CN111647760A - Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber - Google Patents
Method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber Download PDFInfo
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Abstract
The invention discloses a method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, which comprises the following steps: (1) crushing and grinding the bismuth-doped quartz optical fiber, and mixing the crushed bismuth-doped quartz optical fiber with an alkali material to obtain a mixture; (2) heating the mixture for alkali fusion to obtain an alkali fusion material; (3) soaking the alkali fusion material in water, and then carrying out solid-liquid separation to obtain bismuth slag and a germanium-containing solution; (4) leaching the bismuth slag to obtain bismuth-containing leachate, and performing cyclone electrolysis on the bismuth-containing leachate to obtain bismuth powder; (5) adsorbing the germanium-containing liquid by using ion exchange resin to obtain germanium-enriched liquid and adsorbed liquid, and then desorbing the germanium-enriched liquid by using an desorbing agent to obtain germanium-containing desorption liquid; (6) and adding a surfactant into the adsorbed solution for aging, filtering, drying and calcining to obtain the silicon dioxide. The method realizes the selective and efficient recovery of germanium, bismuth and silicon in the bismuth-doped silica optical fiber, and has the advantages of no pollution to the environment, simple process, less reagent consumption, high comprehensive recovery degree, stronger practicability and the like.
Description
Technical Field
The invention relates to treatment of electronic waste materials, in particular to a treatment method of bismuth-doped silica optical fibers.
Background
Germanium is a typical rare metal, has good semiconductor performance, is one of the most important metals in the modern information industry, and is listed as a strategic reserve resource by countries in the world. Germanium and its compounds have wide application in the fields of electronic industry, infrared optics, optical fiber communication, chemical catalysts and the like. Optical fiber communication is the foundation of the information age, germanium is added into optical fiber, the transmission loss of the optical fiber can be greatly reduced, the refractive index is improved, and the germanium used in the current germanium-doped optical fiber industry accounts for more than 30% of the total germanium requirement of the world. The light-emitting spectrum band of the bismuth-doped silica fiber is near the non-zero dispersion wavelength 1310nm, and the communication system has application advantages when working in the band. In addition, the laser of the bismuth-doped silica fiber in the 1100-1300nm wave band can directly realize the conversion of the 550-650nm (yellow light wave band) laser by the frequency doubling technology, which has more advantages than the current semiconductor laser frequency doubling technology. With the development of information technology and optical fiber manufacturing technology, the global demand for optical fibers is increasing at a rate of 10% per year, resulting in an increase in the amount of waste optical fibers year by year, and therefore, it is important to recover valuable metals from waste optical fibers.
The bismuth-doped silica optical fiber preform is usually manufactured by a chemical vapor deposition (MCDV) process combined with a solution doping method, and then the optical fiber preform is drawn to finally obtain the bismuth-doped silica optical fiber. The silicon, germanium and bismuth in the optical fiber are uniformly doped, the separation and recovery of the silicon, the germanium and the bismuth are always important problems, the properties of the silicon and the germanium belong to the same group of elements and are similar, and the separation of the silicon and the germanium is also an industrial problem.
The recovery method of common optical fiber waste mainly comprises the following steps: high-temperature reduction volatilization method and hydrofluoric acid leaching method. The high temperature reduction volatilization method is to volatilize germanium to enrich and recover under strong reducing atmosphere, namely, carbon powder is added into the material, the mixture is evenly mixed and placed in a furnace to be heated to 600-800 ℃, inert gas is introduced or the pressure of the heating furnace is reduced, so that the germanium volatilizes in GeO form, and then a catcher is used for catching the GeO. The process equipment is complex, the process is difficult to control, the recovery rate of Ge is always lower than 70%, bismuth can be volatilized, and the process needs to be added to realize the separation of the Ge and the bismuth. The hydrofluoric acid leaching method is to add fluoride during acid leaching or directly leach with HF acid. The process has high germanium and bismuth leaching rate, but the method has the problems of serious corrosion to equipment, troublesome fluorine ion treatment and the like. And subsequent bismuth recovery requires hydrolysis, neutralization or replacement and other operations, so that the problems of complex process flow, long production period, high material consumption, high production cost and the like exist.
Patent CN109439909A adopts a sulfurizing volatilization technology to enrich and separate germanium from optical fiber production waste containing silicon and germanium, to obtain germanium sulfide or a mixture of germanium sulfide and germanium dioxide, and then to perform oxidizing roasting or direct sulfuric acid oxidizing leaching, and then to recover germanium from the leachate by a conventional method, but the method has the problems of high roasting temperature, high sulfur content in smoke and environmental pollution, etc. In patent CN110386606A, metal salt is added and pH value is adjusted to carry out silicon precipitation and germanium precipitation procedures, but in the method, a large amount of germanium is precipitated together with silicon in the silicon precipitation process, so that the recovery rate of germanium is low, germanium resources are not fully utilized, and impurity ions are introduced.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide a method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber with high efficiency, high recovery rate and short flow. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, comprising the steps of:
(1) crushing and grinding the bismuth-doped quartz optical fiber to a particle size of 0.125-0.25mm, and mixing the bismuth-doped quartz optical fiber with an alkali material to obtain a mixture;
(2) heating the mixture for alkali fusion to obtain an alkali fusion material;
(3) soaking the alkali fusion material in water, and then carrying out solid-liquid separation to obtain bismuth slag and a germanium-containing solution;
(4) leaching the bismuth slag to obtain bismuth-containing leachate, and performing cyclone electrolysis on the bismuth-containing leachate to obtain bismuth powder; the electrolyzed solution returns to the bismuth slag leaching process, and bismuth powder is refined to obtain refined bismuth;
(5) adsorbing the germanium-containing liquid by using ion exchange resin to obtain germanium-enriched liquid and adsorbed liquid, and then desorbing the germanium-enriched liquid by using an desorbing agent to obtain germanium-containing desorption liquid;
(6) and adding a surfactant into the adsorbed solution for aging, filtering, drying and calcining to obtain the silicon dioxide.
In the above method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, preferably, the mass content of germanium in the bismuth-doped silica optical fiber is 2-15%, the mass content of silicon is 30-70%, and the mass content of bismuth is 5-20%. The bismuth-doped silica fiber has the characteristics of high silicon and bismuth contents, difficult material treatment and difficult silicon germanium separation. By adopting the method, the selective step-by-step efficient recovery of germanium, bismuth and silicon can be realized under the combined action of the steps.
In the above method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, preferably, the mass ratio of the bismuth-doped silica optical fiber to the alkali is (0.8-2): 1, the alkali material is sodium hydroxide. The selection of the dosage of the alkali materials is closely related to the components of the bismuth-doped silica optical fiber. When the alkali ratio is too low, germanium is not completely converted into germanate and remains in leaching residues because germanium is wrapped by silicon, so that germanium resource loss is caused; when the ratio of the alkali to the base is too high, the alkalinity of the water extract is higher, more acid is needed for neutralization when the pH is adjusted, and the production cost is increased.
In the above method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica fiber, preferably, the mixture is further added with a salt additive NaCl or KCl, and the mass ratio of the salt additive to the bismuth-doped silica fiber is (0.1-0.3): 1. the invention reduces the activation energy of reaction by adding the salt additive in the alkaline smelting process, enhances the fluidity, avoids the caking phenomenon in the alkaline smelting process, and is more beneficial to the separation of metal in the water leaching process. Too small amount of salt additive can cause agglomeration of roasted products, the reaction can not be fully carried out and is not beneficial to water immersion, and too much salt additive can increase production cost and energy consumption and is not beneficial to the implementation of the process of aging and recovering silicon.
In the method for selectively recovering germanium, bismuth and silicon from the bismuth-doped silica fiber, preferably, the heating is carried out to the temperature of 350-600 ℃ during the alkali fusion, and then the temperature is kept for 1-4 h; and during water leaching, controlling the solid-liquid ratio of the alkali fusion material to water to be 1: (3-8) (g: ml) at a temperature of 60-85 ℃. The heating temperature is too low, the alkali can not be converted into molten alkali, so that the alkali can not fully react with the materials, and the energy consumption can be increased due to too high temperature.
In the method for selectively recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber, preferably, the leaching agent is 3-5mol/L hydrochloric acid when the bismuth slag is leached, and the liquid-solid ratio is controlled to be (4-6): 1 (g: ml) (more preferably 4: 1), leaching temperature of 70-80 ℃, leaching time of 2-4h (more preferably 2 h); the current density is controlled to be 150-300A/m during the cyclone electrolysis2(more preferably 200A/m)2) The electrolysis temperature is 40-60 deg.C (more preferably 50 deg.C), and the circulation flow rate is 300-400L/h (more preferably 400L/h).
In the above method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica optical fiber, preferably, before adsorbing the germanium-containing liquid by using ion exchange resin, adding acid to adjust the pH of the germanium-containing liquid to 6-10, and adding citric acid as a complexing agent, wherein the molar ratio of citric acid to germanium is (2-6): 1; the resolving agent is ammonia water solution with the mass concentration of 10-20%. The acid used in the pH adjustment is hydrochloric acid or sulfuric acid, and the concentration of the acid is 1-6 mol/L. Too high pH can cause hydrolysis of citric acid and low germanium adsorption rate; too low a pH may cause partial hydrolysis of germanium and silicon, affecting germanium recovery. Before ion exchange is carried out on germanium, catechol and germanium are added to form an anion complex, and then separation of silicon and germanium is realized through large-aperture anion exchange resin.
In the above method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, preferably, the ion exchange resin is D363 resin, and the particle size of the D363 resin is 0.315-1.25 mm. The D363 resin is macroporous weakly-alkaline styrene anion exchange resin, and researches show that compared with common germanium adsorption resin, the D363 resin has the advantages of large adsorption capacity, low possibility of poisoning, high exchange speed, good silicon-germanium separation effect, good stability and the like, particularly for a germanium solution system with high silicon content, the D363 resin and the complexing agent citric acid have the best matching relationship, and the D363 resin and the complexing agent citric acid have synergistic effect, so that the high-efficiency separation of germanium and silicon can be realized, and the absorption rate of germanium reaches more than 97%.
In the method for selectively recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber, preferably, when the germanium-containing liquid is adsorbed by using the ion exchange resin, the pH is controlled to be 2-6, the temperature is controlled to be 25-30 ℃, and the adsorption time is 0.5-3 h.
In the above method for selectively recovering germanium, bismuth and silicon from bismuth-doped silica fiber, preferably, chlorination distillation is performed on the germanium-containing desorption solution, germanium tetrachloride is collected by condensation, and then redistillation, rectification, hydrolysis, filtration and drying are sequentially performed on the germanium tetrachloride to obtain high-purity germanium dioxide.
In the above method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, preferably, in the step (6), the surfactant is cetyltrimethylammonium bromide, the aging temperature is 70-80 ℃ (more preferably 80 ℃), the aging time is 2-5h, and the calcination temperature is 400-.
In the invention, the main chemical reaction equations involved are as follows:
SiO2+2NaOH＝Na2SiO3+H2O；
GeO2+2NaOH＝Na2GeO3+H2O；
Bi2O3+6HCl＝2BiCl3+3H2O。
the invention realizes the selective fractional recovery of germanium, bismuth and silicon in the bismuth-doped quartz optical fiber, and the germanium and the silicon in the waste optical fiber are converted into soluble germanate and silicate by low-temperature alkaline smelting (the advantage is obvious compared with direct alkaline leaching), and then the germanate and the silicate are dissolved in alkaline leaching solution and filtered to obtain germanium-containing solution, and the bismuth does not react with the alkali and enters bismuth slag, thereby realizing the separation and recovery of the bismuth, the silicon and the germanium; and adjusting the pH value of the germanium-containing liquid, and then performing ion exchange on the germanium-containing liquid by using D363 resin and citric acid as additives, wherein the adsorption rate of germanium is more than 97%, and the total recovery rate of germanium is more than 94%. The bismuth slag realizes the recovery of bismuth by an acid leaching-cyclone electrolysis mode, the electrolyzed liquid can return to the bismuth slag for leaching, the recovery rate of bismuth reaches more than 94 percent, and bismuth powder with 3N purity is obtained. And finally, the silicon dioxide obtained by aging the adsorbed liquid can be sold without adjusting the pH value, so that the reagent consumption is saved.
Compared with the prior art, the invention has the advantages that:
1. the method realizes the separation of bismuth from silicon and germanium by low-temperature alkaline smelting, realizes the recovery of bismuth by an acid leaching-cyclone electrolysis mode, does not need neutralization, replacement and other operations, has the recovery rate of bismuth up to over 94 percent, and obtains bismuth powder with the purity of 3N.
2. The method of the invention uses ion exchange resin to adsorb and separate germanium, has high recovery rate, avoids the problems of high production cost, complex process equipment and environmental pollution caused by adopting the traditional method to deposit germanium, and does not introduce metal impurity ions.
3. The invention realizes the recycling of silicon in the waste optical fiber, and the silicon dioxide obtained by recycling can be used for preparing monocrystalline silicon and silicon dioxide films, thereby being beneficial to the recycling of silicon resources.
4. Compared with the prior art, the method has no procedures of neutralization hydrolysis or replacement and the like by a wet method, and has the advantages of no environmental pollution, simple flow, less reagent consumption, high comprehensive recovery degree, stronger practicability and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an XRD analysis of the bismuth-doped silica fiber of example 1.
FIG. 3 is a SEM-EDS image of a bismuth-doped silica optical fiber in example 1 of the present invention.
FIG. 4 is an XRD analysis chart of the residue after water immersion in example 1 of the present invention.
Fig. 5 shows a cyclone electrolyzer in embodiments 1, 2 and 3 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the main chemical components of the waste bismuth-doped silica optical fiber recovered from a certain factory are shown in table 1. By XRD analysis (FIG. 2), Bi was the main component in the waste optical fiber4(GeO4)3No SiO detection2Probably due to SiO in the waste fiber2Is amorphous. The SEM image (fig. 3) shows that germanium is uniformly doped in silicon.
Table 1: chemical composition of waste bismuth-doped silica optical fiber
As shown in fig. 1, a method for recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber comprises the following steps:
(1) firstly weighing 5kg of waste optical fiber, crushing and grinding the waste optical fiber until the particle size is 0.125-0.25mm, wherein the mass ratio of the waste optical fiber raw material to sodium hydroxide is 1: 1.2, weighing 6kg of sodium hydroxide, and mixing the waste optical fiber raw material and NaCl according to the mass ratio of 1: 0.1, weighing 0.5kg of NaCl, and uniformly mixing to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 400 ℃ in a muffle furnace, and then preserving heat for 3 hours to obtain an alkali fusion material;
(3) and (3) mixing the alkali fusion material obtained in the step (2) with water according to a solid-to-liquid ratio of 1: 8, adding the bismuth-containing solution into water at the temperature of 85 ℃ for leaching, filtering and separating the leached solution to obtain bismuth slag and a germanium-containing solution, sending the germanium-containing solution to ICP (inductively coupled plasma) for detection, and calculating the leaching rates of Ge and Si to be 97.6% and 98.5% respectively; drying and grinding the obtained filter residue, and detecting by XRD (figure 4) that the main components are Bi and Bi2O3Because Bi element does not react with molten alkali, and germanium and silicon elements basically enter into the germanium-containing liquid;
(4) and (3) adding the bismuth slag obtained in the step (3) into a hydrochloric acid solution with the concentration of 3mol/L and the liquid-solid ratio of 4: 1. leaching for 2 hours at the leaching temperature of 80 ℃, wherein the leaching rate of bismuth reaches 97 percent;
(5) adding the bismuth-containing leachate obtained in step (4) into a cyclone electrolysis device (as shown in FIG. 5, adding the bismuth-containing leachate into a multi-mouth bottle), heating the electrolyte by an electric heating sleeve, heating the electrolyte to 50 deg.C, turning on a delivery pump, regulating the flow rate of a flow meter to 400L/h, turning on a DC power supply to control the current density to 200A/m2Carrying out cyclone electrolysis, taking out cathode sediment and collecting electrolyzed liquid after the electrolysis end point is reached; the electrolyzed solution can return to the bismuth slag leaching procedure, the chemical composition of the obtained bismuth powder is shown in table 2, and the recovery rate of bismuth reaches 94 percent;
table 2: chemical composition of bismuth powder in example 1
(6) Adding 2mol/L hydrochloric acid into the germanium-containing solution obtained in the step (3) to adjust the pH value to about 8, then carrying out ion exchange adsorption on the solution by adopting D363 resin and citric acid as a complexing agent to obtain germanium enriched solution and adsorbed solution, wherein the experimental conditions comprise that the pH value is about 6, the particle size of the resin is 0.42-0.59mm, the extraction temperature is 25 ℃, the adsorption time is 1h, and the molar ratio of the citric acid to the germanium is 4: 1, the adsorption rate of germanium reaches 97 percent; after adsorption is finished, 10% ammonia water solution is used as an analytical agent for analysis to obtain germanium-containing analytical solution, and the recovery rate of germanium reaches 94.6%;
(7) adding hexadecyl trimethyl ammonium bromide into the solution after adsorption, aging for 2h at 80 ℃, filtering, drying, and calcining for 2h at 500 ℃ to obtain silicon dioxide;
(8) chloridizing and distilling the germanium-containing analysis solution to make germanium to be GeCl4After the germanium tetrachloride is condensed and received, the produced germanium tetrachloride is subjected to processes of redistilling, rectifying, hydrolyzing, filtering, drying and the like to obtain high-purity germanium dioxide.
Example 2:
the chemical components of waste optical fibers recovered from a certain plant are shown in Table 3.
Table 3: chemical composition of waste bismuth-doped silica optical fiber
As shown in fig. 1, a method for recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber comprises the following steps:
(1) firstly weighing 5kg of waste optical fiber, crushing and grinding the waste optical fiber until the particle size is 0.125-0.25mm, wherein the mass ratio of the waste optical fiber raw material to sodium hydroxide is 1: 1.4, weighing 7kg of sodium hydroxide; according to the mass ratio of the waste optical fiber raw material to NaCl of 1: 0.2, weighing 1kg of NaCl, and uniformly mixing to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 450 ℃ in a muffle furnace, and then preserving heat for 3h to obtain an alkali fusion material;
(3) and (3) mixing the alkali fusion material obtained in the step (2) with water according to a solid-to-liquid ratio of 1: 6, adding the mixture into water at the temperature of 70 ℃ for leaching, filtering and separating the leached solution to obtain filter residue and a germanium-containing solution, sending the germanium-containing solution to ICP (inductively coupled plasma) for detection, and calculating the leaching rates of Ge and Si to be 98.2% and 98.6% respectively;
(4) and (3) adding the bismuth slag obtained in the step (3) into a hydrochloric acid solution with the concentration of 3mol/L and the liquid-solid ratio of 4: 1. leaching for 2 hours at the leaching temperature of 80 ℃, wherein the leaching rate of bismuth reaches 98 percent;
(5) adding the bismuth-containing leachate obtained in the step (4) into a cyclone electrolysis device, heating the electrolyte through an electric heating sleeve, heating the electrolyte to 50 ℃, turning on a delivery pump, adjusting the flow of a flowmeter to 400L/h, turning on a direct-current power supply to control the current density to 200A/m2Carrying out cyclone electrolysis, taking out cathode sediment and collecting electrolyzed liquid after the electrolysis end point is reached; the electrolyzed solution can return to the bismuth slag leaching procedure, the chemical composition of the obtained bismuth powder is shown in Table 4, and the recovery rate of bismuth reaches 95 percent;
table 4: chemical composition of bismuth powder in example 2
(6) Adding 3mol/L hydrochloric acid into the germanium-containing solution obtained in the step (3) to adjust the pH value to be about 7, then adopting D363 resin and citric acid as complexing agents to carry out ion exchange adsorption on the solution to obtain germanium enriched solution and adsorbed solution, wherein the experimental conditions comprise that the pH value is about 5, the particle size of the resin is 0.59-0.84mm, the extraction temperature is 25 ℃, the adsorption time is 1.5h, and the molar ratio of the citric acid to the germanium is 5: 1, the adsorption rate of germanium reaches 98 percent; after adsorption is finished, 10% ammonia water solution is used as an analytical agent for analysis to obtain germanium-containing analytical solution, and the recovery rate of germanium reaches 96.2%;
(7) adding hexadecyl trimethyl ammonium bromide into the solution after adsorption, aging for 2h at 80 ℃, filtering, drying, and calcining for 2h at 500 ℃ to obtain silicon dioxide;
(8) chloridizing and distilling the germanium-containing analysis solution to make germanium to be GeCl4After the germanium tetrachloride is condensed and received, the produced germanium tetrachloride is subjected to processes of redistilling, rectifying, hydrolyzing, filtering, drying and the like to obtain high-purity germanium dioxide.
Example 3:
the chemical components of waste optical fibers recovered from a certain plant are shown in Table 5.
Table 5: chemical composition of waste bismuth-doped silica optical fiber
As shown in fig. 1, a method for recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber comprises the following steps:
(1) firstly weighing 5kg of waste optical fiber, crushing and grinding the waste optical fiber until the particle size is 0.125-0.25mm, wherein the mass ratio of the waste optical fiber raw material to sodium hydroxide is 1: 0.7, weighing 3.5kg of sodium hydroxide, and uniformly mixing to obtain a mixture;
(2) heating the mixture obtained in the step (1) to 250 ℃ in a muffle furnace, and then preserving heat for 3 hours to obtain an alkali fusion material;
(3) and (3) mixing the alkali fusion material obtained in the step (2) with water according to a solid-to-liquid ratio of 1: 6 adding the bismuth slag into water with the temperature of 70 ℃ for leaching, filtering and separating the leached bismuth slag and the germanium-containing liquid to obtain bismuth slag and the germanium-containing liquid, sending the germanium-containing liquid to ICP (inductively coupled plasma) for detection, and calculating that the leaching rates of Ge and Si are respectively 42.1% and 50.3% (because the temperature is low and no salt additive is added, the leaching rates of Ge and Si are low);
(4) and (3) adding the bismuth slag obtained in the step (3) into a hydrochloric acid solution with the concentration of 3mol/L and the liquid-solid ratio of 4: 1. leaching for 2 hours at the leaching temperature of 80 ℃, wherein the leaching rate of bismuth reaches 85 percent;
(5) adding the bismuth-containing leachate obtained in the step (4) into a cyclone electrolysis device, heating the electrolyte through an electric heating sleeve, heating the electrolyte to 50 ℃, turning on a delivery pump, adjusting the flow of a flowmeter to 400L/h, turning on a direct-current power supply to control the current density to 200A/m2Carrying out cyclone electrolysis, taking out cathode sediment and collecting electrolyzed liquid after the electrolysis end point is reached; the electrolyzed solution can return to the bismuth slag leaching procedure, the chemical composition of the obtained bismuth powder is shown in Table 6, and the recovery rate of bismuth reaches 82 percent;
table 6: chemical composition of bismuth powder in example 3
(6) Adding 3mol/L hydrochloric acid into the germanium-containing liquid obtained in the step (3) to adjust the pH value to about 8, and then carrying out ion exchange adsorption by adopting D363 resin to obtain germanium-enriched liquid and adsorbed liquid, wherein the experimental conditions comprise that the pH value is about 6, the particle size of the resin is 0.59-0.84mm, the extraction temperature is 25 ℃, the adsorption time is 1h, and the adsorption rate of germanium reaches 52.3%; after adsorption, 10% ammonia water solution is used as an analytical agent for analysis to obtain germanium-containing analytical solution, and the recovery rate of germanium reaches 22% (because no complexing agent is added, the ionic radii of silicate and germanate are similar, a large amount of silicon is also adsorbed);
or, adding 3mol/L hydrochloric acid into the germanium-containing solution obtained in the step (3) to adjust the pH value to about 8, then adopting D301 resin and citric acid as a complexing agent to perform ion exchange adsorption on the solution to obtain germanium-enriched solution and adsorbed solution, wherein the experimental conditions comprise that the pH value is about 3, the particle size of the resin is 0.42-0.59mm, the extraction temperature is 25 ℃, the adsorption time is 1.5h, and the molar ratio of the citric acid to the germanium is 4: 1, the adsorption rate of germanium reaches 82.2%; after adsorption is finished, 1mol/LHCl solution is used as an analytical agent to analyze to obtain germanium-containing analytical solution, and the recovery rate of germanium reaches 34.6%;
(7) and adding hexadecyl trimethyl ammonium bromide into the solution after adsorption, aging for 2h at 80 ℃, filtering, drying, and calcining for 2h at 500 ℃ to obtain the silicon dioxide.
In this embodiment, both of the germanium-containing solutions obtained by the two ion exchange adsorption methods in step (6) contain a certain amount of silicon, and silica gel is formed from silicate during the subsequent chlorination distillation with hydrochloric acid, which affects the recovery of germanium, and it is difficult to obtain high-purity germanium dioxide.
Claims (10)
1. A method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber, comprising the steps of:
(1) crushing and grinding the bismuth-doped quartz optical fiber, and mixing the crushed bismuth-doped quartz optical fiber with an alkali material to obtain a mixture;
(2) heating the mixture for alkali fusion to obtain an alkali fusion material;
(3) soaking the alkali fusion material in water, and then carrying out solid-liquid separation to obtain bismuth slag and a germanium-containing solution;
(4) leaching the bismuth slag to obtain bismuth-containing leachate, and performing cyclone electrolysis on the bismuth-containing leachate to obtain bismuth powder;
(5) adsorbing the germanium-containing liquid by using ion exchange resin to obtain germanium-enriched liquid and adsorbed liquid, and then desorbing the germanium-enriched liquid by using an desorbing agent to obtain germanium-containing desorption liquid;
(6) and adding a surfactant into the adsorbed solution for aging, filtering, drying and calcining to obtain the silicon dioxide.
2. The method of claim 1, wherein the bismuth-doped silica optical fiber comprises germanium in an amount of 2-15% by mass, silicon in an amount of 30-70% by mass, and bismuth in an amount of 5-20% by mass.
3. The method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber according to claim 1, wherein the mass ratio of the bismuth-doped silica optical fiber to the alkali is (0.8-2): 1, the alkali material is sodium hydroxide.
4. The method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber according to claim 1, wherein a salt additive NaCl or KCl is further added into the mixture, and the mass ratio of the salt additive to the bismuth-doped silica optical fiber is (0.1-0.3): 1.
5. the method as claimed in claim 1, wherein the heating is performed by heating to 350-600 ℃ and then maintaining the temperature for 1-4 h; and during water leaching, controlling the solid-liquid ratio of the alkali fusion material to water to be 1: (3-8) the temperature is 60-85 ℃.
6. The method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber according to any one of claims 1 to 5, wherein a leaching agent in leaching bismuth slag is 3 to 5mol/L hydrochloric acid, and the liquid-solid ratio is controlled to be (4 to 6): 1, leaching at the temperature of 70-80 ℃ for 2-4 h; the current density is controlled to be 150-300A/m during the cyclone electrolysis2The electrolysis temperature is 40-60 ℃, and the circulation flow is 300-400L/h.
7. The method for selectively recovering germanium, bismuth and silicon from the bismuth-doped silica optical fiber according to any one of claims 1 to 5, wherein before adsorbing the germanium-containing liquid by using the ion exchange resin, acid is added to adjust the pH of the germanium-containing liquid to 6 to 10, and citric acid is added as a complexing agent, wherein the molar ratio of the citric acid to the germanium is (2-6): 1; when the germanium-containing liquid is adsorbed by using ion exchange resin, controlling the pH value to be 2-6, controlling the temperature to be 25-30 ℃ and controlling the adsorption time to be 0.5-3 h; the resolving agent is ammonia water solution with the mass concentration of 10-20%.
8. The method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber according to any one of claims 1 to 5, wherein the ion exchange resin is D363 resin, and the particle size of the D363 resin is 0.315-1.25 mm.
9. The method for selectively recovering germanium, bismuth and silicon from a bismuth-doped silica optical fiber according to any one of claims 1 to 5, wherein the germanium-containing desorption solution is subjected to chlorination distillation, germanium tetrachloride is collected by condensation, and then the germanium tetrachloride is subjected to redistillation, rectification, hydrolysis, filtration and drying in sequence to obtain high-purity germanium dioxide.
10. The method for selectively recovering Ge, Bi and Si from a Bi-doped silica optical fiber according to any one of claims 1 to 5, wherein in the step (6), the surfactant is cetyltrimethylammonium bromide, the aging temperature is 70 to 80 ℃, the aging time is 2 to 5h, and the calcination temperature is 400-600 ℃.
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