps of: subsequently separating the molybdate-containing ion solution from the selective adsorbent 10" of the regenerated molybdenum. In addition, the molybdate-containing ion solution and the regenerated molybdenum selective adsorbent 10" are subjected to static precipitation separation for a predetermined time (for example, stopping stirring and standing for 30 minutes), and gradually generating from the molybdate-containing ion solution. The selective adsorbent 10" of the regenerated molybdenum precipitates downward.

Referring to FIG. 3 again, the method for recovering molybdenum containing molybdenum wastewater treated according to a preferred embodiment of the present invention comprises the steps of: subsequently collecting the solution containing molybdate ions, and leaving the selection of the regenerated molybdenum for regeneration. The adsorbent 10". For example, the molybdenum-containing ion solution is discharged to a subsequent processing device (not shown) or collected to a predetermined collection tank (not shown). Thus, the present invention obtains high purity. The molybdenum ion-containing solution can be used as a raw material for producing molybdate such as metal molybdenum or sodium molybdate, ammonium molybdate or potassium molybdate.

4 is a schematic flow chart showing a method for preparing a selective adsorbent for molybdenum according to a preferred embodiment of the present invention, which comprises the steps of preparing a reaction solution, a step of mixing a solution, a step of adjusting a base, a step of heating, a step of supplying a reaction gas, and a preliminary separation of solid and liquid. Step, conditioning step and final separation step of solid and liquid. Referring to FIG. 4, a preferred embodiment of the present invention for producing a selective adsorbent for molybdenum comprises the steps of: first, preparing a reaction solution step to prepare a A ferrous ion solution and at least one or more divalent cation-containing solutions. For example, the divalent cation is selected from the group consisting of nickel ions, copper ions, cobalt ions, titanium ions, barium ions, calcium ions, magnesium ions, zinc ions, manganese ions, or any combination thereof.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, a method for producing a selective adsorbent for molybdenum comprises the steps of: subsequently, performing a solution mixing step of ferrous ion-containing solution and divalent in a reaction system; The cation solution is mixed to obtain a mixed solution. For example, the ferrous ion-containing solution is selected from the group consisting of ferrous sulfate or ferrous chloride, and the divalent cation-containing solution is selected from the group consisting of nickel nitrate, nickel sulfate, nickel chloride or other sources of nickel. For example, the volume fraction of the ferrous sulfate and nickel nitrate is preferably: [Ni ²⁺ ]=0.1M to 1.0M, [Fe ²⁺ ]=0.2M to 5.0M; : [Ni ²⁺ ] = 0.5 M, [Fe ²⁺ ] = 2.5 M solution.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, the method for producing a selective adsorbent for molybdenum comprises the steps of: subsequently, performing a alkali-adjusting step, preferably adjusting the mixed solution to an acidic solution or an alkaline solution to The pH is in the range of 7 to 14 to obtain a pH adjusted solution. For example, the mixed solution is optimally adjusted to a pH between about 8.9 and 9.1.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, the method for producing a selective adsorbent for molybdenum comprises the steps of: subsequently performing a heating step of heating the adjusted pH solution for a predetermined period of time. For example, the temperature of the pH-adjusted solution is preferably from 50 ° C to 100 ° C, and the heating temperature is preferably about 90 ° C.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, the method for producing a selective adsorbent for molybdenum comprises the steps of: subsequently, performing a reaction gas supply step of supplying a reaction gas to the heated pH solution; In the pH-adjusted solution, a partial solid of ferrous oxide is reacted to form a solid crude product doped with a ferrite lattice. For example, the reactive gas is selected from the group consisting of oxygen, air, or a combination thereof. For example, the present invention compares A preferred embodiment of the method for producing a selective adsorbent for molybdenum maintains a reaction time of preferably 10 minutes or more, and the reaction time is preferably maintained at 80 minutes.

Referring to FIG. 4 again, a preferred embodiment of the present invention for preparing a selective adsorbent for molybdenum comprises the steps of: subsequently performing a preliminary separation step to obtain a solid amount of the doped ferrite lattice in a predetermined amount. In the case of the product, the solid crude product of the doped ferrite lattice is subjected to preliminary separation. For example, the present invention selectively preliminarily separates solids from the solid crude product of the doped ferrite lattice by magnetic force.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, the method for producing a selective adsorbent for molybdenum further comprises the steps of: subsequently performing a conditioning step, the preferred embodiment of the present invention is a solid doped ferrite lattice The crude product is conditioned with an acidic solution (e.g., nitric acid or other acid), i.e., the conditioning step is employed or omitted as desired. For example, in the present invention, the solid is preferably immersed in dilute nitric acid having a pH of 2 to 7 for 10 to 120 minutes. The present invention preferably immerses the solid in dilute nitric acid having a pH of 3 for 60 minutes.

Referring to FIG. 4 again, in the preferred embodiment of the present invention, the method for producing a selective adsorbent for molybdenum further comprises the steps of: subsequently, performing a final separation step of solid-doped solid solution of the doped ferrite lattice with an acidic solution. Perform the final separation. For example, the present invention selects the solid crude product of the doped ferrite lattice to be finally separated by magnetic force to obtain a selective adsorbent product of molybdenum.

Referring to FIG. 4 again, the selective adsorbent for molybdenum according to a preferred embodiment of the present invention comprises a ferrite lattice and at least one divalent cation. The ferrite lattice body includes a divalent iron ion, a ferric ion, and an oxygen ion, and the divalent iron ion, the trivalent iron ion, and the oxygen ion combine to form the ferrite lattice. The divalent cation is incorporated into the ferrite lattice by synthetic means to form a doped ferrite lattice. The divalent cation changes the characteristics of the doped ferrite lattice, such that the doped ferrite lattice selectively adsorbs molybdenum ions.

For example, the divalent cation of the preferred embodiment of the invention It is selected from the group consisting of nickel ions, copper ions, cobalt ions, titanium ions, barium ions, calcium ions, magnesium ions, zinc ions, manganese ions or any combination thereof, for example, a selective adsorbent or copper specially made of nickel-iron molybdenum. A selective adsorbent for iron molybdenum. The selective adsorbent of molybdenum according to a preferred embodiment of the present invention is dried and ground into a powdery product.

For example, in the preferred embodiment of the present invention, the molybdenum selective adsorbent is a gravity type adsorbent, so that the adsorption/desorption operation can be completed by a simple device by utilizing the high specific gravity characteristic peculiar to the adsorbent material. Alternatively, the molybdenum selective adsorbent is a magnetic type adsorbent, so that the electromagnet can be used to accelerate the adsorption/desorption operation speed by utilizing the paramagnetic characteristic peculiar to the adsorbent material. For example, the molybdenum selective adsorbent of the preferred embodiment of the present invention is a slurry type adsorbent or a dry powder type adsorbent. For example, the molybdenum selective adsorbent of the preferred embodiment of the present invention is a nano-sized adsorbent having a particle size distribution between about 40 nm and 150 nm.

Figure 5 is a schematic view showing a curve of surface electrical change (zero potential point shift) of a selective adsorbent of molybdenum according to a preferred embodiment of the present invention after nickel incorporation, which corresponds to the selectivity of molybdenum in Figure 4 Adsorbent. Referring to FIG. 5, for example, a preferred embodiment of the present invention selects three ratios of Ni/Fe [Ni/Fe=1/2, 1/5, and 1/10] in comparison with Fe ₃ O ₄ . Surface electrical changes.

Fig. 6 is a schematic view showing the magnetic expression property of the selective adsorbent of molybdenum according to a preferred embodiment of the present invention [in the form of a nickel-iron system], which corresponds to the selective adsorbent of molybdenum in Fig. 4. Referring to FIG. 6, for example, a preferred embodiment of the present invention selects three ratios of Ni/Fe [Ni/Fe=1/2, 1/5, and 1/10] in comparison with Fe ₃ O ₄ . Magnetic properties. For example, the saturation magnetic flux can reach 60emu/g, which can be separated by magnetic force and solid-liquid separation, and the saturated adsorption amount can reach 110mg(Mo)/g, and the equilibrium adsorption amount of the solution concentration of 10mg(Mo)/L can reach 80 mg (Mo) / g.

As shown in Figures 5 and 6, the above experimental data is in a specific strip. The preliminary experimental results obtained under the section are only for easy understanding or reference to the technical content of the present invention, and other experiments are still required. The experimental data and its results are not intended to limit the scope of the invention.

The foregoing preferred embodiments are merely illustrative of the invention and the technical features thereof, and the techniques of the embodiments can be carried out with various substantial equivalent modifications and/or alternatives; therefore, the scope of the invention is subject to the appended claims. The scope defined by the scope shall prevail. The copyright limitation of this case is used for the purpose of patent application in the Republic of China.

10‧‧‧Selective adsorbent for molybdenum

20‧‧‧pH value meter

Claims (10)

A method for treating molybdenum-containing wastewater, comprising: adding a selective adsorbent of molybdenum to a wastewater containing molybdenum; mixing the wastewater with a selective adsorbent of molybdenum to selectively adsorb the molybdenum in the wastewater The agent adsorbs molybdenum ions, and the selective adsorbent of the molybdenum comprises a ferrite lattice and at least one divalent metal cation, and the ferrite lattice comprises divalent iron ions, ferric ions and oxygen ions, wherein Synthesizing the divalent metal cation into the ferrite lattice to form a doped ferrite lattice, and thus the doped ferrite lattice is composed of the divalent iron ion, the ferric ion, Oxygen ions and doped divalent metal cations are formed in a combined arrangement, and the divalent metal cation is selected from the group consisting of nickel ions, copper ions, cobalt ions, titanium ions, barium ions, calcium ions, magnesium ions, zinc ions or manganese ions; The molybdenum selective adsorbent selectively adsorbs molybdate ions, and the molybdenum selective adsorbent is not interfered by sulfate ions, phosphate ions, nitrate ions, acetate ions, chloride ions; the wastewater and molybdenum selected Separating adsorbent, has been used to obtain an adsorbent with a molybdenum treated wastewater; and the treated wastewater discharge, and leave the adsorbent is molybdenum. The method for treating molybdenum-containing wastewater according to claim 1, wherein the wastewater is stirred and mixed with a selective adsorbent of molybdenum for a predetermined period of time. The method for treating molybdenum-containing wastewater according to claim 1, wherein the wastewater and the selective adsorbent of molybdenum are subjected to static precipitation for a predetermined period of time. The method for treating molybdenum-containing wastewater according to claim 1, wherein the molybdenum selective adsorbent is an adsorbent having a nanometer-sized particle size. The method for treating molybdenum-containing wastewater according to claim 1, wherein the molybdenum adsorbent has been used to form a saturated molybdenum adsorbent. A method for recovering molybdenum containing molybdenum wastewater treatment, comprising: adding a molybdenum desorbing agent to a selective adsorbent using molybdenum, Molybdenum ion is adsorbed by a selective adsorbent using molybdenum; the selective adsorbent using molybdenum is mixed with a molybdenum desorbing agent to remove molybdenum ions from the selective adsorbent using molybdenum to form a a molybdenum ion solution and a selective adsorbent for regenerating molybdenum; separating the molybdenum ion-containing solution from the selective adsorbent of the regenerated molybdenum; and discharging and collecting the molybdenum-containing ion solution, and leaving the selection of the regenerated molybdenum a selective adsorbent, wherein the selective adsorbent for using or regenerating molybdenum comprises a ferrite lattice and at least one divalent metal cation, and the ferrite lattice comprises divalent iron ions, ferric ions and oxygen An ion in which the divalent metal cation is incorporated into the ferrite lattice by a synthetic method to form a doped ferrite lattice, and thus the doped ferrite lattice is composed of the divalent iron ion and trivalent Iron ions, oxygen ions and doped divalent metal cations are formed in a combined arrangement; and the molybdenum selective ion is selected to be adsorbed by the molybdenum selective adsorbent, and the selective adsorbent using or regenerating molybdenum is not subjected to sulfuric acid Ion, phosphate ion, nitrate ion, acetate ion, the chloride ion interference. The molybdenum recovery method for treating molybdenum-containing wastewater according to claim 6 of the patent application, wherein the molybdenum desorbing agent is selected from an alkaline solution. The molybdenum recovery method for treating molybdenum-containing wastewater according to claim 6 of the patent application, wherein the molybdenum desorbing agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide or any combination thereof. The molybdenum recovery method for molybdenum-containing wastewater treatment according to claim 6, wherein the selective adsorbent using molybdenum is stirred and mixed with the molybdenum desorbing agent for a predetermined time. The method for recovering molybdenum containing molybdenum wastewater treated according to claim 6 of the patent application, wherein the molybdenum ion-containing solution and the regenerated molybdenum selective adsorbent are subjected to static precipitation for a predetermined time, or the molybdenum ion-containing solution is prepared. Selective adsorbents with regenerated molybdenum are selected using a magnetic force to increase the rate of sedimentation separation.