CN110394146A - A kind of preparation method of palladium ion adsorption material and product thereof - Google Patents

Abstract

The invention discloses a preparation method of a palladium ion adsorption material and its product. The invention first activates the silica gel with acid, and then uses γ-aminopropyltriethoxysilane, aniline and the activated silica gel to react to realize the Amino functional groups are introduced into the surface of silica gel to prepare SiO ₂ ‑NH ₂ , and then further introduce cyano functional groups on the surface of SiO ₂ ‑NH ₂ to obtain a composite material, and then introduce amino groups on the surface of the composite material by chemical grafting to obtain Palladium ion adsorption material. This preparation process can realize the introduction of a large number of amino functional groups into the surface of silica gel, and prepare _SiO2 composite materials containing amino groups, and then realize the high adsorption rate of the adsorption material for palladium ions and good selectivity for ions in the solution.

Description

A kind of preparation method of palladium ion adsorption material and product thereof

technical field

The invention belongs to the field of separation, recovery and utilization of palladium ions, and specifically discloses a preparation method of a palladium ion adsorption material and a product thereof.

Background technique

The main source of palladium-containing waste liquid is electroplating waste liquid such as activation and passivation in the process production of various electronic industries. The waste liquid is weakly acidic and the palladium content is ~50ppm. Palladium, gold and other precious metal production waste liquid contains ~ 10ppm of palladium. The workpiece cleaning wastewater after the metallization of printed circuit board holes, plastic electroplating and various non-metallic electroplating activation also contains a certain amount of palladium, and its content is ~ 1ppm. The study found that a large amount of palladium-containing waste liquid in the electroplating industry is discharged as ordinary wastewater, which not only increases the difficulty of subsequent wastewater treatment, but also causes a waste of resources. According to statistics, about 3 tons of metal palladium in the palladium-containing waste liquid produced by my country's electroplating and circuit board industries cannot be effectively recovered. In addition, the accumulation of palladium emissions in the environment will endanger human health, such as causing diseases such as asthma, allergies and rhinitis. In order to improve the recovery rate of palladium in printed circuit board waste liquid, researchers at home and abroad have successively carried out different researches on technologies such as extraction method, ion exchange method and resin adsorption method. Although these studies have made some progress in some aspects, there are still some shortcomings. Better treatment technology can only reduce the palladium content to 3-4ppm. The different forms of palladium in palladium-containing waste liquid is one of the important reasons for the decrease of palladium recovery.

Some composite materials for adsorption and separation of palladium have also been synthesized in the existing technology, but the use effect is limited. For example, CN102009983A discloses a mercapto-modified SBA-15 molecular sieve and its preparation and use method. It utilizes adding SBA-15 molecular sieve into the prepared mercapto-modifier ethanol aqueous solution and stirring at room temperature for 36-48 hours to obtain mercapto-modified SBA -15 molecular sieve product. It uses ethanol as a medium, and the reaction time is too long, and the final product efficiency is also unsatisfactory. CN1136960C discloses a method for preparing sulfhydryl functionalized MCM-48 mesoporous molecular sieve. It is prepared by using MCM-48 mesoporous molecular sieve and mercaptopropyltrimethoxysilane toluene solution to reflux for 12 to 24 hours, but it adopts the reaction method of direct reflux of mesoporous molecular sieve and mercaptopropyltrimethoxysilane toluene solution to prepare the Product adsorption is limited. CN201510379076.4 discloses a carboxyl-terminated dendritic polymer adsorption material and a preparation method thereof. The disclosed technical scheme is to dissolve cyanuric chloride in acetone or tetrahydrofuran and add it to the acetone solution of dibasic alcohols to obtain The crude product of the first-generation hydroxyl-terminated dendritic polymer is purified to obtain the first-generation hydroxyl-terminated dendritic polymer; the second-generation and third-generation hydroxyl-terminated dendritic polymers are obtained by using cyanuric chloride as the core and the first-generation hydroxyl-terminated dendritic polymer as the branch unit The crude product is purified again; the hydroxyl-terminated dendritic polymer is dispersed in water, and maleic anhydride and p-toluenesulfonic acid are added to obtain a crude carboxyl-terminated dendritic polymer, which is purified to obtain a carboxyl-terminated dendritic polymer adsorption material. This patent utilizes carboxyl adsorption properties, but its disclosed technical solutions all use polymer materials, which have high cost and complicated process conditions.

Contents of the invention

In view of the technical defects in the prior art, the purpose of the present invention is to provide a method for preparing a palladium ion adsorption material, and the prepared product can effectively adsorb palladium ions.

Concrete technical scheme of the present invention is:

1, a kind of preparation method of palladium ion adsorption material, comprises the steps:

1) Disperse the activated silica gel in toluene, slowly add γ-aminopropyltriethoxysilane and aniline under the condition of uniform stirring, heat the reactant to 60-120°C and stir the reaction for 8-24h to obtain the Amino silica gel composite material, and labeled as SiO ₂ -NH ₂ ;

2) Disperse the SiO ₂ -NH ₂ obtained in step 1) in acrylonitrile, and stir the reaction at 100-130°C for 6-12 hours, and the obtained product is marked as SiO ₂ @CN;

3) Disperse the SiO ₂ @CN obtained in step 2) in an amine solvent, stir and react at a temperature of 100-150°C for 8-12 hours, and after the reaction is completed, the solid is obtained by suction filtration, which is the palladium ion adsorption material, which is marked as SiO ₂ @CN-NH ₂ .

Preferably, the preparation method of the activated silica gel described in step 1) is: disperse the chromatography silica gel in one or more of 1-10 mol/L hydrochloric acid, sulfuric acid, nitric acid or sulfonic acid, and heat it to 60-120°C , stirred and reacted for 3-24 hours, then filtered with suction, washed with deionized water until neutral, and dried in a drying oven at 110°C for 12 hours to obtain activated silica gel.

Preferably, the mass volume ratio (g/mL) of the activated silica gel to toluene in step 1) is 1 to 10:25, and the mass volume ratio (g/mL) of the activated silica gel to γ-aminopropyltriethoxysilane mL) is 1:0.3~2, and the mass volume ratio (g/mL) between activated silica gel and aniline is 100:0.1~5.

Preferably, the mass volume ratio (g/mL) of SiO ₂ -NH ₂ to acrylonitrile in step 2) is 0.03˜0.4:1.

Preferably, the amine solvent in step 3) includes one or more of diethylenetriamine, ethylenediamine, triethylenetetramine, and tetraethylenepentamine.

Preferably, the mass volume ratio (g/mL) of SiO ₂ @CN to the amine solvent in step 3) is 0.03˜0.4:1.

Preferably, the solid obtained in step 3) is further washed repeatedly with a large amount of deionized water to neutrality, then rinsed with absolute ethanol for 2 to 3 times, and dried in a vacuum oven at 70°C for 8-12 hours to obtain palladium ion adsorption Material.

2. The palladium ion adsorption material obtained according to the preparation method described in any one of the above.

The beneficial effect of the present invention lies in that: the present invention first uses acid to activate the silica gel, and then uses γ-aminopropyltriethoxysilane, aniline to react with the activated silica gel, so that the silica gel surface has amino groups, that is, SiO ₂ -NH ₂ , Then further modify the surface of SiO ₂ -NH ₂ to introduce cyano groups, and then graft amino groups on the surface of the composite material. This preparation process can realize the introduction of a large number of amino functional groups into the surface of silica gel, and prepare SiO ₂ composite materials containing amino groups. , and then realize that the adsorption material has a high adsorption rate for palladium ions, and has a good selectivity for ions in the solution.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

Example 1

The preparation method of palladium ion adsorption material, comprises the steps:

1) Add 60g of chromatographic silica gel and 500mL of 6mol/L hydrochloric acid solution into a 1000mL three-neck flask, heat to 110°C, stir and reflux for 8h, wash it with a large amount of deionized water until neutral after the reaction is completed, and place it at 110°C Dry 12h to obtain activated silica gel;

2) Weigh 5.0g of activated silica gel in a 250mL three-neck flask, add 100mL of toluene as a solvent, add 5mL of γ-aminopropyltriethoxysilane under stirring conditions, and finally add 0.2mL of aniline, and heat to Stir and reflux at 110°C for 24 hours. After suction filtration, dry in a drying oven at 110°C for 12 hours. The dried product taken out is the amino silica gel composite material;

3) Disperse 5g of amino silica gel in 125mL of acrylocyanide, stir and heat in an oil bath at 130°C for 8h, filter and dry in a vacuum oven at 70°C for 12h to obtain cyanosilica gel SiO ₂ @CN;

4) Disperse 5g of cyanosilica gel SiO ₂ @CN in 125mL of diethylenetriamine, stir and heat in an oil bath at 130°C for 10h, wash it with a large amount of deionized water after the reaction is complete, and then wash it with anhydrous Rinse with ethanol three times, and dry in a vacuum oven at 70°C for 12 hours to obtain the SiO ₂ @CN-NH ₂ composite material.

Example 2

The preparation method of palladium ion adsorption material, comprises the steps:

1) Add 60g of chromatographic silica gel and 500mL of 6mol/L hydrochloric acid solution into a 1000mL three-neck flask, heat to 110°C, stir and reflux for 8h, wash it with a large amount of deionized water until neutral after the reaction is completed, and place it at 110°C Dry 12h to obtain activated silica gel;

2) Weigh 5.0g of activated silica gel in a 250mL three-neck flask, add 100mL of toluene as a solvent, add 5mL of γ-aminopropyltriethoxysilane under stirring conditions, and finally add 0.2mL of aniline, and heat to Stir and reflux at 110°C for 24 hours. After suction filtration, dry in a drying oven at 110°C for 12 hours. The dried product taken out is the amino silica gel composite material;

3) Disperse 5g of amino silica gel in 160mL of acrylocyanide, stir and heat in an oil bath at 130°C for 8h, filter and dry in a vacuum oven at 70°C for 12h to obtain cyanosilica gel SiO ₂ @CN;

4) Disperse 5g of cyanosilica gel SiO ₂ @CN in 160mL of diethylenetriamine, stir and heat in an oil bath at 130°C for 10h, wash it with a large amount of deionized water to neutral after the reaction is completed, and then wash it with anhydrous Rinse with ethanol three times, and dry in a vacuum oven at 70°C for 12 hours to obtain the SiO ₂ @CN-NH ₂ composite material.

Adsorption palladium ion performance test:

The composite material that embodiment 1 and embodiment 2 obtains is weighed 3.0g respectively, packs in the fixed bed (diameter 6mm, height 100mm), will contain the waste water that palladium initial concentration is 100mg/L to pass through the fixed bed, the penetration volume respectively It can reach 7.6L and 7.7L, the maximum dynamic saturated adsorption capacity can reach 254.3mg/g and 255.1mg/g respectively, and the enrichment factor can reach 633 and 642 respectively.

The composite material after adsorption was eluted with a mixed solution composed of 12mL, 6mol/L hydrochloric acid and 30g/L thiourea. The concentration of palladium ions in the eluent was as high as 60g/L and 62.8g/L respectively. Neither the maximum dynamic saturated adsorption capacity nor the enrichment factor is significantly reduced, and the separation and recovery of all palladium ions in the wastewater solution can be realized. The above examples further demonstrate that the composite material disclosed in the present invention has a high adsorption rate for palladium ions, good selectivity for palladium ions in solution, and the material can be reused many times, and the adsorption performance is basically unchanged.

Finally, it is noted that the specific embodiments of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiments. Make various changes below.

Claims (8)

1. a kind of preparation method of palladium ion adsorbent material, which comprises the steps of:

1) it disperses activated silica gel in toluene, is slowly added to gamma-aminopropyl-triethoxy-silane under conditions of uniform stirring And aniline, being heated to being stirred to react 8-24h under the conditions of 60-120 DEG C of temperature for reactant, to obtain the silica gel containing amino compound Material, and it is labeled as SiO₂-NH₂；

2) by SiO obtained by step 1)₂-NH₂It is scattered in propylene cyanogen, and is stirred to react 6- under the conditions of 100~130 DEG C of temperature 12h, products obtained therefrom are labeled as SiO₂@CN；

3) by SiO obtained by step 2)₂@CN is scattered in amine solvent, it is stirred to react 8 under the conditions of 100~150 DEG C of temperature~ 12h, filter after the reaction was completed solid to get palladium ion adsorbent material, and be labeled as SiO₂@CN-NH₂。

2. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that living described in step 1) SiClx glue the preparation method comprises the following steps: by chromatographic silica gel be scattered in one of hydrochloric acid, sulfuric acid, nitric acid or sulfonic acid of 1-10mol/L or It is several, it is heated to 60-120 DEG C, is filtered after being stirred to react 3-24h, is washed with deionized water to neutrality, in 110 DEG C of dryings Dry 12h, obtains activated silica gel in case.

3. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that the step 1) activation The mass volume ratio (g/mL) of silica gel and toluene is 1~10:25, the activated silica gel and gamma-aminopropyl-triethoxy-silane Mass volume ratio (g/mL) is 1:0.3~2, and the mass volume ratio (g/mL) between activated silica gel and aniline is 100:0.1~5.

4. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that the step 2) SiO₂- NH₂Mass volume ratio (g/mL) with propylene cyanogen is 0.03~0.4:1.

5. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that the step 3) amine Solvent includes one or more of diethylenetriamine, ethylenediamine, triethylene tetramine, tetraethylenepentamine.

6. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that the step 3) SiO₂@ The mass volume ratio (g/mL) of CN and amine solvent is 0.03~0.4:1.

7. a kind of preparation method of palladium ion adsorbent material according to claim 1, which is characterized in that further by step 3) Obtained solid is washed to neutrality repeatedly with a large amount of deionized waters, then is rinsed 2~3 times with dehydrated alcohol, and 70 DEG C of vacuum drying are placed in Dry 8-12h is in case to get palladium ion adsorbent material.

8. the palladium ion adsorbent material that any one of claim 1~7 preparation method obtains.