JPS5959715A - Chelate group-containing phenolic resin, its production and adsorption treatment - Google Patents

Abstract

PURPOSE:The titled resin capable of selectively adsorbing and recovering valuable metals even from a solution containing a large quantity of Al<3+> ions, having 2-methyl-8-hydroquinone as a ligand. CONSTITUTION:A chelate group-containing phenolic resin containing 2-methyl-8- hydroxyquinoline as the chelate group shows excellent complexing and separating abilities for metal ions and can adsorb metals, for example, Ga, Mo, and In, even from a solution containing a large quantity of Al<3+> ions. This resin can be obtained by reacting 2-methyl-8-hydroxyquinoline with an aldehyde under an alkaline condition to obtain an initial product, and either reacting the initial product with a phenol and an aldehyde to convert it into a three-dimensional structure by crosslinking, or by reacting the initial product with a phenol, an aldehyde and an aliphatic polyamine to convert it into a three-dimensional structure by crosslinking.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel chelating group-containing phenol j+t which has excellent complex-forming ability and separation ability for metal ions.
18 (hereinafter referred to as phenolic chelate mfIlf), its production method, and adsorption treatment method.

Chelate resins are currently attracting attention as a social problem due to the environmental pollution caused by heavy metal ions contained in industrial wastewater and research laboratory wastewater. highly praised,
Widely used in industry. In particular, polystyrene resin,
Chelate resins, which have polyacrylic acid resins and phenolic resins as the resin base, and into which chelate groups such as iminodiacetic acid, polyamines, and dithiocarbamic acid are introduced, have been put to practical use as effective heavy metalloid treatment 3E and are commercially available. ,
For example, Dowθx A=l (manufactured by Dow Chemical Company).

Tire Ioshi cR-〇I, 2 (1 (manufactured by Mitsubishi Chemical Corporation),
Examples include UNINAREC UR-10 to UR-50 (manufactured by Unitika), Sumikire-1/MO-30 (manufactured by Sumitomo Chemical), and the like. However, most of these items have poor selectivity for metal ions (F), and certain metal ions (
For example, there are limits to more selective adsorption treatment of aluminum sulfate (for example, recovery of gallium from aluminum sulfate), and fi12 has sufficient selectivity for gold 17'Ti ions and is low cost. If a chelate resin of n is obtained, it has many uses. Particularly, in the field of marine wire making, KIRE-1 resin is desired, which can be applied to the recovery of specific metals, for example, valuable metals such as gallium-7-molybdeno and indium, from aqueous solutions containing aluminum.

ing.

In response to this current situation, the inventor of the tree conducted intensive research with the aim of providing a chelate resin that can selectively adsorb the valuable metals mentioned above, even in solutions containing large amounts of aluminum ions. As a result, 2-methyl-8-
It was discovered that a phenolic chelate resin containing hydroxyquinoline as a ligand is suitable for the above purpose7.
We have arrived at the present invention.

That is, the present invention relates to a phenol resin having a chelate group, characterized in that it has 2-methyl-8-hydroxyquinoline as a chelate group, and a phenol resin having a chelate group, 2-methyl-8-hydroxyquinoline, phenols, and A method for producing a phenolic resin having chelate-forming ability, which comprises crosslinking aldehydes into three-dimensional forms in the presence or absence of aliphatic polyamines, and using 2-methyl-8-hydroxyquinoline as the chelate group. This is an adsorption treatment method characterized by adsorbing gold ions in an aqueous solution in large quantities using a phenolic resin having the following properties.

The phenols used in the present invention include, for example,
Phenol, 〇-ethylphenol゛m-ethylphenol/p-ethylphenol/bisphenol A-0-
Cresol・ml/ Sole・p-cresol・2
,8-xylenol・2,5-xylenol・8.4-
Alkyl-substituted phenols such as xylenol and 8.5-xylenol, polyhydric phenols such as resorcinol and catechol, and compounds with phenolic hydroxyl groups such as σ-naphthol and β-naphthol. These can be used alone or in combination. Among them, phenol, bisphenol A, o-cresol, m-cresol, p-cresol, 8.5-xylenol, resorcinol, and catechol are preferred, and phenol and resorcinol are particularly preferred.

The aldehydes used in the present invention include Tatoha,
Aldehydes such as formaldehyde, parapormaldehyde, and hexamethylene retetramine; aliphatic aldehydes such as %4, acetaldehyde, and propionaldehyde; aromatic aldehydes such as benzaldehyde; and heterocyclic aldehydes such as furfural. These can be used alone or in combination, but formaldehyde, paraformaldehyde, and hexamethylene retetramine are particularly preferred.

Examples of the aliphatic polyamides used in the present invention include diethylenetriane, triethylenetetramine, and the like having the general formula (1) % formula % (1) (where n represents an integer from 1 to 1o). Compounds represented by the general formula (rll H,, N(C!H2)mNH,, (Ill (where m represents an integer from 2 to 1o) such as ethylene diamisi and l-rimethylene diamine) Compounds are preferred.Also, linear or branched polyethyleneimine can also be used.As for its molecular weight, for example,
aOO~70.000 is suitable, especially 8oo~i,
Soa is preferred.

To produce the chelate resin of the present invention, 2-methyl-8
- Three-dimensional crosslinking of hydroxyquinolines, phenols and aldehydes in the presence or absence of aliphatic polyamines. For this purpose, it is preferable to react the 2-methyl-8-hydroxyquinoline and the aldehyde under alkaline conditions in the first step to obtain the initial product.

In this case, the ratio of raw materials is 1 to 1 to 1 mole of aldehyde to 1 mole of 2-methyl-8-hydroxyquinoline.
It may be added at a rate of 8 mol, preferably 1.5 to 2.5 mol. Further, the alkali may be added in an amount of 1 mole or more per mole of 2-methyl-8-hydroxyquinoline, and usually 4 to 10% by weight of alkali metal hydroxide is used. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide,
Examples include lithium hydroxide, but sodium hydroxide is particularly preferred. Unfortunately, the temperature conditions for the synthesis reaction of the initial product are generally 10~50''C1, preferably 15~50''C1.
It was carried out at a temperature range of 35°C, and the reaction time was 5.
Minutes to 6() minutes, preferably 10 minutes to 80 minutes are sufficient. If the reaction time exceeds 60 minutes, it is not preferable because precipitates are formed and the initial product tends to be difficult to obtain.

Next, in the second step, the initial product obtained in the first step is cross-linked into three dimensions by reacting with phenols and aldehydes, or is reacted with phenols, aldehydes, and aliphatic polyamines. It is preferable to react to form a three-dimensional crosslinked structure. At that time, 2-methyl-8-
It may be added at a ratio of 0.8 to 2.0 moles, preferably 07 to 12 moles, per mole of hydroxyquinoline. In addition, aldehydes are added in an amount of 2 to 10 mol, preferably 8 to 10 mol, per 1 mol of 2-methyl-8-hydroxyquinoline.
It may be added at a ratio of 7 moles. Further, as aliphatic polyamines, 0.1 to 2.0 mol, preferably 0.3 to 0.0 mol, per 1 mol of 2-methyl-8-hydroxyquinoline.
It may be added at a ratio of 8 moles. Although the use of these aliphatic polyamines is not necessarily necessary for the chelate resin of the present invention, by adding them, a resin with excellent alkali resistance can be obtained, and furthermore, the separation ability for aluminum can be obtained. It has the advantage that the amount of adsorption does not decrease even when a small amount of ferric ion coexists.

In addition, the temperature and time required for the three-dimensional crosslinking reaction are not necessarily constant depending on the type of raw materials, the type of reaction solvent, and other conditions, but are generally 40 to 150'C and 1 to
The IO time may be selected preferably between 2 and 7 hours at 180°C.The shape of the resin may be spherical, powder, block, filament, etc. Although it can be molded into a nail shape, it is usually preferable to form it into small spheres. Conventionally, organic resins that do not mix with water are made using a method that is completely the same as the method for producing known small sphere-shaped phenolic chelate resins. By carrying out Bar condensation in a solvent, granulation and three-dimensional crosslinking can be carried out at the same time to obtain a small spherical chelate resin. Examples of the organic solvent used at this time include carbon tetrachloride, carbon tetrachloride, halogenated aliphatic hydrocarbons such as chloroform, trichlorethylene, perchlorethylene, chloral, dichloroethylene, dichloroethane, 1,2-dichloroethylene;

Halogenated aromatic hydrocarbons such as chlorobenzene, 0-dichlorobenzene, 1]-dichlorobenzene, bromobenzene, benzene, l-/L/E:/, O-xylene, m-xylene, p- Aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as cyclohexane and cyclopropane, and cyclohexanol.

Cyclic alcohols such as cyclopentanol can be used. The reaction temperature and reaction time during Parr army condensation are not necessarily constant depending on the vl of the reaction product, the type of solvent, and other conditions, but are usually 60 to 15 (1'
c for 1 to 7 hours, preferably 90 to 18 hours (2 to 5 hours at 1℃)
The temperature of the polycondensation reaction should be adjusted to 20°C to obtain a chelate resin with as uniform a composition as possible.
It is desirable to control the temperature to ~90°C and then gradually raise the temperature. Finally, the reaction is allowed to proceed under reflux while being kept at 90 to 130°C, and when the desired condensation stage is reached, dehydration is performed by heating under reduced pressure or normal pressure to obtain the desired resin composition. be able to.

The resin produced as described above is used as a chelate resin as it is or after washing.

The chelate resin of the present invention can be used in various ways depending on its shape. For example, the resin of the present invention may be used by filling a column or tower and passing a metal-containing solution through the column. It can be used by immersing it in a metal-containing solution. In this case, the temperature of the metal-containing solution is 5
~8(1℃) is suitable, and 15~5()℃ is preferable.The time for contacting the metal particles with the resin is appropriate for 1 minute to 50 hours, 10 minutes. -2 hours is preferable.

Furthermore, recovery of metal ions from the resin of the present invention that has adsorbed metal ions can be easily carried out by contacting with an aqueous mineral acid solution or an aqueous alkaline solution in the same way as with general commercially available chelate resins and ion exchange resins. It will be played again
: The resin can be used repeatedly.

The chelate resin of the present invention exhibits an immediate scavenging effect on various metal ions, and is effective for capturing metal ions such as gold scrap ions in aqueous solutions.
hismuth, cadmium, chromium.

Kobal 11. Copper, gallium, iron, indium, manganese, nickel, silver, titanium, zinc, molybdenum.

Forms complexes with tungsten, vanadium/etc. .

However, since almost no complexes are formed with aluminum, the difference in selectivity between these metals and aluminum can be used to adsorb the target valuable metal.

The KIRE-1 resin of the present invention is particularly suitable for systems where aluminum coexists, for example, recovering gallium from aluminum sulfate.
Separation of aluminum in zinc smelting, molybdenum from sulfuric acid leaching liquid of red mud.

It can be used for gallium recovery, etc. Moreover, it has excellent physical stability, chemical and mechanical stability, and can be used repeatedly by simple acid or alkali treatment, making it practical and compared to commercially available products. It can be used for different purposes than chelate resins.

Next, the present invention will be explained in more detail with reference to Examples.

Note that % in Examples does not indicate weight %.

In addition, the separation coefficient α is calculated as follows.
(Ga)sol.

(Al)sol is Ga in the liquid phase at equilibrium,
Concentration of A'L (represents (1)) Example 1 8.0 g of 2-methyl-8-hydroxyquinoline
)% sodium hydroxide aqueous solution (87.5 g),
879L5hok 7 phosphorus 16.2 g 25-80'
When the mixture was added dropwise under C, a homogeneous bath solution was obtained, and stirring was then continued for 20 minutes under ilO''c to obtain a -C initial product.

Next, add 5.5 g of resorcin to this initial product + 78. +
Dissolved in 87.5 g of 1% aqueous sodium hydroxide solution and added the aqueous solution so as not to exceed 8 (1'(j'', p), then added 16.2 g of X+796 formalin,
A reaction solution was obtained by heating and stirring at 5°C for 1 hour. This reaction solution was subjected to Pearl military condensation using perchlorethylene as a solvent in a conventional manner while water was distilled out of the system, yielding 22 g of a crosslinked three-dimensional resin in the form of small spheres.

After washing this resin with water, it was treated with 4.096 hydrochloric acid,
After washing with water, it was neutralized with a 4.0% aqueous sodium hydroxide solution. After that, if you wash it thoroughly with water, it will turn into a blackish brown resin.
Its moisture content was 55%, and its apparent density was 160 (it).

Example 2 159g of 2-methyl-8-hydroxyquinoline was 8.0g
9b Dispersed in 75g of sodium hydroxide aqueous solution, 37%
When 324 g of formalin was added dropwise at 25-30°C, a homogeneous solution was obtained, so (7)'! : 1 at 480°C
Stirring was continued for 0 minutes to obtain an initial product.

To this initial product, 11.0 g of resorcin was added at 8.0%.
Aqueous solution dissolved in 75 g of sodium hydroxide aqueous solution, 3.6 g of ethylene diamic acid and 82 g of 37% formalin aqueous solution
．． 4 g was added and stirred at 30° C. for 20 minutes to obtain a reaction solution. This reaction solution was subjected to barr condensation using perchlorethylene as a solvent in a conventional manner while water was distilled out of the system, yielding 48 g of a crosslinked three-dimensional resin in the form of small spheres.

When this resin was washed in the same manner as in Example 1, a dark brown resin was obtained with a water content of 53% and an apparent density of 780 g/l.

Example 8 When performing bar polycondensation in reaction 11k of Example 2, water was distilled out of the system (then, when the reaction was allowed to proceed for 15 hours at 100'C under reflux, cross-linked three-dimensional particles formed into small spheres were formed. A resin with a certain temperature was obtained.

After separating this resin by filtration, it was washed in the order of methanol, acetone, and water, and then treated with 40% hydrochloric acid 7. After washing with water, 4j
i Neutralize with aqueous sodium hydroxide solution. after that,
After thorough washing with water, a reddish-brown resin was obtained with a water content of 7896 and an apparent density of 680 q/1.

Example 4 5.9 g of 2-methyl-8-hydroxyquinolino was dispersed in 758 aqueous sodium hydroxide solution, and 82.4 g of 3796 formalin was added dropwise at 25 to 30 τ to obtain a homogeneous solution. I got f, so I left it at 30.
Stirring was continued for 20 minutes at °C to obtain the initial product.

To this initial product were added 94 g of phenol, 6.2 g of diethylenetriamine, 16.2 g of 87% formalin, and 4.0 g of sodium hydroxide, and the mixture was heated and stirred at 60° C. for 1 hour to obtain a reaction solution. When this reaction solution was subjected to bar polycondensation using chlorobenzene as a solvent in a conventional manner, 42
A cross-linked three-dimensional resin in the form of small spheres of g was obtained.
To .

When this resin was washed in the same manner as in Example 1, a blackish brown resin was obtained with a water content of 50% and an apparent density of 780 g7N.

Examples 5-8. Comparative Example 1 ], 100 my/l in a 00 me Erlenmeyer flask
Concentrated aqueous aluminum sulfate solution containing gallium 5
0me and the chelate resins produced in Examples 1 to 4 in a wet state. Add Om/ and shake at 80°.
for 24 hours. After the adsorption treatment, the resin was filtered and thoroughly washed with water, and then placed in a P+ degree 1 old 1 mP Erlenmeyer flask with water drained, and 50 me of 2N hydrochloric acid was added.
By contacting at 80°C for 24 hours, the adsorbed metal 2' was eluted.

Next, the gallium and aluminum concentrations in this 2N hydrochloric acid solution were measured by muntin absorption spectrophotometry, and the adsorption amount of each safe and the separation coefficient a (v) of gallium from aluminum were determined.

A] The results are shown in Table 1.

The composition of the gallium-containing aluminum sulfate aqueous liquid was as follows, l='.

(Ga, ; 100 mq/l,
A], ; 10,0 old 1 why/
For comparison, measurements were made in the same manner using a commercially available iminodiacetic acid group chelate pile (styrene type manufactured by 1M Co., Ltd.).

The results are also listed.

From Table 1, the KIRE-1 resin of the present invention has superior ability to separate aluminum and gallium compared to commercially available iminodiacetic acid type chelate resins, and almost selectively removes only Ga from high-strength aluminum salt solutions. It is clear that it is adsorbed to

Example 9. Comparative Example 2 The chelate resin obtained in Example 8 and the commercially available iminodiacetic acid type chelate resin (manufactured by M Company) were each packed into a glass column with an inner diameter of 9 mm as wet resin, and an aqueous solution of aluminum sulfate containing gallium was added. The liquid is passed in a downward flow at a space velocity of 5 hr' (adsorption step). When the adsorption of gallium reaches saturation, that is, when the gallium concentration after passing the liquid exceeds 50 mp/z, the liquid is passed through. Stop 7, then wash the resin for 1 hour at a space velocity of 5 hr', then rinse with 2N
Hydrochloric acid was passed through the solution for 2 hours at a space velocity of 2 hr' (desorption step), and the concentrations of gallium and aluminum in the eluent at a bed volume of 0.5 to 1.0 were measured.

The results are shown in Table 2.

The composition of the gallium-containing aluminum sulfate aqueous solution is as follows.

(Ga, ; LOOmIr/e, Al i 12
．． (1110-1, PH=8.1>Table 2 From the results in Table 2, the clear resin of the present invention has a higher concentration of aluminum than the commercially available imino di+"ip acid type chelate resin. It is clear that only gallium can be selectively adsorbed among the 11 components.

Example 10 ~] 1 1 oo m each in a 100+++t' Erlenmeyer flask
50 mC of a concentrated aluminum aqueous solution containing y/l of gallium and ferric iron and 1.0 me of the chelate resin produced in Example 1.2 were added in a wet state and brought into contact at 30°C for 24 hours with shaking. Thereafter, the concentration of metal ions in the treatment solution was measured by atomic absorption spectrophotometry.

The results are not shown in Table 8.

The composition of the aluminum sulfate aqueous solution is as follows.

(Ga; 102mp/l, Fe(III);
100mp/r, Al; 10,000my/
i, PH8,1) According to Table 3, those to which aliphatic polyamines were added were Fe
Even if (Ill) coexists with Ga at the same concentration, the adsorption i+i does not decrease, and the separation coefficient from ferric iron is also large.

Claims (4)

[Claims] (1) In a phenolic resin that forms a chelate group,
4. A phenolic resin having a group to Kir-1, characterized in that 2-methyl-8-hydroxyquinoline is in the η phase as Kir-+-'Jk. (2) Presence of 2-methyl-8-hydroxyquinoline, phenols, and aliphatic polyamines
Is it possible to cross-link three-dimensionally in the presence or absence of a compound? A method for producing a phenolic resin having 2-methyl-8-hydroxyquinoline as a chelate group. (3) 2-Methyl-8-hydroxyquinoline and aldehydes are reacted under alkaline conditions to obtain an initial product, and then the obtained initial product is reacted with phenols and aldehydes to form a tertiary cross-linked product. The manufacturing method according to claim 2, which comprises converting the polyamine into three-dimensional crosslinks by reacting with phenols, aldehydes, and aliphatic polyamines. (4) As a key note base? - An adsorption treatment method characterized by selectively adsorbing metal ions in aqueous solution using a phenol tree 1.1f having methyl-8-hydroxyquinoline.