CN115537584B - Method for reinforcing tannin germanium precipitation through ultrasonic and tannic acid modification - Google Patents
Method for reinforcing tannin germanium precipitation through ultrasonic and tannic acid modification Download PDFInfo
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Abstract
The invention relates to a method for strengthening tannin germanium precipitation by ultrasonic synergistic tannin modification, and belongs to the technical field of rare-dispersed metal enrichment and extraction. Aiming at the problem of high and essential consumption of tannic acid, namely that the tannic acid solution has the property of semi-colloidal solution, and hydrogen bonds or dipole effects exist among tannin molecules in the tannic acid solution to enable the tannin molecules to be easily associated with each other, so that the germanium precipitation efficiency of the tannic acid is greatly reduced, the ultrasonic wave and the deflocculant are provided to be synergistically enhanced, the shearing force generated by sonochemistry is strong enough to destroy the hydrogen bonds or dipole effects, the colloid adsorption effect during the dissolution of the tannic acid is reduced, meanwhile, the deflocculant can disperse tannic acid micelles, and liquid microjet generated after ultrasonic wave cavitation bubbles are broken is enough to enable the dispersed micelles to be broken to generate active chemical substances, so that the germanium precipitation effect of the tannic acid can be enhanced under triple effects, and the dosage of the tannic acid is greatly reduced. The method can reduce the content of the tannic acid by 50 to 66.67 percent, simultaneously reduce the content of tannin, reduce the adsorption impurities, and improve the grade of the germanium concentrate from about 25 percent of the existing level to 47 to 59 percent.
Description
Technical Field
The invention relates to a method for strengthening tannin germanium precipitation by ultrasonic and tannin synergistic modification, and belongs to the technical field of rare-dispersion metal enrichment and extraction.
Background
Germanium is a scarce, limited, important strategic resource. Germanium and compounds thereof have the advantages of higher infrared refraction coefficient, higher photoelectric conversion efficiency, lower transmission loss and the like, and have no value in the fields of national defense industry, aerospace, modern communication and the like. Germanium is mainly extracted from germanium-containing zinc oxide smoke dust in China, a tannin germanium precipitation process is mainly adopted, and because tannin solution has the property of semi-colloidal solution and hydrogen bonds or dipole effects exist among tannin molecules in the tannin solution, the tannin semi-colloidal solution has association effect and influences the germanium precipitation effect of tannic acid, the usage amount of tannic acid is up to more than 30 times of the germanium content, the production cost is high, and when the usage amount of tannic acid is high, a large amount of impurities can be adsorbed, so that the prepared germanium concentrate has low grade which is only about 25%.
In order to reduce the using amount of tannic acid, in the method for strengthening tannin complexation germanium precipitation by using step ultrasound, a masking agent is added to reduce the reaction of tannin and impurity ions, and seed crystals and step ultrasound are introduced to strengthen tannin germanium precipitation; in the method for precipitating the germanium by the aid of the tannic acid in a circulating mode, precipitated germanium tannate is returned to be used as a germanium precipitation crystal nucleus, two sections of germanium precipitators are used for achieving formation of the germanium tannate crystal nucleus and growth of particles, and the germanium tannate is precipitated efficiently.
At present, the tannin is reduced mainly by adding seed crystals, and the colloid property and modification of tannin are not researched.
Disclosure of Invention
The invention provides a method for strengthening tannin germanium deposition by modifying tannin through ultrasonic cooperation, aiming at the problems of high tannin dosage, low germanium deposition efficiency and the like in the prior art, the tannin dosage is greatly reduced through the cooperative strengthening of the ultrasonic and a deflocculant, the shearing force generated by sonochemistry is strong enough to destroy hydrogen bonds or dipole effects, the colloid adsorption effect during the dissolution of the tannin is reduced, meanwhile, the deflocculant can disperse tannin micelles, and in addition, liquid micro-jet flow generated after ultrasonic cavitation bubble rupture is enough to break the bonds of the dispersed micelles to generate active chemical substances, so that the tannin germanium deposition efficiency is strengthened.
A method for strengthening tannin germanium precipitation through ultrasonic cooperative tannin modification comprises the following specific steps:
(1) Under the ultrasonic condition, adding tannic acid and a coagulant into water to dissolve to form tannic acid liquid;
(2) Adding the tannin liquid into the germanium-containing leachate to perform tannin germanium precipitation, and performing liquid-solid separation to obtain a germanium precipitation solution I and a tannin residue I;
(3) Adding the tannin residue I into industrial water, performing ultrasonic slurrying to obtain mixed slurry, mixing the mixed slurry with the germanium-precipitated solution I, performing tannin germanium precipitation, and performing liquid-solid separation to obtain a germanium-precipitated solution II and tannin residue II;
(4) Directly neutralizing the germanium-precipitated liquid II, purifying and electrodepositing, purifying the tannin residue II by industrial water, and performing liquid-solid separation to obtain tannin residue III and purified liquid; oxidizing and roasting the tannin residue III to obtain germanium concentrate, and returning the purified liquid to the step (1) to dissolve the tannic acid and the deflocculant.
The dissolving temperature in the step (1) is 50 to 70 ℃, the dissolving pH is 1 to 3, and the ultrasonic strength is 0.3 to 0.6W/cm 2 The ultrasonic frequency is 16-20kHz, the concentration of tannic acid is 10-20wt.%, the concentration of a deflocculant is 0-5wt.%, and the deflocculant is ethanol, acetic acid, glycerol or glucose.
The content of germanium in the germanium-containing leaching solution in the step (2) is 50 to 200mg/L, and Fe 3+ The content is 10 to 50mg/L, and the zinc content is 100 to 150g/L.
Further, the pH value of the germanium-containing leachate obtained in the step (2) is 1 to 3, the mass of tannic acid in the tannic acid solution is 10 to 15 times of that of germanium in the germanium-containing leachate, the temperature of tannic germanium deposition is 60 to 70 ℃, and the germanium deposition time is 10 to 30min.
Further, the pH value of the liquid I after germanium precipitation is 1 to 2, the temperature is 60 to 65 ℃, the content of germanium in the liquid I after germanium precipitation is 20 to 80mg/L, and Fe 3+ The content is 5 to 30mg/L, and the zinc content is 99.4 to 148.4g/L; the content of zinc in the tannin germanium slag I is 4.53-12.52%, the content of Fe is 0.60-0.77%, and the content of Ge is 3.63-4.66%.
The pH value of the industrial water in the step (3) is 4-5, the slurry liquid-solid mass ratio is 1 2 The pulping temperature is 50 to 70 ℃, and the pulping pH is 1 to 3.
And (4) the temperature of tannin germanium precipitation in the step (3) is 60 to 65 ℃, and the germanium precipitation time is 20 to 40min.
Further, the pH value of the liquid II after germanium precipitation is 2 to 3, the temperature is 55 to 60 ℃, the content of germanium in the liquid II after germanium precipitation is 0.01 to 0.1mg/L, and the content of Fe 3+ The content is 1 to 5mg/L, and the zinc content is 99 to 148g/L; the content of zinc in the tannin germanium slag II is 14.62 to 34.82 percent, the content of Fe is 0.62 to 1.26 percent, and the content of Ge is 3.45 to 5.62 percent.
The liquid-solid mass ratio of the industrial water for purification to the tannin slag II in the step (4) is 2 to 4, the purification pH value is 1 to 2, and the purification is finishedThe melting temperature is 40 to 60 ℃, the zinc content in the tannin slag III is 0.8 to 1.5 percent, and Fe 3+ The content is 0.4 to 0.8 percent, and the content of Ge is 5.2 to 19.4 percent.
The content of effective tannin in the liquid purified in the step (4) is 0.5 to 1 percent, the content of Zn is 70.46 to 86.38g/L, and Fe 3+ The content is 0.66 to 2.80mg/L, and the Ge content is 0.12 to 5.44mg/L.
The beneficial effects of the invention are:
(1) Aiming at the problem of high and substantial tannin consumption that tannin solution has the property of semi-colloidal solution and hydrogen bonds or dipole effect exist among tannin molecules in the tannin solution, so that the tannin semi-colloidal solution has association effect and the germanium precipitation efficiency of tannin is greatly reduced, the invention provides a cooperative strengthening means of ultrasound and a deflocculant, the shearing force generated by sonochemistry is strong enough, the hydrogen bonds or dipole effect can be destroyed, the colloid adsorption effect when tannin is dissolved is reduced, and meanwhile, the deflocculant can disperse tannin micelles; liquid micro-jet flow generated after ultrasonic cavitation bubble rupture can lead dispersed micelle to generate bond fracture to generate active chemical substances, and can strengthen the germanium precipitation effect of tannic acid under triple actions, thereby greatly reducing the dosage of tannic acid;
(2) The method can reduce the consumption of the tannic acid by 50-66.67%, the cost of germanium precipitation per ton is reduced by 63-84 ten thousand calculated by 4.2 ten thousand per ton of the tannic acid, simultaneously the consumption of the tannic acid is reduced, the adsorption impurities are reduced, and the grade of the germanium concentrate is improved to 47-59% from about 25% of the existing level.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a GPC chart of tannin germanium residue obtained without the addition of ultrasound and a deflocculant;
FIG. 3 is a GPC chart of tannin germanium slag III obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for strengthening tannin germanium precipitation through ultrasonic cooperative tannin modification comprises the following specific steps:
(1) TanninDissolving: under the conditions of 50 ℃ and ultrasonic treatment, adding tannic acid and a deflocculant (glycerol) into industrial water with the pH value of 1 to dissolve for 5min to form tannic acid liquid; wherein the tannin in the tannin solution is 10 times of germanium in the germanium-containing leachate, and the ultrasonic power density is 0.3W/cm 2 The ultrasonic frequency is 16kHz, the concentration of tannic acid in the tannic acid liquor is 10wt.%, and the concentration of a deflocculant (glycerol) is 5wt.%;
(2) And (3) tannin germanium precipitation: adding tannin acid solution into germanium-containing leachate, performing tannin germanium precipitation for 10min, and performing liquid-solid separation to obtain germanium-precipitated solution I and tannin residue I; wherein the germanium content in the germanium-containing leachate is 50mg/L, and the Fe content is 3+ The content is 10mg/L, the zinc content is 100g/L, the pH value is 1, and the temperature is 60 ℃; the germanium content in the solution I after germanium precipitation is 20mg/L, fe 3+ The content is 5mg/L, the zinc content is 99.4g/L, the pH value is 1, and the temperature is 60 ℃; the zinc content of the tannin germanium slag I is 12.52 percent, the Fe content is 0.60 percent, and the Ge content is 3.63 percent;
(3) Pulping tannin residues and precipitating germanium: adding the tannin residue I into industrial water with the pH value of 4, and performing ultrasonic slurrying at the temperature of 60 ℃ for 20min to obtain mixed slurry, wherein the solid-liquid mass ratio of the tannin residue I to the industrial water is 1 2 ；
Mixing the mixed slurry with the germanium precipitation solution I, performing tannin germanium precipitation for 20min at the temperature of 60 ℃, and performing liquid-solid separation to obtain germanium precipitation solution II and tannin residue II; the germanium content in the solution II after germanium precipitation is 0.01mg/L, fe 3+ The content is 1mg/L, the zinc content is 99g/L, the pH is 2, and the temperature is 55 ℃; the content of zinc in the tannin germanium slag II is 34.82 percent, the content of Fe is 0.62 percent, and the content of Ge is 3.45 percent;
(4) Purifying and roasting tannin slag: the liquid II after germanium precipitation is directly neutralized and then purified and electrodeposited, the tannin residue II is purified by industrial water, and the liquid-solid separation is carried out to obtain tannin residue III and purified liquid, wherein the liquid-solid mass ratio of the industrial water for purification to the tannin residue II is 2, the purification pH is 1, the purification temperature is 40 ℃, the zinc content in the tannin residue III is 0.8%, and the Fe content in the tannin residue III is 0.8% 3+ The content is 0.4 percent, and the content of Ge is 5.2 percent; oxidizing and roasting the tannin residue III to obtain germanium concentrate, and returning the purified liquid to the step (1) to dissolve tannic acid and a deflocculant; the purified solution contains effective tannin 0.5%, zn 70.46g/L, and Fe 3+ The content is 1.78mg/L, and the Ge content is 0.12mg/L;
the GPC chart of the tannin germanium residue obtained under the condition of not adding ultrasonic and deflocculating agent (other conditions are not changed) is shown in FIG. 2, the GPC chart of the tannin germanium residue III obtained in the embodiment is shown in FIG. 3, and as can be seen from FIG. 2, the number average molecular weight Mn of the tannin germanium residue III obtained under the condition of not adding ultrasonic and deflocculating agent is 3197, and the distribution coefficient PDI is 1.45; in the embodiment, under the combined action of the ultrasonic and the deflocculant (glycerol), the number average molecular weight Mn of the obtained tannin germanium residue III is 532, and the distribution coefficient PDI is 1.36, which proves that the combined action of the ultrasonic and the deflocculant can reduce the association effect of tannin colloid, and the formed tannin germanium residue has smaller molecular weight and more uniform molecular weight distribution;
the grade of the germanium concentrate prepared by the embodiment is 47.02%.
Example 2: a method for strengthening tannin germanium precipitation through ultrasonic cooperative tannin modification comprises the following specific steps:
(1) Tannin dissolution: under the conditions of 60 ℃ and ultrasonic treatment, adding tannic acid and a deflocculant (acetic acid) into industrial water with the pH value of 2 to dissolve for 10min to form tannic acid liquid; wherein the ultrasonic power density is 0.5W/cm 2 The ultrasonic frequency is 18kHz, the concentration of tannic acid in the tannic acid solution is 15wt.%, and the concentration of a deflocculant (acetic acid) is 0.5wt.%;
(2) And (3) tannin germanium precipitation: adding tannin acid solution into germanium-containing leachate, performing tannin germanium precipitation for 20min, and performing liquid-solid separation to obtain germanium-precipitated solution I and tannin residue I; wherein the tannin in the tannin acid solution is 12 times of germanium in the germanium-containing leachate, the germanium content in the germanium-containing leachate is 100mg/L, and Fe 3+ The content is 15mg/L, the zinc content is 120g/L, the pH is 2, and the temperature is 65 ℃; the germanium content in the solution I after germanium precipitation is 30mg/L, fe 3+ The content is 8mg/L, the zinc content is 118.9g/L, the pH is 1.5, and the temperature is 62 ℃; the zinc content of the tannin germanium slag I is 8.70%, the Fe content is 0.40%, and the Ge content is 4.08%;
(3) Pulping tannin residues and precipitating germanium: adding the tannin residue I into industrial water with the pH value of 4.5, and performing ultrasonic slurrying at the temperature of 60 ℃ for 20min to obtain mixed slurry, wherein the solid-liquid mass ratio of the tannin residue I to the industrial water is 1m 2 ；
Mixing the mixed slurry with the germanium precipitation solution I, performing tannin germanium precipitation for 30min at the temperature of 62 ℃, and performing liquid-solid separation to obtain germanium precipitation solution II and tannin residue II; the germanium content in the solution II after germanium precipitation is 0.05mg/L, fe 3+ The content is 2mg/L, the zinc content is 118.5g/L, the pH is 2.5, and the temperature is 58 ℃; the zinc content of the tannin germanium slag II is 21.09 percent, the Fe content is 0.50 percent, and the Ge content is 3.82 percent;
(4) Purifying and roasting tannin slag: the liquid II after germanium precipitation is directly neutralized and then purified and electrodeposited, the tannin residue II is purified by industrial water, and the liquid-solid separation is carried out to obtain tannin residue III and purified liquid, wherein the liquid-solid mass ratio of the industrial water for purification to the tannin residue II is 3, the purification pH is 1.5, the purification temperature is 50 ℃, the zinc content in the tannin residue III is 1%, and Fe content in the tannin residue III is 1% 3+ The content is 0.6 percent, and the content of Ge is 7.5 percent; oxidizing and roasting the tannin residue III to obtain germanium concentrate, and returning the purified liquid to the step (1) to dissolve tannic acid and a deflocculant; the purified solution contains effective tannin 0.75%, zn 68.62g/L, and Fe 3+ The content is 0.66mg/L, and the Ge content is 0.13mg/L;
the grade of the germanium concentrate prepared by the embodiment is 50.31%.
Example 3: a method for strengthening tannin germanium precipitation by ultrasonic and tannic acid modification comprises the following specific steps:
(1) Tannin dissolution: adding tannic acid into industrial water with pH of 3 at 70 deg.C under ultrasonic condition, and dissolving for 20min to obtain tannic acid solution; wherein the ultrasonic power density is 0.6W/cm 2 Ultrasonic frequency is 20kHz, and the concentration of tannic acid in the tannic acid liquid is 20wt.%;
(2) And (3) tannin germanium precipitation: adding the tannin liquid into the germanium-containing leachate, performing tannin germanium precipitation for 30min, and performing liquid-solid separation to obtain a germanium-precipitated liquid I and a tannin residue I; wherein the tannin in the tannin liquid is 15 times of germanium in the germanium-containing leachate, the germanium content in the germanium-containing leachate is 200mg/L, and Fe is added 3+ The content is 50mg/L, the zinc content is 150g/L, the pH is 3, and the temperature is 70 ℃; the germanium content in the solution I after germanium precipitation is 80mg/L, fe 3+ The content is 30mg/L, the zinc content is 148.4g/L, the pH is 2, and the temperature is 65 ℃; the content of zinc in the tannin germanium slag I is 12.52 percent, the content of Fe is 0.77 percent, and the content of Ge is 4.66 percent;
(3) Pulping tannin residues and precipitating germanium: adding the tannin residue I into industrial water with the pH value of 5, and performing ultrasonic slurrying at the temperature of 70 ℃ for 15min to obtain mixed slurry, wherein the solid-liquid mass ratio of the tannin residue I to the industrial water is 1 2 ；
Mixing the mixed slurry with the germanium precipitation solution I, performing tannin germanium precipitation for 40min at the temperature of 65 ℃, and performing liquid-solid separation to obtain germanium precipitation solution II and tannin residue II; the germanium content in the solution II after germanium precipitation is 0.1mg/L, fe 3+ The content is 5mg/L, the zinc content is 148g/L, the pH is 3, and the temperature is 60 ℃; the content of zinc in the tannin germanium slag II is 14.62 percent, the content of Fe is 1.26 percent, and the content of Ge is 5.62 percent;
(4) Purifying and roasting tannin slag: after the liquid II after germanium deposition is directly neutralized, purifying electrodeposition is carried out, the tannin residue II is purified by industrial water, and liquid-solid separation is carried out to obtain tannin residue III and purified liquid, wherein the liquid-solid mass ratio of the industrial water for purification to the tannin residue II is 4 3+ The content is 0.8 percent, and the content of Ge is 19.4 percent; oxidizing and roasting the tannin residue III to obtain germanium concentrate, and returning the purified liquid to the step (1) to dissolve the tannin; the effective tannin content in the purified solution is 1%, the Zn content is 86.38g/L, and Fe 3+ The content is 2.80mg/L, and the Ge content is 5.44mg/L;
the grade of the germanium concentrate prepared by the embodiment is 58.86%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A method for strengthening tannin germanium precipitation through ultrasonic cooperative tannin modification is characterized by comprising the following specific steps:
(1) Under the ultrasonic condition, adding tannic acid and a coagulant into water to dissolve to form tannic acid liquid; the deflocculant is ethanol, acetic acid, glycerol or glucose; the dissolution temperature is 50 to 70 ℃, the dissolution pH is 1 to 3, and the ultrasonic intensity is 0.3 to 0.6W/cm 2 The ultrasonic frequency is 16-20kHz, the concentration of tannic acid is 10-20wt.%, and the concentration of a resolidifying agent is 0-5wt.%;
(2) Adding tannin acid solution into germanium-containing leachate for tannin germanium precipitation, and performing liquid-solid separation to obtain germanium precipitation solution I and tannin residue I;
(3) Adding the tannin residue I into industrial water, performing ultrasonic slurrying to obtain mixed slurry, mixing the mixed slurry with the germanium-precipitated solution I, performing tannin germanium precipitation, and performing liquid-solid separation to obtain a germanium-precipitated solution II and tannin residue II; the pH value of industrial water is 4 to 5, the slurry liquid-solid mass ratio is 1 2 Pulping at 50-70 ℃ and pH 1-3;
(4) Directly neutralizing the germanium-precipitated liquid II, purifying and electrodepositing, purifying the tannin residue II by industrial water, and performing liquid-solid separation to obtain tannin residue III and purified liquid; oxidizing and roasting the tannin residue III to obtain germanium concentrate, and returning the purified liquid to the step (1) to dissolve the tannic acid and the deflocculant.
2. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 1, wherein the method comprises the following steps: the content of germanium ions in the germanium-containing leaching solution in the step (2) is 50 to 200mg/L, and Fe 3+ The content is 10 to 50mg/L, and the content of zinc ions is 100 to 150g/L.
3. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 1 or 2, wherein: the pH value of the germanium-containing leachate is 1 to 3, the mass of tannic acid in the tannic acid solution is 10 to 15 times of the mass of germanium ions in the germanium-containing leachate, the temperature of tannic germanium deposition is 60 to 70 ℃, and the germanium deposition time is 10 to 30min.
4. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 3, wherein the method comprises the following steps: the pH value of the solution I after germanium precipitation is 1 to 2, the temperature is 60 to 65 ℃, the content of germanium ions in the solution I after germanium precipitation is 20 to 80mg/L, and Fe 3+ The content is 5 to 30mg/L, and the zinc ion content is 99.4 to 148.4g/L; the content of zinc element in the tannin germanium slag I is 4.53-12.52%, the content of Fe element is 0.60-0.77%, and the content of Ge element is 3.63-4.66%.
5. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 1, wherein the method comprises the following steps: and (3) the temperature of tannin germanium precipitation is 60-65 ℃, and the time of germanium precipitation is 20-40min.
6. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 5, wherein the method comprises the following steps: the pH value of the liquid II after germanium precipitation is 2 to 3, the temperature is 55 to 60 ℃, the content of germanium ions in the liquid II after germanium precipitation is 0.01 to 0.1mg/L, and Fe 3+ The content is 1 to 5mg/L, and the zinc ion content is 99 to 148g/L; the content of zinc element in the tannin germanium slag II is 14.62 to 34.82 percent, the content of Fe element is 0.62 to 1.26 percent, and the content of Ge element is 3.45 to 5.62 percent.
7. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 1, wherein the method comprises the following steps: and (4) the liquid-solid mass ratio of the industrial water for purification to the tannin slag II is 2 to 4, the purification pH value is 1 to 2, the purification temperature is 40 to 60 ℃, the zinc content of the tannin slag III is 0.8 to 1.5%, and the Fe content is as follows 3+ The content is 0.4 to 0.8 percent, and the content of Ge ions is 5.2 to 19.4 percent.
8. The method for strengthening tannin germanium precipitation by ultrasonic cooperative tannin modification as claimed in claim 1 or 7, wherein: the content of effective tannin in the purified liquid obtained in the step (4) is 0.5 to 1 percent, the content of Zn ions is 70.46 to 86.38g/L, and Fe
3+ The content is 0.66 to 2.80mg/L, and the content of Ge ions is 0.12 to 5.44mg/L.
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