CN117089728B - Method for efficiently adsorbing and recycling germanium - Google Patents
Method for efficiently adsorbing and recycling germanium Download PDFInfo
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- CN117089728B CN117089728B CN202311051195.8A CN202311051195A CN117089728B CN 117089728 B CN117089728 B CN 117089728B CN 202311051195 A CN202311051195 A CN 202311051195A CN 117089728 B CN117089728 B CN 117089728B
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 105
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011975 tartaric acid Substances 0.000 claims abstract description 16
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003795 desorption Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 8
- 239000013307 optical fiber Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 150000002500 ions Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- -1 germanium ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical group CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for efficiently absorbing and recycling germanium, which comprises the steps of utilizing macroporous strong alkaline styrene-divinylbenzene anion exchange resin as an adsorbent, using tartaric acid as a complexing agent, and using sulfuric acid as a medium to perform static and dynamic absorption, so as to realize the method for efficiently absorbing, recycling and purifying germanium from leaching liquid, and simultaneously removing the influence of other impurity elements (such as copper, zinc, iron, manganese, nickel, aluminum, magnesium, cobalt and the like) and organic matters on the purity of germanium. And desorbing the resin after adsorbing germanium by sodium hydroxide to obtain the germanium-containing solution with high concentration. The method for efficiently adsorbing and recycling germanium greatly shortens the process flow, improves the recycling rate of germanium, and can effectively avoid the influence of organic matters on adsorption separation, thereby realizing efficient independent separation of germanium.
Description
Technical Field
The invention relates to the technical field of germanium recovery, in particular to a method for efficiently adsorbing and recovering germanium.
Background
Tartaric acid is an organic carboxylic acid, is commonly used for preparing medicines, mordants, tanning agents and the like, is also an acidulant in food additives, and can be used as a complexing agent due to the unique molecular structure. Tartaric acid is a strong complexing agent with strong coordination capacity, and because it is a valence ligand, it forms a very stable complex coordination compound with metal ions, called a complex.
China is the largest production country and export country of gallium and germanium metal products in the global scope. Gallium is known as "new food of the semiconductor industry", while germanium is also one of the important materials for semiconductors. Germanium is an important scattered metal, is an important strategic resource, has good semiconductor performance, and has wide and important application in the fields of 5G communication, infrared optics, aerospace, solar cells, nuclear physical detection, chemical catalysts, biomedicine and the like. The ascertained germanium resource reserves are rare in the world, independent germanium mineral products hardly exist in the nature, the germanium is often associated with other nonferrous metal mineral products, the content of the germanium is low, most commonly, the germanium is recycled as a byproduct of zinc processing, the problems of complex process flow, high energy consumption, high cost and the like exist in refining the germanium in the mineral products, and the germanium resource in the mineral products is gradually exhausted after continuous exploitation and utilization. With the continuous development of the emerging industries such as the 5G technology in China, the demand of China for germanium resources is increased year by year, and China is a main country of germanium resource export, and the germanium is recycled from secondary resources, so that the problem of resource shortage can be effectively relieved, the strategic targets of carbon peak and carbon neutralization can be realized in a boosting way, and the method has important strategic and economic significance. At present, the main recovery method of germanium is extraction, zinc powder precipitation and the like, but the precipitation method is suitable for a solution with larger germanium concentration, and the precipitation method is easy to cause coprecipitation of other metal ions to influence the purity, so that the precipitation step is complicated; the extraction method is added with a diluent and a regulator, which is easy to cause organic pollution and influence the subsequent process, for example, the zinc electrolysis is often influenced by extracted organic matters to influence the zinc electrolysis efficiency and quality, and the operation environment of the extraction process is poorer, and the service life of the extractant is lower.
In addition, research adsorbents are also used for recovering germanium from a solution, for example, patent CN110368908a discloses a method for recovering germanium, wherein chitosan has metal active sites of amino groups and hydroxymethyl groups and has certain chelating ability on metal ions, and the adsorbent has an adsorption effect on germanium after being modified by polyphenol, but has poor selectivity and low saturated adsorption capacity. Patent CN111647760a discloses a method for selectively recovering germanium, bismuth and silicon from bismuth-doped quartz optical fiber, which uses D363 resin and citric acid as additives to perform ion exchange on germanium-containing liquid, but has lower adsorptivity to germanium and poorer recovery rate of germanium. Patent CN111118293a discloses a method for recovering germanium from germanium-containing solution and application thereof, which uses strong alkaline anion exchange resin containing meglumine functional groups to adsorb and uses hydrochloric acid to desorb the adsorption resin, but the adsorption resin containing meglumine functional groups has poor adsorptivity to germanium and poor desorption capability of hydrochloric acid to the adsorption resin, so that the recovery rate of germanium is low and the process is complex.
Disclosure of Invention
The invention aims to provide a method for efficiently adsorbing and recycling germanium, which is characterized in that tartaric acid is added as a complexing agent to effectively selectively adsorb germanium ions from a solution onto anion exchange resin, so that the separation of germanium and other impurity elements is realized, the content of the impurity elements is reduced, the purity of germanium is integrally improved, and technical support is provided for the purification and refining of germanium.
In order to achieve the above object, the present invention provides a method for efficiently adsorbing and recovering germanium, comprising the following steps: adding complexing agent into germanium-containing solution, adjusting pH value, pumping into adsorption column filled with adsorption resin by peristaltic pump, desorbing the adsorption resin, and recycling;
the complexing agent is tartaric acid; the adsorption resin is macroporous strong-alkaline styrene anion exchange resin containing quaternary ammonium; the desorbent is sodium hydroxide.
Preferably, the molar ratio of the added amount of the tartaric acid to germanium is 1:1; the pH was adjusted with H 2SO4.
Preferably, the concentration of the sodium hydroxide is 5mol/L.
Preferably, the germanium-containing solution is a leaching solution obtained by treating zinc metallurgy waste slag, waste optical fibers and fly ash with H 2SO4.
Preferably, the adsorption time is 2 hours and the adsorption temperature is 25 ℃.
Preferably, the adsorption resin is rinsed with ultra pure water before desorption, and then dried.
Preferably, the resolved adsorption resin is neutralized and washed by hydrochloric acid for recycling.
Therefore, the method for efficiently adsorbing and recovering germanium effectively adsorbs germanium ions from the solution to the anion exchange resin by adding tartaric acid as a complexing agent, so that the separation of germanium and other impurity elements is realized, the content of the impurity elements is reduced, the purity of germanium is integrally improved, and technical support is provided for the purification and refining of germanium. Meanwhile, the utilization rate of germanium can be effectively improved, the harm of solid waste accumulation to the ecological environment is reduced, and the problem of resource shortage is solved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a process flow diagram of a method for efficiently adsorbing and recovering germanium in accordance with the present invention;
FIG. 2 is a graph of acid adsorption rate for a method of efficiently adsorbing and recovering germanium according to the present invention;
FIG. 3 is a graph of saturated adsorption capacity for acidic static adsorption of a method for efficiently adsorbing and recovering germanium according to the present invention;
FIG. 4 is a selective adsorption drawing of a method for efficiently adsorbing and recovering germanium according to the present invention;
FIG. 5 is a graph showing the influence factors of the desorption rate of a method for efficiently adsorbing and recovering germanium according to the present invention: (a) the effect of different desorbents, (b) the effect of desorbent concentration, (c) the effect of time and temperature on desorption, (d) cycle performance;
fig. 6 is a graph of desorption rates for a method of efficiently adsorbing and recovering germanium according to the present invention: (a) ph=0, (b) ph=2.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The adsorption capacities of the different adsorption resins and additives for germanium are different, and the adsorption capacities of the different materials for germanium are shown in table 1:
TABLE 1 comparison of the adsorbent Performance of different materials
The saturated adsorption capacity of the HR resin was 212.1mg/g as calculated by column adsorption, and the adsorption capacity of the adsorbent of the present invention was highest as compared with other adsorbents (shown in Table 1).
The desorbing effect of the desorbing agent species, concentration, desorption time and desorption temperature is shown in fig. 5, with different species, concentration, desorption time and desorption temperature. As can be seen from FIG. 5, the desorption of sodium hydroxide at a concentration of 5mol/L for 180 minutes at 15℃was the best.
Treating solid waste zinc smelting waste slag with H 2SO4, and discarding optical fibers and fly ash leaching liquid to obtain germanium-containing solution, wherein the content of each ion in the solution is shown in table 2:
TABLE 2 sulfuric acid leach solution mixed ion concentration
Example 1
As shown in fig. 1, the invention provides a method for efficiently adsorbing and recovering germanium, which comprises the following steps:
(1) Pretreatment: treating solid waste zinc smelting waste slag by using H 2SO4, and discarding optical fibers and fly ash leaching liquid to obtain germanium-containing solution;
(2) Complexing: adding tartaric acid to the germanium-containing solution, and adjusting the pH of the solution to = 2 with H 2SO4;
(3) Column adsorption: putting HR resin into an adsorption column, pumping a mixed solution containing germanium through the HR resin by a peristaltic pump for adsorption, wherein the flow rate of the mixed solution is 10mL/h, the adsorption time is 2h, the temperature is 25 ℃, as shown in figure 4, other ion adsorption conditions are the same as those of adsorption germanium, at the moment, the adsorption effect on Fe 3+ ions except germanium is shown, fe 3+ is reduced into Fe 2+ by adding iron powder, the HR resin has no adsorption effect on Fe 2+, and the adsorption performance of the HR resin on germanium is not influenced by iron powder; as shown in fig. 6, when the pH of the solution=2, the HR resin shows excellent selectivity, and in the mixed solution in which Zn and Cu ions exist at high concentration, only the adsorption effect on germanium is shown, and separation and recovery of germanium are realized;
When the content of organic carbon in the solution after adsorption is zero, the tartaric acid is completely adsorbed into the HR resin, so that the pollution of the organic acid to the environment is avoided;
(4) Washing: washing the adsorbed HR resin with ultrapure water, and drying to remove surface moisture;
(5) And (3) desorption: desorbing the adsorbed HR resin by using sodium hydroxide solution, wherein the resolution ratio is 98%, the concentration of germanium in the desorbed solution is 881mg/L, and the impurity elements are hardly detected in the desorbed solution;
(6) And (3) recycling: the resolved HR resin is neutralized by hydrochloric acid to ensure that the HR resin presents weak acidity or neutrality and is used for recycling the adsorption germanium solution.
Example 2
As shown in fig. 1, the invention provides a method for efficiently adsorbing and recovering germanium, which comprises the following steps:
(1) Pretreatment: treating solid waste zinc smelting waste slag by using H 2SO4, and discarding optical fibers and fly ash leaching liquid to obtain germanium-containing solution;
(2) Complexing: adding tartaric acid to the germanium-containing solution, and adjusting the pH of the solution to = 0 with H 2SO4;
(3) Column adsorption: putting HR resin into an adsorption column, pumping a mixed solution containing germanium through the HR resin by a peristaltic pump, adsorbing for 2 hours at the flow rate of 10mL/h and the temperature of 25 ℃, wherein other ion adsorption conditions are the same as those of the adsorbed germanium, and the adsorption capacity of the germanium is slightly reduced compared with that of the solution with the pH=2, so that the adsorption rate of the germanium is about 70%; but only shows adsorption effect on germanium, a series of treatment on Fe 3+ ions is avoided, meanwhile, the pH=0 of the solution is more in line with the acidity of the solution after sulfuric acid leaching, and the industrial application is more practical; as shown in fig. 6, when the pH of the solution=0, the HR resin exhibits excellent selectivity, and in the mixed solution in which Zn and Cu ions exist at high concentration, only the adsorption effect on germanium is exhibited, and separation and recovery of germanium are achieved;
When the content of organic carbon in the solution after adsorption is zero, the tartaric acid is completely adsorbed into the HR resin, so that the pollution of the organic acid to the environment is avoided;
(4) Washing: washing the adsorbed HR resin with ultrapure water, and drying to remove surface moisture;
(5) And (3) desorption: desorbing the adsorbed HR resin by using sodium hydroxide solution, wherein the impurity elements are hardly detected in the desorbed solution;
(6) And (3) recycling: the resolved HR resin is neutralized by hydrochloric acid to ensure that the HR resin presents weak acidity or neutrality and is used for recycling the adsorption germanium solution.
Example 3
As shown in fig. 1, the invention provides a method for efficiently adsorbing and recovering germanium, which comprises the following steps:
(1) Pretreatment: treating solid waste zinc smelting waste slag by using H 2SO4, and discarding optical fibers and fly ash leaching liquid to obtain germanium-containing solution;
(2) Complexing: adding tartaric acid to the germanium-containing solution, and adjusting the pH of the solution to = 3 with H 2SO4;
(3) Column adsorption: putting HR resin into an adsorption column, pumping mixed solution containing germanium through the HR resin by a peristaltic pump for adsorption, wherein the flow speed of the mixed solution is 10mL/h, the adsorption time is 2h, the temperature is 25 ℃, as shown in figure 4, other ion adsorption conditions are the same as those of adsorbing germanium, the adsorption resin only shows adsorption to germanium and no adsorption to other ions, the influence on the adsorption of germanium caused by the treatment of other ions is avoided, and the adsorption rate of the adsorption resin is 98% at the moment; when the content of organic carbon in the solution after adsorption is zero, the tartaric acid is completely adsorbed into the HR resin, so that the pollution of the organic acid to the environment is avoided;
(4) Washing: washing the adsorbed HR resin with ultrapure water, and drying to remove surface moisture;
(5) And (3) desorption: desorbing the adsorbed HR resin by using sodium hydroxide solution, wherein the impurity elements are hardly detected in the desorbed solution;
(6) And (3) recycling: the resolved HR resin is neutralized by hydrochloric acid to ensure that the HR resin presents weak acidity or neutrality and is used for recycling the adsorption germanium solution.
Therefore, the method for efficiently adsorbing and recovering germanium effectively adsorbs germanium ions from the solution to the anion exchange resin by adding tartaric acid as a complexing agent, so that the separation of germanium and other impurity elements is realized, the content of the impurity elements is reduced, the purity of germanium is integrally improved, and technical support is provided for the purification and refining of germanium. Meanwhile, the utilization rate of germanium can be effectively improved, the harm of solid waste accumulation to the ecological environment is reduced, and the problem of resource shortage is solved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (4)
1. A method for efficiently adsorbing and recycling germanium is characterized by comprising the following steps: the method comprises the following steps: adding complexing agent into germanium-containing solution, adjusting pH value, pumping into adsorption column filled with adsorption resin by peristaltic pump, desorbing adsorption resin by desorbing agent, and recycling;
The complexing agent is tartaric acid; the adsorption resin is macroporous strong-alkaline styrene anion exchange resin HR resin containing quaternary ammonium; the desorbent is sodium hydroxide; the molar ratio of the added amount of the tartaric acid to germanium is 1:1; the pH value is regulated by H 2SO4; the concentration of the sodium hydroxide is 5mol/L; the adsorption time was 2 hours and the adsorption temperature was 25 ℃.
2. The method for efficiently adsorbing and recovering germanium according to claim 1, wherein: the germanium-containing solution is leaching solution obtained by treating zinc smelting waste slag, waste optical fibers and fly ash with H 2SO4.
3. The method for efficiently adsorbing and recovering germanium according to claim 2, wherein: the adsorption resin is washed by ultrapure water before desorption and then dried.
4. A method for efficient adsorption recovery of germanium according to claim 3, wherein: and the desorbed adsorption resin is neutralized and washed by hydrochloric acid and recycled.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525332A (en) * | 1984-02-02 | 1985-06-25 | Cominco Ltd. | Recovery of germanium from aqueous solutions |
| CN1030562A (en) * | 1987-07-15 | 1989-01-25 | 阿斯图·里安纳迪津公司 | From germanium-containing solution, reclaim the method for germanium |
| US7407587B1 (en) * | 2006-03-24 | 2008-08-05 | Layne Christensen Company | Method and sorbent for selective removal of contaminants from fluids |
| CN101538653A (en) * | 2009-02-25 | 2009-09-23 | 云南五鑫实业有限公司 | Method for producing germanium concentrated ore from germanium-containing industrial liquor |
| CN104357688A (en) * | 2014-11-19 | 2015-02-18 | 辽宁大学 | Method for separating germanium from levextrel resin by adsorptive extraction |
| CN109161685A (en) * | 2018-09-11 | 2019-01-08 | 辽宁大学 | A method of based on dynamic adsorption method absorption extraction germanium |
| CN114269954A (en) * | 2020-07-22 | 2022-04-01 | 环保金属有限公司 | Method for producing germanium concentrates from metallurgical residues |
-
2023
- 2023-08-21 CN CN202311051195.8A patent/CN117089728B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525332A (en) * | 1984-02-02 | 1985-06-25 | Cominco Ltd. | Recovery of germanium from aqueous solutions |
| CN1030562A (en) * | 1987-07-15 | 1989-01-25 | 阿斯图·里安纳迪津公司 | From germanium-containing solution, reclaim the method for germanium |
| US7407587B1 (en) * | 2006-03-24 | 2008-08-05 | Layne Christensen Company | Method and sorbent for selective removal of contaminants from fluids |
| CN101538653A (en) * | 2009-02-25 | 2009-09-23 | 云南五鑫实业有限公司 | Method for producing germanium concentrated ore from germanium-containing industrial liquor |
| CN104357688A (en) * | 2014-11-19 | 2015-02-18 | 辽宁大学 | Method for separating germanium from levextrel resin by adsorptive extraction |
| CN109161685A (en) * | 2018-09-11 | 2019-01-08 | 辽宁大学 | A method of based on dynamic adsorption method absorption extraction germanium |
| CN114269954A (en) * | 2020-07-22 | 2022-04-01 | 环保金属有限公司 | Method for producing germanium concentrates from metallurgical residues |
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