CN107321314B - Preparation method and application of green high-efficiency palladium magnetic adsorbent - Google Patents
Preparation method and application of green high-efficiency palladium magnetic adsorbent Download PDFInfo
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Abstract
The invention provides a preparation method of a green high-efficiency palladium magnetic adsorbent, which comprises the following steps: step S101, adding a certain amount of CaCO into waste glass serving as a main raw material3、SiC、H3BO3And iron powder, crushing, sieving, uniformly mixing, and carrying out temperature programming to obtain the magnetic porous microcrystalline glass; step S102, suspending a certain amount of the magnetic porous microcrystalline glass obtained in the step S101 in toluene, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing, filtering, and drying at room temperature to obtain a microcrystalline solid; and S103, suspending the microcrystalline solid obtained in the step S102 in methanol, adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde respectively, refluxing, filtering and drying in vacuum to obtain the palladium magnetic adsorbent. The preparation method of the green high-efficiency palladium magnetic adsorbent provided by the invention can be used for effectively adsorbing palladium ions in sewage, and is simple in preparation process, low in production cost and good in environmental friendliness.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a preparation method of an efficient magnetic adsorbent taking palladium as an adsorption target.
Background
Palladium has unique physical and chemical properties, plays an increasingly important role in the fields of petrochemical industry, national defense research and the like, but has excellent physicochemical properties, and is widely applied to the fields of shape-selective catalysis, automobile element manufacturing and the like. The demand for palladium will also increase with the development of society. However, the palladium resource is very limited, the earth crust content is only 0.01g/t, and the palladium is often coexisted with other elements, so that the extraction is difficult. The palladium is mainly produced from byproducts of nickel and copper ores, has low yield and low grade, and can not meet the market demand. However, with the development of electronic information products and integrated circuit industries, a large amount of waste materials such as waste gas, waste residue, and waste liquid containing palladium must be generated in the production process of various electronic products. If the waste is not recycled, not only the ecological environment and the human health are seriously harmed, but also a great deal of waste of precious metals such as platinum, palladium and the like contained in the waste is caused.
In order to recover and reuse palladium, various methods such as a precipitation separation method, a solvent extraction method, an ion exchange method, an electrolytic deposition method, and the like have been developed. The precipitation separation method, the ion exchange method, the electrolytic precipitation method and the like have complex production process and high cost in the practical application process and are difficult to realize; therefore, from the viewpoint of economy and operability, a solvent extraction method is widely used at present. However, the solvent extraction method of the prior art generally uses a large amount of extraction solvent or adsorbent, and the production cost of the extraction solvent or adsorbent is high, the preparation process is complicated, secondary damage to the environment is easily caused in the using process, and problems in the aspects of safety and environmental burden exist.
Disclosure of Invention
In order to solve the problems, the invention aims to design a preparation method of a green high-efficiency palladium magnetic adsorbent, which can effectively adsorb palladium ions in sewage, realize resource recovery of noble metal palladium, realize resource utilization of waste by using waste glass as a raw material, and has the advantages of simple preparation process, low production cost and good environmental protection.
According to the invention, waste glass is used as a main raw material, CaCO3, SiC, iron powder and H3BO3 are added to prepare the magnetic porous microcrystalline glass, the magnetic porous microcrystalline glass is used as a substrate, an efficient adsorbent for heavy metal palladium is obtained by loading organic functional groups, and resource recovery of precious metals is realized.
The invention adopts the following technical scheme to realize the aim:
a preparation method of a green high-efficiency palladium magnetic adsorbent comprises the following steps:
step S101, adding a certain amount of CaCO into waste glass serving as a main raw material3、SiC、H3BO3And iron powder, crushing, sieving, mixing homogeneously, and programmed heating to obtain magnetic porous microcrystal glass；
Step S102, suspending a certain amount of the magnetic porous microcrystalline glass obtained in the step S101 in toluene, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing, filtering, and drying at room temperature to obtain a microcrystalline solid;
and S103, suspending the microcrystalline solid obtained in the step S102 in methanol, adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde respectively, refluxing, filtering and drying in vacuum to obtain the palladium magnetic adsorbent.
Preferably, the waste glass and CaCO are prepared by the method3、SiC、H3BO3The weight ratio of the iron powder to the iron powder is as follows: 85-95: 2-6: 2-6: 0.5-1.5: 0.5 to 1.5.
Specifically, in step S101, the programmed temperature rise is performed by: raising the temperature to 800-900 ℃ at the speed of 20-30 ℃/min, keeping the temperature for 30-40 min, then raising the temperature to 1100-1200 ℃ at the speed of 20-30 ℃/min, and keeping the temperature for 10-30 min.
Specifically, the step S102 is: suspending the magnetic porous microcrystalline glass obtained in the step S101 in dry toluene, stirring for 1-2 hours, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing for 8-12 hours, filtering, washing with ethanol or dichloromethane, drying at room temperature, extracting a residual reagent with ethanol or dichloromethane in a Soxhlet manner, and drying under a vacuum environment at a temperature of 343K to obtain a microcrystalline solid.
Specifically, step S103 is: suspending the microcrystalline solid obtained in the step S102 in methanol, respectively adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde, refluxing for 8-12 hours, filtering, drying, performing Soxhlet extraction on the residual reagent by using ethanol, and drying under vacuum at the temperature of 343K to obtain the palladium magnetic adsorbent.
A palladium magnetic adsorbent prepared by the preparation method.
The application of the magnetic adsorbent prepared by the preparation method comprises the following steps: putting the magnetic adsorbent into the wastewater containing palladium for adsorption; and (3) putting the adsorbed magnetic adsorbent into a mixed solution of hydrochloric acid and thiourea, stirring, and filtering to obtain a recovered palladium ion solution.
Preferably, the time for the magnetic adsorbent to adsorb is 30-60 minutes.
Preferably, the concentration ratio of the hydrochloric acid to the thiourea of the mixed solution of the hydrochloric acid and the thiourea is (0.5-1.5): 1.
Compared with the prior art, the preparation method of the green high-efficiency palladium magnetic adsorbent provided by the invention has the following advantages:
(1) the invention realizes the reclamation of waste by using the waste glass as the main raw material, fully utilizes the melting characteristic of the waste glass, and mixes the waste glass with CaCO3And H3BO3The mixing not only solves the problem of large-scale utilization of waste glass, but also obviously reduces the production cost of the porous microcrystalline glass, simplifies the production process and has obvious economic and environmental protection benefits;
(2) according to the invention, the adsorbent with a specific adsorption effect on palladium is obtained by loading 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde on the surface of the porous glass ceramics, so that an effective way for recovering palladium from sewage is obtained, and the adsorption efficiency is high;
(3) according to the invention, a certain amount of iron powder is added into the raw materials, so that the obtained adsorbent has magnetism, and the problem that the solid-liquid separation is difficult after the powdery adsorbent is used is solved;
(4) the method realizes resource utilization of the noble metal palladium while treating the electroplating wastewater, and has obvious environmental and economic benefits.
Drawings
Embodiments of the invention are further described below with reference to the accompanying drawings, in which:
FIG. 1 is a flow chart of a method for preparing a green high-efficiency palladium magnetic adsorbent according to the invention;
FIG. 2 is a graph showing the adsorption effect of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
The invention provides a preparation method of a green high-efficiency palladium magnetic adsorbent, which solves the problems of complex preparation process and high manufacturing cost of the traditional adsorbent while realizing the recycling of waste glass. By adding magnetism, the adsorbent is easy to recover, and the loss of palladium is reduced.
The preparation method takes waste glass as a main raw material and adds foaming agent CaCO3SiC, iron powder and binder H3BO3The magnetic porous microcrystalline glass is prepared and used as a substrate, and an organic functional group is loaded on the substrate to obtain the high-efficiency adsorbent for heavy metal palladium, so that the resource recovery of the noble metal palladium is realized.
The preparation method of the invention is divided into two parts of preparation of magnetic porous microcrystalline glass and loading of organic functional groups. Firstly, preparing magnetic porous microcrystalline glass by using a programmed heating method, and secondly, loading organic functional groups by using a two-step loading method to obtain an adsorbent, namely the efficient specific magnetic adsorbent for palladium. Referring to fig. 1, the preparation method of the green high-efficiency palladium magnetic adsorbent of the present invention specifically includes the following steps:
step S101, adding a certain amount of CaCO into waste glass serving as a main raw material3、SiC、H3BO3And iron powder, crushing, sieving, mixing homogeneously, and programmed heating to obtain the magnetic porous microcrystal glass.
The porous microcrystalline glass is a microcrystalline material containing closed pores or interconnected pores obtained by heat treatment of an inorganic amorphous material, and the performance of the porous microcrystalline glass depends on the proportion and the structure of pores, crystalline phase and amorphous phase. At present, the discharge amount of waste glass is very high, which accounts for about 4 percent of the urban domestic garbage, the utilization rate is only 13 to 15 percent, most of the waste glass is not fully and effectively utilized, and most of the waste glass is treated in a landfill mode. The porous glass ceramics is produced by utilizing the waste glass, so that the problem of large-scale utilization of the waste glass is solved, the production cost of the porous glass ceramics is obviously reduced, the production process is simplified, and the method has obvious economic and environmental benefits.
The invention takes waste glass as main raw material and CaCO is added3Acting as a blowing agent, H3BO3The porous glass ceramics is prepared by a programmed heating method by matching with SiC as a binder, and a certain amount of iron powder is added to ensure that the obtained adsorbent has magnetism. The prepared magnetic porous microcrystalline glass has the excellent performances of low density, large specific surface area, small heat conductivity coefficient, high strength, good damping performance and the like, and can effectively load organic functional groups.
The magnetic porous microcrystalline glass is prepared by adopting a programmed heating method, and the reaction formula is as follows:
CaCO3＝CaO+CO2↑；
SiC+2O2＝SiO2+CO2↑；
3Fe+2O2＝Fe3O4；
in particular, the waste glass and CaCO3、SiC、H3BO3The weight ratio of the iron powder to the iron powder is as follows: 85-95: 2-6: 2-6: 0.5-1.5: 0.5 to 1.5. The components can fully react under the condition of the components, and the prepared magnetic porous microcrystalline glass has small density, large specific surface area and can effectively load organic functional groups in unit volume.
The temperature programming specifically comprises the following steps: raising the temperature to 800-900 ℃ at the speed of 20-30 ℃/min, keeping the temperature for 30-40 min, then raising the temperature to 1100-1200 ℃ at the speed of 20-30 ℃/min, and keeping the temperature for 10-30 min to obtain the magnetic porous glass ceramics. Porous glass ceramics are microcrystalline materials obtained by heat treatment of inorganic amorphous materials, and the performance of the porous glass ceramics depends on the proportion and the structure of air holes, crystalline phases and amorphous phases. Different heat treatment processes directly affect the proportion and the structure of the air holes, the crystalline phase and the amorphous phase, and further affect the performance of the porous glass ceramics. The magnetic porous microcrystalline glass prepared by the programmed heating method has good performance, strong adsorption force and large specific surface area.
And S102, suspending a certain amount of the magnetic porous microcrystalline glass obtained in the step S101 in toluene, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing, filtering, and drying at room temperature to obtain a microcrystalline solid.
Specifically, the magnetic porous microcrystalline glass obtained in the step S101 is suspended in dry toluene, stirred for 1-2 hours, 3-aminopropyltriethoxysilane is added under the dry nitrogen atmosphere, heating and refluxing are performed for 8-12 hours, filtering is performed, the magnetic porous microcrystalline glass is washed with ethanol or dichloromethane, drying is performed at room temperature, then residual reagent is soxhlet extracted with ethanol or dichloromethane, and drying processing is performed under vacuum at a temperature of 343K, so that microcrystalline solid is obtained.
And S103, suspending the microcrystalline solid obtained in the step S102 in methanol, adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde respectively, refluxing, filtering and drying in vacuum to obtain the palladium magnetic adsorbent.
Specifically, suspending the microcrystalline solid obtained in the step S102 in methanol, adding 2-mercaptobenzimidazole, refluxing for 8-12 hours, filtering, drying, performing Soxhlet extraction on the residual reagent with ethanol, and drying under vacuum at the temperature of 343K to obtain the palladium magnetic adsorbent.
After magnetic porous microcrystalline glass is obtained from waste glass, organic groups are loaded on the surface of the magnetic porous microcrystalline glass by utilizing a two-step loading method of the step S102 and the step S103, 3-aminopropyltriethoxysilane is loaded on the surface of the prepared magnetic porous microcrystalline glass in the first step, and 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde are loaded on the basis in the second step, so that the efficient specific magnetic adsorbent for the noble metal palladium in the industrial waste liquid is obtained. Functional groups such as 3-aminopropyltriethoxysilane, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde can perform specific adsorption on palladium ions in sewage, and the adsorption performance is good.
The efficient specific magnetic adsorbent for palladium obtained by the preparation method has the characteristics of large specific surface area, superparamagnetism and the like, can perform specific adsorption on palladium ions in sewage, and realizes resource recovery of noble metal palladium through magnetic recovery and thiourea elution. The preparation method has the characteristics of simple preparation process and low production cost, and realizes the recycling of wastes by using the waste glass as a main raw material. The obtained high-efficiency specific magnetic adsorbent for palladium has good adsorption performance and better magnetic responsiveness.
The magnetic adsorbent prepared by the preparation method can be used for recycling palladium in wastewater, and specifically comprises the following steps:
firstly, putting the magnetic adsorbent into wastewater containing palladium for adsorption; the optimal time for the magnetic adsorbent to adsorb is 30-60 minutes;
then, putting the adsorbed magnetic adsorbent into a mixed solution of hydrochloric acid and thiourea for elution, stirring and filtering to obtain a recovered palladium ion solution; the concentration ratio of the hydrochloric acid to the thiourea of the mixed solution of the hydrochloric acid and the thiourea is (0.5-1.5) to 1.
The first embodiment is as follows:
the preparation method of the high-efficiency specific magnetic adsorbent for palladium takes waste door and window glass as a raw material and comprises the following steps:
(1) preparation of magnetic porous microcrystalline glass
The magnetic porous microcrystalline glass is prepared by adopting a programmed heating method. Firstly, grinding and sieving waste glass, and mixing the ground waste glass and the sieved waste glass according to a ratio of 90: 4: 4: 1: 1, weighing the waste glass and CaCO3、SiC、H3BO3And iron powder. After being mixed evenly, the mixture is put into a muffle furnace for temperature programming. Raising the temperature to 800 ℃ at the speed of 20 ℃/minute, keeping the temperature for 30 minutes, then raising the temperature to 1133 ℃ at the speed of 20 ℃/minute, keeping the temperature for 10 minutes, and obtaining the magnetic porous glass ceramics.
(2) Support of organofunctional groups
Suspending 2g of the magnetic porous microcrystalline glass in 70mL of dry toluene, stirring for 1 hour, adding 1g of 3-aminopropyltriethoxysilane under a dry nitrogen atmosphere, heating and refluxing for 12 hours, filtering, washing with ethanol or dichloromethane, and drying at room temperature. The reagent residue is then soxhlet extracted with ethanol or dichloromethane and dried in vacuo 343K. Suspending 2g of the solid in 100mL of methanol, respectively adding 1.07g of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde, refluxing for 8 hours, filtering, drying, performing Soxhlet extraction with ethanol, and performing vacuum drying at 343K to obtain the efficient specific magnetic adsorbent for palladium.
The prepared efficient specific magnetic adsorbent for palladium is used for performing magnetic response performance characterization analysis by using an alternating gradient magnetometer. Tests show that the saturation magnetization of the efficient specific magnetic adsorbent for palladium is 45emu/g, the coercive force is zero, and the residual magnetization is zero, which indicates that the efficient specific magnetic adsorbent for palladium has superparamagnetism.
10mg of the magnetic adsorbent prepared in the first embodiment is added into water with a palladium ion concentration of 10mg/L, and the mixture is oscillated in a constant temperature oscillator at a speed of 220rpm for 3 hours at a temperature of 25 ℃, and meanwhile, a control experiment of adding magnetic porous glass ceramics and adding 2-mercaptobenzimidazole and an adsorption experiment of a high-efficiency specific magnetic adsorbent of palladium on palladium ions are carried out.
FIG. 2 is a graph showing the adsorption effect of the magnetic adsorbent of the present invention, in which MPG represents a porous glass-ceramic without a functional group, TAMPG-1 represents a porous adsorbent loaded with 2-mercaptobenzimidazole, TAMPG-2 represents a porous adsorbent loaded with 2-mercaptobenzothiazole, and TAMPG-3 represents a porous adsorbent loaded with 2-thiophenecarboxaldehyde. Tests show that the adsorption efficiency of the 2-mercaptobenzimidazole to palladium ions is improved by the load of the magnetic porous microcrystalline glass, the adsorption rate of the high-efficiency specific magnetic adsorbent of palladium to palladium ions is higher than that of the magnetic porous microcrystalline glass and the 2-mercaptobenzimidazole, and meanwhile, the high-efficiency specific magnetic adsorbent of palladium can be quickly separated from water after the adsorption process is finished. Therefore, the porous glass ceramics are adopted to adsorb the functional groups of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde, and a good adsorption effect can be achieved.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a green high-efficiency palladium magnetic adsorbent is characterized by comprising the following steps:
step S101, adding a certain amount of CaCO into waste glass serving as a main raw material3、SiC、H3BO3Mixing with iron powder, pulverizing, sieving, mixing, and heating to obtain the final productTo magnetic porous glass ceramics;
step S102, suspending a certain amount of the magnetic porous microcrystalline glass obtained in the step S101 in toluene, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing, filtering, and drying at room temperature to obtain a microcrystalline solid;
and S103, suspending the microcrystalline solid obtained in the step S102 in methanol, adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde respectively, refluxing, filtering and drying in vacuum to obtain the palladium magnetic adsorbent.
2. The method for preparing the green high-efficiency palladium magnetic adsorbent as claimed in claim 1, wherein the waste glass, CaCO3、SiC、H3BO3The weight ratio of the iron powder to the iron powder is as follows: 85-95: 2-6: 2-6: 0.5-1.5: 0.5 to 1.5.
3. The method for preparing a green high-efficiency palladium magnetic adsorbent according to claim 1, wherein in the step S101, the temperature programming is specifically as follows:
raising the temperature to 800-900 ℃ at the speed of 20-30 ℃/min, keeping the temperature for 30-40 min, then raising the temperature to 1100-1200 ℃ at the speed of 20-30 ℃/min, and keeping the temperature for 10-30 min.
4. The method for preparing a green high-efficiency palladium magnetic adsorbent according to claim 1, wherein the step S102 specifically comprises:
suspending the magnetic porous microcrystalline glass obtained in the step S101 in dry toluene, stirring for 1-2 hours, adding 3-aminopropyltriethoxysilane in a dry nitrogen atmosphere, heating and refluxing for 8-12 hours, filtering, washing with ethanol or dichloromethane, drying at room temperature, extracting a residual reagent with ethanol or dichloromethane in a Soxhlet manner, and drying under a vacuum environment at a temperature of 343K to obtain a microcrystalline solid.
5. The method for preparing a green high-efficiency palladium magnetic adsorbent according to claim 1, wherein the step S103 is specifically:
suspending the microcrystalline solid obtained in the step S102 in methanol, respectively adding 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 2-thiophenecarboxaldehyde, refluxing for 8-12 hours, filtering, drying, performing Soxhlet extraction on the residual reagent by using ethanol, and drying under vacuum at the temperature of 343K to obtain the palladium magnetic adsorbent.
6. A magnetic palladium adsorbent, obtained by the method of any one of claims 1 to 6.
7. Use of the magnetic adsorbent obtained by the preparation method according to any one of claims 1 to 5, comprising:
putting the magnetic adsorbent into the wastewater containing palladium for adsorption;
and (3) putting the adsorbed magnetic adsorbent into a mixed solution of hydrochloric acid and thiourea, stirring, and filtering to obtain a recovered palladium ion solution.
8. The use according to claim 7, wherein the magnetic adsorbent is adsorbed for 30 to 60 minutes.
9. The use according to claim 7, wherein the concentration ratio of the hydrochloric acid to the thiourea of the mixed solution of the hydrochloric acid and the thiourea is (0.5-1.5): 1.
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| CN201710483417.1A CN107321314B (en) | 2017-06-22 | 2017-06-22 | Preparation method and application of green high-efficiency palladium magnetic adsorbent |
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| CN107321314B true CN107321314B (en) | 2020-02-14 |
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| CN110354800A (en) * | 2019-07-05 | 2019-10-22 | 重庆科技学院 | One kind modifying SiO with ghiourea group2Preparation method of composite material and products thereof and application |
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| CN114797785A (en) * | 2022-05-20 | 2022-07-29 | 南华大学 | 2-mercaptobenzothiazole composite material, preparation method and application thereof, and method for separating palladium ions in palladium-containing acidic solution |
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