CN112691647A - Propylene glycol modified chitosan adsorbent, preparation method thereof and application thereof in germanium adsorption - Google Patents
Propylene glycol modified chitosan adsorbent, preparation method thereof and application thereof in germanium adsorption Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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Abstract
The invention belongs to the technical field of effective recovery of metal germanium and preparation of biomass derivative adsorption materials, and particularly relates to a propylene glycol modified chitosan adsorbent, a preparation method thereof and application thereof in germanium adsorption. The technical scheme is as follows: proper amount of chitosan is firstly mixed with hydroxyethyl methacrylate and K2S2O8、Na2S2O3Soaking in water to generate free radical polymerization reaction. And then the intermediate product polymer and 3-chlorine-1, 2 propylene glycol are refluxed and reacted for 24h, and vicinal diol functional groups are introduced into chitosan molecules on introduced hydroxyl groups to be used as Ge (IV) adsorption sites, so that the propylene glycol modified chitosan HEMA-IDOI-CS is obtained. Book (I)Advantages of the disclosed adsorbents include: the preparation process is simple; the cost is low; the raw material chitosan is prepared from crab shells and has wide sources; the adsorption capacity is large; the adsorption rate is high, and the method has practical applicability.
Description
Technical Field
The invention belongs to the technical field of effective recovery of metal germanium and preparation of biomass derivative adsorption materials, and particularly relates to a biomass material modified chitosan adsorbent which is formed by a simple and low-cost modified chitosan adsorbent and aims to effectively adsorb germanium from a solution containing metal ion germanium.
Background
Germanium (Ge) is a carbon group rare-earth element, has very high resistance, and is an important semiconductor material; in the seventies, the consumption market of germanium in the world has been expanded from the single semiconductor field to the fields of infrared, optical fiber, catalyst and the like, imaging parts such as windows, lenses, optical filters and the like of infrared lasers, thermal imagers, infrared thermometers and the like are manufactured by using metal germanium in military and civil use, and germanium is also used in optical fiber as an ideal dopant for improving the refractive index of a fiber core. In recent years, various organogermanium compounds having biological activity have been widely used in the fields of medicine and biology. With the rapid development of science and technology, germanium is increasingly used in high-tech industries, the consumption of metal germanium is increasing day by day, the germanium resource is deficient at home and abroad, and the demand is short, so that the effective extraction and recovery of germanium become more and more important.
There are many techniques for recovering germanium, but each has advantages and disadvantages. Wherein, the acid leaching method is used for extracting germanium from zinc concentrate to obtain high leaching rate, but the environmental pollution is serious due to large consumption of acid; the alkaline leaching method is simple to operate, and alkali can be regenerated and reused, but when the concentration of the alkali in the leaching solution is higher, liquid-solid separation is difficult; although the extraction method is industrialized, the problems of easy emulsification, high oil content of the purified solution and the like exist, and the extractant is an organic solvent and has great pollution to the environment; the ion exchange method has the advantages of large adsorption capacity, high speed, high metal removal rate, recyclability, high price and long process flow, so that the application is limited; the adsorption method has the characteristics of high selectivity, environmental friendliness and the like, and is an important research direction for extracting and separating low-content scattered metals. At present, the research on germanium separation by adsorption is less, and particularly, a selective separation mechanism from a specific component in a complex system needs to be explored.
The biomass material is a natural multifunctional substance, has the characteristics of environmental protection, greenness, sustainable substitution and the like when being applied to adsorption, almost has no cost, and can improve the adsorption selectivity and efficiency by a plurality of ways such as modification and the like. Chitosan, which is known as (1,4) -2-amino-2-deoxy-alpha-D glucan, is an important derivative of natural polysaccharide chitin, widely exists in shells of crustaceans such as shrimps and crabs and insects and cell walls of many lower plants such as bacteria and algae, shows outstanding chemisorption properties, and has been widely applied in the fields of food industry, medicine, printing and dyeing, papermaking, immobilized materials, environmental protection and the like in recent decades, so that chitosan and derivatives thereof have great potential and application prospects in the fields of water treatment ion adsorption and the like.
Disclosure of Invention
The chitosan molecule has hydroxyl and amino, and other groups can be introduced into the repeating unit of the chitosan molecule by controlling reaction conditions, so that the physical and chemical properties of the chitosan molecule are changed, more characteristic functions are endowed, and the requirements of multiple fields are met.
The invention is realized by the following technical scheme: the modified chitosan adsorbent is obtained by utilizing rich amino and hydroxyl sites of chitosan to perform diol dihydroxyl functionalization on the chitosan by a grafting method.
The preparation method of the propylene glycol modified chitosan adsorbent comprises the following steps:
1) washing with tap water to remove soluble organic matters and impurities on the crab shells, drying at 50-60 ℃, grinding the crab shells into powder, and performing decalcification, deproteinization and decoloration treatment to obtain white solid chitin;
2) taking dry chitin, adding 40-50% NaOH solution, and reacting for 7 hours at 100 ℃ to finally obtain white chitosan solid;
3) mixing the chitosan with hydroxyethyl methacrylate and K2S2O8、Na2S2O3Dispersing in water, soaking moderately to obtain intermediate product, mixing the intermediate product with 3-chloro-1, 2-propanediol dispersed in 1, 4-dioxane and NaOH dissolved in methanol in a round-bottom flask, refluxing and reacting at 70 ℃ for 24h, washing, filtering, and drying to obtain the chitosan adsorbent HEMA-IDOI-CS modified by the propylene glycol method.
According to the preparation method of the propylene glycol modified chitosan adsorbent, the mass ratio of chitosan: and (3) hydroxyethyl methacrylate is 5: 2-3.
The propylene glycol modified chitosan adsorbent is applied to adsorbing Ge (IV).
The application and the method are as follows: taking a composition containing [ Ge4+]Adjusting the pH value of the solution to 3-8 and adding the modified chitosan adsorbent of claim 1, wherein the solid-to-liquid ratio is 1g to 1L, the temperature is 303K, and the adsorption time is 24 h.
In the application, the concentration of the germanium solution is 20 mg/L-300 mg/L.
The application comprises the following steps of (1) preparing a chitosan adsorbent according to a solid-to-liquid ratio: 1g of germanium solution: 2-300L.
In the application, the adsorption time is 24-48 h.
The application comprises an elution step, wherein 10mL of different desorbents are added into the dried modified chitosan adsorbent with saturated adsorption, and the mixture is shaken for 24 h.
The use as described above, characterized in that the eluents are each1-3 mol/L HCl and/or 0.5-1 mol/L HNO3。
The invention has the beneficial effects that:
1) in the invention, the substrate chitosan of the modified chitosan HEMA-IDOI-CS is prepared from river crab shells, has wide sources, is non-toxic and harmless, and has good economic and environmental benefits.
2) The invention utilizes simple organic reagent to modify chitosan, has simple and convenient preparation method and mild reaction condition, introduces a large amount of alcoholic hydroxyl groups into chitosan molecules as adsorption sites of Ge (IV), and improves the content of the alcoholic hydroxyl groups in HEMA-IDOI-CS to 2.3mmol/g compared with the content of the alcoholic hydroxyl groups of the original chitosan molecules of 0.5 mmol/g.
3) The modified chitosan adsorbent HEMA-IDOI-CS prepared by the invention has large adsorption capacity and high adsorption efficiency on Ge (IV), wherein the adsorption rate of HEMA-IDOI-CS obtained by decolorizing and deproteinizing chitosan on Ge (IV) can reach more than 90% within the pH range of 3-8.
4) The modified chitosan adsorbent HEMA-IDOI-CS prepared by the invention has good selective adsorption capacity on Ge (IV). In the presence of other ions including Zn (II), Cu (II), Mn (II), Pb (II), Fe (III) and the like, the adsorption rates of HEMA-IDOI-CS on Zn (II), Mn (II) and As (III) are all very low in the whole acidity range, the adsorption rate of HEMA-IDOI-CS on germanium is over 90% under the weak acid condition of pH 3-8, and the selectivity factors of germanium ions and other metal ions are almost greater than or far greater than 1.5 in the acidity range of pH 1-6.
Drawings
FIG. 1 shows a comparison of adsorption performance of HEMA-IDOI-CS on various metal ions at different acidity.
FIG. 2 is a synthetic route for glycol-modified chitosan.
FIG. 3 is an infrared spectrum of crab chitosan and HEMA-IDOI-CS, wherein a is chitosan and b is HEMA-IDOI-CS.
FIG. 4 is a scanning electron micrograph of chitosan before and after glycol modification, wherein a is chitosan and b is HEMA-IDOI-CS.
Figure 5 effect of glycol-modified chitosan on germanium adsorption behavior at different acidity.
FIG. 6 adsorption isotherms of glycol-modified chitosan adsorbents for adsorbing germanium.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting.
Example 1 preparation of propylene glycol modified Chitosan adsorbent
Preparation of (mono) propylene glycol modified chitosan adsorbent
Selecting river crab shell as raw material, washing with tap water to remove soluble organic matter and impurities, drying at 60 deg.C, and grinding into powder. The subsequent treatment comprises the following steps:
decalcification: cleaning and drying crab shells, adding 2-6% HCl solution for soaking, continuously stirring to dissolve inorganic salt in the shells to soften the shells, and removing the inorganic salt after soaking for 10-15 h. Deproteinization: crab shells are washed to be neutral, added with 8 to 10 percent of NaOH solution and heated to 90 ℃ for reaction for 4 hours. And (3) decoloring: washing the crab shell treated by acid and alkali to be neutral, and adding l% of KMnO4And NaHSO3And respectively rinsing the solution for 1h, and then cleaning and drying to obtain a white solid product chitin. Taking dry chitin, adding 40-50% NaOH solution, and reacting for 7h at 100 ℃. A white chitosan solid, abbreviated CS, was finally obtained.
5g of CS, 2g of hydroxyethyl methacrylate and 0.5g K2S2O8、0.3g Na2S2O3The chitosan adsorbent modified by the propylene glycol method is obtained by soaking the chitosan adsorbent in 50mL of water moderately to obtain 5g of intermediate product, dissolving 3.016g of 3-chloro-1, 2-propanediol in 24mL of 1, 4-dioxane and 0.806g of NaOH in 24mL of methanol, then placing the two obtained solutions and 1g of intermediate product in a round-bottomed flask, carrying out reflux reaction for 24 hours at 70 ℃, washing the obtained product with distilled water and ethanol in sequence, carrying out suction filtration and drying. According to the same synthesis steps, four kinds of chitin with different treatment modes of decalcification and deproteinization, decoloration and decalcification, decoloration and decoloration are respectively adopted as raw materials to synthesize chitosan to prepare the adsorbent, and products are respectively abbreviated as HEMA-IDOI-CS1、HEMA-IDOI-CS2、HEMA-IDOI-CS3、HEMA-IDOI-CS4. The synthetic scheme is shown in figure 2.
(II) detection
FIG. 3 shows the IR spectra of crab chitosan and HEMA-IDOI-CS. Panel a is an infrared spectrum of chitosan CS, wherein 3458cm-1The absorption peak is-NH in chitosan22950cm-11562cm of C-H stretching vibration peak-1Is treated as the in-plane bending vibration peak of N-H bond in primary amine, 1300cm-1The left and right are absorption peaks of alcoholic hydroxyl; FIG. b is an infrared spectrum of the adsorbent obtained by modifying with 3-chloro-1, 2-propanediol at 3400cm-1The absorption peak nearby is changed from broad peak to peak, which shows that the amino functional group in the chitosan participates in the reaction in the modification process, and the absorption peak is 1294cm-1A new absorption peak appears at the left and right, which is a characteristic absorption peak of primary alcohol, and shows that the 3-chloro-1, 2-propanediol is successfully grafted to the surface of chitosan through modification.
From the elemental analysis of CS and HEMA-IDOI-CS, the C content of the raw material CS was 39.8%, the H content was 7.37%, and the N content was 7.11%. The C, N content in the adsorbent changed to varying degrees after modification, and the C/N value in CS was calculated to be 16.8, and the C/N value in HEMA-IDOI-CS was calculated to be 20.45 after modification, indicating that 3-chloro-1, 2-propanediol and diethanolamine were successfully introduced onto the chitosan surface by increasing the elemental content ratio of C to N.
Fig. 4 is a scanning electron microscope image of chitosan before and after being modified by glycol, and as can be seen from fig. 4, the surface structure and the morphological characteristics of the chitosan after being modified by glycol are changed, and the surface of the modified adsorbent becomes smooth by comparison.
As shown by the surface functional groups and BET measurement of CS and HEMA-IDOI-CS, the content of alcoholic hydroxyl in CS is 0.5mmol/g, and the content of alcoholic hydroxyl in HEMA-IDOI-CS is 2.3mmol/g, so that the content of alcoholic hydroxyl in the adsorbent modified by alcoholic hydroxyl is obviously increased.
Example 2 Effect of glycol-modified Chitosan on adsorption behavior at different acidity
The method comprises the following steps: adding modified chitosan adsorbent into germanium-containing solution at solid-to-liquid ratio of 1g:1LIn ionic solution, [ Ge ]4+]20mg/L, 303K and 24 h. The results are shown in FIG. 5.
As can be seen from FIG. 5, the adsorption rate of Ge (IV) by the adsorbent is gradually increased with the increase of pH, and the Chitosan (CS) is decolorized and deproteinized2) The adsorbent prepared by modifying with 3-chloro-1, 2-propanediol has better adsorption performance on Ge (IV), and the adsorption rate on germanium is up to 99.32% within the range of pH 4-6.
Furthermore, the adsorption behavior of HEMA-IDOI-CS on different ions Zn (II), Cu (II), Mn (II), Pb (II), Fe (III) was examined under different acidity conditions, as shown in FIG. 1, and the data are shown in Table 1. The adsorption rate of HEMA-IDOI-CS on Zn (II), Mn (II), As (III) is very low in the whole acidity range, the adsorption rate of HEMA-IDOI-CS on germanium is more than 90% under the condition of weak acid with pH value of 3-8, the adsorption rate on Cu (II), Pb (II) and Fe (III) is very low in the pH value range of 0-1, the adsorption rate on Cu (II), Pb (II) and Fe (III) is gradually increased in the pH value range of 1-8, and the adsorption rates on Cu (II), Pb (II) and Fe (III) are greatly increased when the acidity of the solution is high+Competitive adsorption with metal cations is formed, and when the solution is alkaline, negative charges on the surface of the adsorbent are increased, so that the adsorption rate of cations is increased.
TABLE 1 adsorption Performance of HEMA-IDOI-CS on different coexisting ions
In order to better study the separation ability of the adsorbent to ge (iv) and other metal ions, according to the formula:
selectivity factors for ge (iv) and other metal ions were calculated as shown in table 2. When Sela/b>At 1.5, Ge (IV) and metal ions can be effectively separated, and in the acidity range of pH 1-6, the selectivity factors of Ge (IV) and metal ions are almost greater than or far greater than 1.5, namelyThe good selective adsorption capacity of HEMA-IDOI-CS on Ge (IV) is shown.
TABLE 2 selectivity factor of HEMA-IDOI-CS for various metal ions at different acidity
Example 3 adsorption isotherm of the glycol-modified Chitosan adsorbent for adsorbing Ge (IV)
The method comprises the following steps: 10mg of HEMA-IDOI-CS adsorbent was weighed, 10mL of germanium solutions of various concentrations (ranging from 20mg/L to 300mg/L) were added, shaken at 303K for 48h, and then filtered to determine the concentration of Ge (IV) in the solution at equilibrium adsorption. The results are shown in FIG. 6.
As can be seen from fig. 6: the saturated adsorption capacity of HEMA-IDOI-CS on Ge (IV) is 74.21mg/g, and the adsorption capacity on germanium is strong because the content of alcoholic hydroxyl groups in HEMA-IDOI-CS is high, and two alcoholic hydroxyl groups in HEMA-IDOI-CS of the 3-chloro-1, 2-propanediol modified adsorbent are in ortho positions, so that Ge (OH) can be easily adsorbed4Forming a coordination structure. The adsorption of Ge (IV) is shown by a linear correlation coefficient to conform to a Langmuir adsorption isothermal model, and the correlation coefficient is the largest and belongs to monolayer adsorption.
Example 4 elution Effect of different eluents on Ge (IV) -adsorbing glycol-modified Chitosan adsorbents
The method comprises the following steps: accurately weigh 100mg HEMA-IDOI-CS adsorbent, add 100mL 1000mg/L Ge (IV) solution of pH 4, shake at 303K for 48h, filter, and dry. Then weighing 10mg of adsorbent with saturated adsorption, and adding 10mL of different eluents containing HCl (0.5-4 mol/L) and HNO with different concentrations3(0.05～1mol/L)、H2O, shaking for 24h, taking out and filtering, and measuring the concentration of Ge (IV) in the solution. The results are shown in Table 3.
As shown in Table 3, 0.5 to 1mol/L HNO was used3And 1-3 mol/L HCl has better elution effect on the adsorbent.
TABLE 3 elution experiment of HEMA-IDOI-CS
Claims (10)
1. The propylene glycol modified chitosan adsorbent is characterized in that the modified chitosan adsorbent is obtained by utilizing rich amino and hydroxyl sites of chitosan to perform diol dihydroxyl functionalization on the chitosan by a grafting method.
2. The preparation method of the propylene glycol modified chitosan adsorbent as claimed in claim 1, which is characterized by comprising the following steps:
1) washing with tap water to remove soluble organic matters and impurities on the crab shells, drying at 50-60 ℃, grinding the crab shells into powder, and performing decalcification, deproteinization and decoloration treatment to obtain white solid chitin;
2) taking dry chitin, adding 40-50% NaOH solution, and reacting for 7 hours at 100 ℃ to finally obtain white chitosan solid;
3) mixing the chitosan with hydroxyethyl methacrylate and K2S2O8、Na2S2O3Dispersing in water, soaking moderately to obtain intermediate product, mixing the intermediate product with 3-chloro-1, 2-propanediol dispersed in 1, 4-dioxane and NaOH dissolved in methanol in a round-bottom flask, refluxing and reacting at 70 ℃ for 24h, washing, filtering, and drying to obtain the chitosan adsorbent HEMA-IDOI-CS modified by the propylene glycol method.
3. The preparation method of the propylene glycol modified chitosan adsorbent according to claim 2, wherein the weight ratio of chitosan: and (3) hydroxyethyl methacrylate is 5: 2-3.
4. Use of the propylene glycol-modified chitosan adsorbent of claim 1 in adsorbing ge (iv).
5. Use according to claim 4, characterized in that the method is as follows: get and contain[Ge4+]Adjusting the pH value of the solution to 3-8 and adding the modified chitosan adsorbent of claim 1, wherein the solid-to-liquid ratio is 1g to 1L, the temperature is 303K, and the adsorption time is 24 h.
6. The use according to claim 5, wherein the concentration of the germanium solution is 20mg/L to 300 mg/L.
7. The use of claim 6, wherein the ratio of chitosan adsorbent: 1g of germanium solution: 2-300L.
8. Use according to claim 7, wherein the adsorption time is 24-48 h.
9. The use according to claim 8, comprising an elution step of adding 10mL of different desorbent to the dried modified chitosan adsorbent saturated in adsorption and shaking for 24 h.
10. The use according to claim 9, wherein the eluent is 1-3 mol/L HCl and/or 0.5-1 mol/L HNO respectively3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113234197A (en) * | 2021-04-30 | 2021-08-10 | 山东大学 | Preparation method and application of cellulose-based cationic adsorbent |
| CN114210311A (en) * | 2021-12-14 | 2022-03-22 | 中南大学 | Germanium adsorbent, preparation method and method for recovering germanium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732432A (en) * | 2017-01-17 | 2017-05-31 | 辽宁大学 | A kind of shitosan/persimmon tannin composite and preparation method thereof and the application in Ti recovery |
| CN110368908A (en) * | 2019-07-24 | 2019-10-25 | 辽宁大学 | A kind of polyphenol modification of chitosan adsorbent and preparation method thereof and the application in germanium recycling |
-
2020
- 2020-12-08 CN CN202011420981.7A patent/CN112691647A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732432A (en) * | 2017-01-17 | 2017-05-31 | 辽宁大学 | A kind of shitosan/persimmon tannin composite and preparation method thereof and the application in Ti recovery |
| CN110368908A (en) * | 2019-07-24 | 2019-10-25 | 辽宁大学 | A kind of polyphenol modification of chitosan adsorbent and preparation method thereof and the application in germanium recycling |
Non-Patent Citations (1)
| Title |
|---|
| 陈晖: ""醇/酚羟基改性的生物质吸附材料对锗分离吸附的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113234197A (en) * | 2021-04-30 | 2021-08-10 | 山东大学 | Preparation method and application of cellulose-based cationic adsorbent |
| CN113234197B (en) * | 2021-04-30 | 2022-07-01 | 山东大学 | Preparation method and application of cellulose-based cationic adsorbent |
| CN114210311A (en) * | 2021-12-14 | 2022-03-22 | 中南大学 | Germanium adsorbent, preparation method and method for recovering germanium |
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