JPH0747084B2 - How to collect valuables with adsorbents - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for collecting a valuable substance from a solution with an adsorbent.

More specifically, valuable substances are adsorbed and collected from a valuable substance solution in which solid impurity particles are mixed or impurities are supersaturated, such as a liquid obtained by leaching ore, slag, waste catalyst, scrap, etc. with acid or alkali. It is about how to get together.

(Conventional method) As an adsorption operation for separating and collecting a valuable substance from a gas or a liquid by using an adsorbent, a contact permeation method (stirring tank method), a fixed bed method, depending on a state in which the adsorbent is in contact with the gas or liquid, It is classified into a moving bed system and a fluidized bed system, and is appropriately selected according to the type, shape and properties of the adsorbent or the types and properties of the gas and liquid to be contacted, as well as the method of collection and regeneration, the throughput, the economic efficiency and the like. .

The contacting method is a method in which a powdery or granular adsorbent is mixed with a liquid and suspended by stirring to adsorb, and is a batch system.

In the fixed bed adsorption method, a gas or a liquid is passed through a bed filled with an adsorbent to perform adsorption.

Further, the transfer amount adsorption method is a method of continuously adsorbing with a moving bed of the adsorbent, which continuously circulates and lowers the adsorbent to bring gas or liquid into countercurrent contact. , Operation becomes complicated.

In the fluidized bed adsorption method, the adsorbent is floated and flowed by the upward flow of gas or liquid without flowing out the adsorbent outside the bed.
Adsorption is performed, and industrially, a multi-stage fluidized bed in which several stages are stacked is often used. However, it has a drawback that the adsorbing effect is poor, and the adsorbent having a small particle size jumps out of the layer depending on the upward flow velocity of gas or liquid.

As the adsorption operation, generally, a fixed bed system in which a valuable material is adsorbed by passing a gas or a liquid through a fixed bed of an adsorbent packed in an adsorption tower is often used because the equipment and operation are simple and efficient adsorption is possible. Has been adopted.

(Problems to be Solved by the Invention) In many cases, a valuable-material-containing solution has insoluble solid impurity particles or impurities dissolved in supersaturation due to the origin of the solution. When such a solution is circulated through the fixed bed of the adsorbent to adsorb the valuable material, solid particles and impurities dissolved in supersaturation are deposited and adhered to the voids of the adsorbent layer, and the adsorbent layer Since the voids are closed, the void ratio becomes small, resulting in a rapid increase in the fluid pressure loss and a reduction in the fluid flow rate.

In such a case, the operation may be stopped to remove the blockages, or the flow direction may be switched to remove the blockages accumulated in the fixed bed by the reverse flow liquid. Is interrupted, and a large amount of time is lost and complicated operations are added, resulting in a decline in the capacity of the facility, which is a serious industrial problem.

In addition, if solid particles in the solution are removed in advance, after removing large particles by sedimentation separation, centrifugation, etc., an additional 10
Small particles of 0 μm or less need to be removed in excess, and if components dissolved in supersaturation are to be removed, it is necessary to cool and precipitate for a long time, and further perform operations such as sedimentation, centrifugation, and excess.

In the present invention, mainly from a solution in which insoluble solid impurity particles are mixed or impurities are supersaturatedly dissolved, such as leaching ore, slag, waste catalyst, scraps of rare metals and precious metals with acid or alkali, etc. It is intended to provide a method for efficiently adsorbing and collecting a valuable substance with an adsorbent without performing troublesome treatment on the solution in advance and using a simple device and operation.

(Means for Solving the Problem) The present invention is to disperse a valuable substance-containing solution in which solid impurity particles are mixed and / or impurities are supersaturated into a solid granular adsorbent layer accumulated in a container, In the method for collecting a valuable substance in the solution, the adsorbent layer is collected by a porous support plate provided on the outlet side of the container, and while the adsorbent layer is unraveled. The method is characterized by circulating the solution.

In the present invention, the valuable substance-containing solution in which solid impurity particles are mixed and / or impurities are supersaturatedly dissolved is any solution as long as the valuable substance can be adsorbed and recovered by an adsorbent. Although applicable, generally, gallium, uranium, indium, germanium, palladium, ruthenium, rhodium, platinum, molybdenum, niobium, tantalum, rare metals such as rare earths, ores containing valuable metals of precious metals, slag, scrap, or waste catalyst Examples include liquids leached with acid or alkali.

More specifically, Bayer method sodium aluminate aqueous solution in which bauxite is leached with alkali, zinc slag, black mine,
Examples include liquids obtained by leaching smoke ash and the like with sulfuric acid, liquids obtained by leaching spent catalysts such as automobile exhaust gas oxidation catalysts and petroleum reforming catalysts with acid or alkali.

The viscosity of the solution is 1-100 CP. The solid impurity particles contained in the solution are metal hydroxides, metal particles, sodium phosphate, silica, and other inorganic substances that are insoluble or sparingly soluble in a solvent, and their size is generally relatively difficult to settle or separate. Those having a particle size of 100 μm or less and having a particle size of 1 μm or more, which is difficult to pass through the voids between the adsorbent particles, correspond to the above.

Impurity components dissolved in supersaturation are derived from raw materials to be leached, and include inorganic compounds such as vanadium, arsenic, phosphorus, and fluorine, and organic compounds such as oxalic acid and humic acid.

As the adsorbent used in the practice of the present invention, any adsorbent can be used as long as it has the ability to adsorb a valuable substance in a solution, and it may be appropriately selected by a preliminary experiment.

As such an adsorbent, for example, (A) =
A resin or compound having a NOH group and (B) a functional group capable of forming a chelate bond via a valuable ion adsorbed to the (A) functional group, a resin or compound having a metal salt of the functional group, an oxine ligand resins or compounds _{having, -NH 2, -OH, -N (} CH 3) 2, = O, -SH, = S, = NOH, -NHOH, -CS 2 H, -COOH,
_{-PO 2, NHCH 2 CH 2 n} , NH 2, Resins or compounds containing one or more functional groups such as can be used. More specifically, a polymer having a nitrile group such as an acrylonitrile-divinylbenzene copolymer having an amine reactive group or a primary and / or secondary amino group, a styrene-divinylbenzene copolymer, a phenol resin, For polymers such as polyvinyl chloride, hydroxylamine, diethylenetriamine, guanidine,
Hydrazine, diethylamine, trimethylamine, dimethylethanolamine, 2,4-diaminophenol, 2,2
-Dihydroxy-5-diethylenetriamino-N, N-ethanediylidene dianiline, acetylacetone, oxalyl chloride, carbon disulfide, iminodiacetic acid, monochloroacetic acid, etc. Examples thereof include resins or compounds having a functional group having a plurality of atoms, or adsorbents obtained by impregnating these resins and compounds into a porous carrier.

The particle size of the adsorbent used in the present invention is not particularly limited as long as it is larger than the solid impurity particles or the precipitated impurities contained in the treatment solution. In order to separate the adsorbent and the solid impurity particles, an adsorbent having a diameter larger than the maximum particle diameter of the solid impurity particles by 50 μm or more is recommended.

Generally, an adsorbent having a particle size of 150 to 1000 μm is preferably adopted. The amount of the adsorbent used is not particularly limited, and it may be appropriately determined by a preliminary experiment depending on the concentration of valuables in the treatment solution, the type of adsorbent used, and the like.

The volume of the adsorbent layer and the length of the layer are determined from the necessary contact time between the valuable substance-containing solution and the adsorbent and the flow rate of the valuable substance-containing solution. These can be appropriately obtained by preliminary experiments.

The layer of adsorbent is formed by accumulating it in a container having a port for the flowing liquid.

Generally, a metal net or a porous support plate such as a perforated plate is attached and filled on the inlet side and the outlet side of the container so that the adsorbent does not flow out. The layer of the adsorbent of the present invention is formed not with the support plates on the inlet side and the outlet side for compressing the adsorbent to perform the unraveling operation, but with a slight margin space.

The adsorbent accumulates on the support plate on the outlet side to form a layer due to the flow of the circulating liquid, and thus the support plate on the inlet side is not always necessary.
This means that if the inlet side of the flowing liquid is the upper part and the outlet side is the lower part, the adsorbent layer is formed in the lower part by gravity as well as by the flow of the liquid, but the inlet side of the flowing liquid is the lower part, and the outlet side is This is because the adsorbent also accumulates on the outlet side of the upper part due to the flow of the liquid in the upper part to form a layer. In the method of the present invention, solid impurity particles are attached to the voids of the adsorbent layer during the flow of the treatment solution, or the supersaturated dissolved impurity components are deposited to fill the voids, which hinders the liquid flow. Prevent by unraveling the adsorbent layer in.

The operation of unraveling the adsorbent layer is carried out continuously or intermittently in order to provide a void through which mixed solid impurity particles and precipitated impurities can pass through the adsorbent layer.

As methods for solving this, there are a method of mechanically stirring or vibrating the adsorbent layer, a method of blowing gas into the adsorbent layer, or a method of jetting a liquid to disturb the layer. Above all, it is preferable in terms of operation to rotate the stirring blade in the adsorbent layer from the top of the device. The voids in the adsorbent layer are expressed by the following Kozeny-Corman formula. ΔP: Pressure loss (pressure difference between outlet and inlet of adsorbent layer) lp: Bed height (layer of adsorbent layer) u: Fluid velocity (flow velocity of the liquid containing the valuable material) ε: Porosity (adsorbent Porosity of the layer) μ: Fluid viscosity (viscosity of the valuable-containing liquid) ^g c: Gravity unit conversion coefficient Dp: Particle size (particle size of adsorbent) If ΔP is large, it is necessary to increase the pressure resistance of the equipment for accommodating the adsorbent layer, and a pump or the like for delivering the valuable substance-containing liquid also needs to have a higher pressure. Is desirable.

Further, if the adsorbent itself deforms due to external pressure, the deformation accompanying the increase of the pressure loss ΔP secondarily decreases the porosity, so that ΔP increases more and more, and finally the liquid passage becomes impossible. It will be possible. Taking these into consideration, the porosity of the adsorbent layer in the passage is preferably 0.3 or more, and at least when the adsorbent layer is unwound, the porosity is preferably 0.3 or more.

By doing so, the valuable substance-containing liquid can be passed continuously without interruption in the middle until the adsorbent is saturated and adsorbed.

As described above, the adsorbent that has adsorbed and collected the valuable substance elutes the valuable substance by a known method. Gallium, uranium,
Indium and germanium should be eluted with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide, iminodiacetic acid, ethylenediaminetetraacetic acid, etc., and molybdenum should be eluted with caustic soda, sodium sulfide, potassium hydroxide, calcium hydroxide, ammonia, etc., or heated. To separate valuables.

Further, the separated valuable materials are collected by a known method,
Further refine. For example, gallium is converted to sodium galmate and electrolyzed as gallium metal, uranium is concentrated as a nuclear fuel, indium is converted to sulfate as indium metal by electrolysis, and germanium is neutralized and dried to form germanium sulfide. Molybdenum is used as a germanium metal by subjecting it to reduction treatment if necessary, Experimental Chemistry Lecture, 10, Manufacturing of Rare Metals,
Issued by Maruzen Co., Ltd. on June 20, 1964, chemically processed by the method described in the above and acquired.

(Examples) Hereinafter, the method of the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

Examples 1-4 of the Bayer process Na ₂ was obtained from the following steps Nitsuma _{O169g / l, Al 2 O 3} 71g /
Sodium aluminate in which 2g / l of aluminum hydroxide with a particle size of 50μm exists with a composition of l, Ga0.189g / l, V0.38g / l, P0.18g / l, organic matter concentration (as sodium oxalate) 19.8g / l A sample consisting of an aqueous solution (50 ° C, specific gravity 1.25) is placed in a column with an inner diameter of 300 mmφ, 6 l of the adsorbent described below with a center particle size of 300 μm and a specific gravity of 1.15 to 1.30, and 11 / min for 12 hours while thoroughly stirring with a stirrer. After passing through the liquid, the pressure difference between the column inlet and the column outlet and the amount of adsorbed gallium obtained the results shown in Table 1.

Comparative Examples 1 to 4 The same sample as in Examples 1 to 4 was used and the same adsorbent and apparatus as those used in Examples 1 to 4 were used. Shown in.

Type of Adsorbent Adsorbent A A resin having an amidoxime group obtained by the reaction of polyacrylonitrile, hydroxylamine hydrochloride and an aqueous solution of sodium hydroxide is referred to as adsorbent A.

Adsorbent B A resin having = NOH group, -NH ₂ group and -OH group obtained by reacting 2-aminomethylbenzaldoxime, resorcin and formalin is referred to as adsorbent B.

Adsorbent C 7- (5,5,7,7-tetramethyl-1-octen-3-yl) -8-hydroxyquinoline, resorcin and formalin are impregnated in activated carbon and then heated to be solvent-inactivated. An adsorbent having an oxine ligand is obtained and is referred to as adsorbent F.

Adsorbent D acrylonitrile polyacrylonitrile obtained by polymerizing impregnated into activated carbon - the composite material of the activated carbon is reacted with an aqueous solution of hydroxylamine and hydrazine, = NOH, -NH _2,
An adsorbent having —NHNH ₂ , ═NH groups is obtained and is called adsorbent D.

Examples 5 to 8 The same samples used in Examples 1 to 4 were cooled to 40 ° C., and the samples in which the impurities were supersaturated were the same adsorbent as used in Examples 1 to 4, while sufficiently stirring with a stirrer with a device. 11 / min
After passing the solution for 12 hours, the pressure difference between the column inlet and the column outlet and the amount of adsorbed gallium obtained the results shown in Table 2.

Comparative Examples 5 to 8 The same sample as in Examples 5 to 8 was used and the same adsorbent and apparatus as those used in Examples 5 to 8 were used, and the results were obtained when the liquid was passed at 11 / min without stirring. Shown in the table.

Example 9 750 mg / l molybdenum, 100 g / l sulfuric acid and particle size 20-60
Molybdenum catalyst containing 0.7 g / l of solid impurity particles of μm
Sulfuric acid leachate was applied to a column with an inner diameter of 20 mmφ, the center particle size was 450 μm,
A chelate bearing a commercially available dithiocarbamic acid group with a specific gravity of 1.30.
Resin Sumichelate 85 ml of Q-10 (Sumitomo Chemical Co., Ltd.)
850ml / while mixing well and stirring with air bubbling
The pressure at the column inlet and column outlet when the solution is passed for 6 hours
The force difference and the amount of molybdenum adsorbed were measured and the results shown in Table 3 were obtained.
It was

Comparative Example 9 Using the same sample and adsorbent as used in Example 9, the pressure difference between the column inlet and the column outlet when 850 ml / hour was passed through the apparatus without stirring and the results in Table 3 were obtained. It was

Examples 10 to 12 Commercially available amidoxime-type chelates for columns with an inner diameter of 30 mmφ
Resin duolite CS-346 (Diamond Shamrock
KU), iminodiacetic acid type chelate resin Sumichelate
MC-30 (Sumitomo Chemical Co., Ltd.), aminomethylene phosphone
Acid type chelating resin Sumichelate MC-95 (Sumitomo Chemical Co., Ltd.
(Manufactured by Mfg. Co., Ltd.) filled with 280 ml each of 350-550 μm particle size product,
Solid impurity particles with a particle size of 10 to 50 μm while stirring with bling
Uranium enrichment containing 100 mg / l uranium containing 0.07 g / l offspring
When seawater was passed for 24 hours at a rate of 1.4l / hour, Table 4
The results shown in are obtained.

Comparative Examples 10 to 12 When the same samples and adsorbents as those used in Examples 10 to 12 were used and the solution was passed through the apparatus at 1.4 l / hour without stirring, the results shown in Table 4 were obtained.

Examples 13 to 16 A commercially available amido oxime type cleaner was applied to a column having an inner diameter of 300 mmφ.
Resin duolite CS-346 (Diamond Shamro
CK), aminomethylenephosphonic acid type chelate resin
Michelate MC-95 (Sumitomo Chemical Co., Ltd.), iminodiacetic acid
Type chelate resin Sumichelate MC-30 (Sumitomo Chemical Co., Ltd.
Made), strong basic ion exchange resin Duolite A-161
(Diamond Siam Rock Co., Ltd.) 350-500μm particle size
Fill the product with 21 each and stir well with a stirrer.
Lead concentration 20g / l, indium concentration 110mg / l, germanium concentration
50 mg / l, pH 1.4 containing 0.5 g / l of 10-50 μm particle size,
A zinc slag leachate with a viscosity of 7.8 cp was passed at 210 l / hour for 6 hours.
The pressure difference between the column inlet and outlet, and indium,
The amount of adsorbed germanium was obtained as shown in Table 6.

Comparative Examples 13 to 16 Table 6 shows the results obtained by using the same samples and adsorbents as those used in Examples 13 to 16 and passing 210 l / hour through the same apparatus without stirring.

(Effects of the Invention) As described in detail above, the present invention is a solution in which solid impurity particles are mixed or a valuable substance-containing solution in which impurities are supersaturated by a simple device or operation, and further exists in solid impurity particles or supersaturation. Even if valuable materials are adsorbed and collected by continuously passing through the adsorbent layer without removing impurities, it is possible to prevent obstacles such as clogging of the adsorbent layer due to solid impurity particles or precipitated impurities, Adsorption can be continuously performed until the adsorption capacity of the adsorbent is saturated, and as a result, the collection amount and collection efficiency of valuables can be increased.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical location C01G 43/00 D (72) Inventor Seiji Fujimoto 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. Within the corporation (56) References JP 62-183810 (JP, A) JP 56-22510 (JP, B2)

Claims (1)

[Claims] 1. A solution containing a valuable substance of a rare metal or a noble metal in which solid impurity particles are mixed and / or impurities are supersaturatedly dissolved is circulated through a solid granular adsorbent layer accumulated in a container, In the method for collecting valuables, the adsorbent layer is collected by a porous support plate provided on the outlet side of the container, and the solution is circulated while the adsorbent layer is unraveled. How to characterize.