CN115537584B - Method for reinforcing tannin germanium precipitation through ultrasonic and tannic acid modification - Google Patents

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

A kind of method that ultrasonic synergistic tannic acid modification strengthens tannin precipitation germanium

technical field

The invention relates to a method for ultrasonically synergistic tannic acid modification and enhanced tannin precipitation of germanium, which belongs to the technical field of enrichment and extraction of scattered metals.

Background technique

Germanium is a scarce and limited important strategic resource. Germanium and its compounds have irreplaceable value in the defense industry, aerospace and modern communication fields due to their high infrared refraction index, high photoelectric conversion efficiency and low transmission loss. my country mainly extracts germanium from germanium-containing zinc oxide dust, and mainly adopts the tannin sinking germanium process. Because the tannin solution has the property of a semi-colloidal solution, and there are hydrogen bonds or dipole interactions between the tannin molecules in the tannin solution, this makes the single Ning semi-colloidal solution has an association effect, which affects the germanium precipitation of tannic acid. The amount of tannic acid is more than 30 times that of germanium, and the production cost is high. When the amount of tannic acid is high, it will absorb a large amount of impurities, resulting in the preparation of germanium concentrate The ore grade is low, only about 25%.

In order to reduce the amount of tannic acid, in the stepwise ultrasonic strengthening method of tannin complexation germanium deposition, the reaction between tannin and impurity ions is reduced by adding a masking agent, and the tannin deposition is strengthened by introducing crystal seeds and stepwise ultrasonic; In the method of cyclic germanium precipitation with nictine acid, the precipitated germanium tannin is returned as a germanium precipitation nucleus, and two-stage germanium precipitation is used to realize the formation of germanium tannin crystal nucleus and particle growth, so as to realize the efficient precipitation of germanium with tannic acid.

At present, the reduction of tannic acid is mainly through the addition of seed crystals, and there is no research on the properties and modification of tannic acid colloids.

Contents of the invention

Aiming at the problems of high dosage of tannic acid and low efficiency of germanium precipitation existing in the prior art, the present invention proposes a method for strengthening tannin precipitation of germanium by ultrasonic synergistic tannic acid modification. The amount of tannic acid is greatly reduced, and the shear force generated by sonochemistry is strong enough to destroy hydrogen bonds or dipole interactions, and reduce the colloidal adsorption when tannic acid is dissolved. At the same time, the decoagulant can disperse the tannic acid micelles. In addition, the liquid microjet generated after the ultrasonic cavitation bubbles are broken is enough to break the bonds of the dispersed micelles, generate active chemical substances, and enhance the efficiency of tannin sinking germanium.

A method for ultrasonically synergistic tannic acid modification and strengthening tannin precipitation of germanium, the specific steps are as follows:

(1) Under ultrasonic conditions, add tannic acid and decoagulant to water to dissolve to form tannic acid liquid;

(2) adding the tannin acid solution into the germanium-containing leaching solution to carry out tannin germanium precipitation, liquid-solid separation to obtain germanium-precipitated liquid I and tannin slag I;

(3) Tannin slag I is added to industrial water for ultrasonic slurrying to obtain a mixed slurry, the mixed slurry is mixed with the germanium-precipitated liquid I, and then tannin-precipitated germanium is carried out, and liquid-solid separation is obtained to obtain germanium-precipitated liquid II and tannin slag II;

(4) After germanium precipitation, the liquid II is directly neutralized and then purified and electrowinning. The tannin slag II is purified by industrial water, and the liquid and solid are separated to obtain the tannin slag III and the purified liquid; the tannin slag III is oxidized and roasted to obtain the germanium concentrate. After purification, the liquid returns to step (1) to dissolve tannic acid and decoagulant.

In the step (1), the dissolution temperature is 50-70°C, the dissolution pH is 1-3, the ultrasonic intensity is 0.3-0.6W/cm ² , the ultrasonic frequency is 16-20kHz, and the tannic acid concentration is 10-20wt.%. The concentration of the decoagulant is 0~5wt.%, and the decoagulant is ethanol, acetic acid, glycerin or glucose.

In the step (2), the germanium content in the germanium-containing leach solution is 50-200 mg/L, the Fe ³⁺ content is 10-50 mg/L, and the zinc content is 100-150 g/L.

Further, the pH of the germanium-containing leaching solution in the step (2) is 1-3, the tannic acid in the tannic acid solution is 10-15 times the mass of germanium in the germanium-containing leaching solution, and the germanium-depositing temperature of the tannins is 60-70 ℃, germanium sinking time is 10~30min.

Further, the pH value of the liquid I after germanium sinking is 1~2, the temperature is 60~65°C, the content of germanium in the liquid I after sinking germanium is 20~80 mg/L, and the content of Fe ³⁺ is 5~30 mg/L. L, the zinc content is 99.4~148.4g/L; the zinc content in tannin germanium slag I is 4.53~12.52%, the Fe content is 0.60~0.77%, and the Ge content is 3.63~4.66%.

The pH of the industrial water in the step (3) is 4~5, the mass ratio of slurry to liquid is 1:1, the ultrasonic slurry frequency is 16-20kHz, the ultrasonic intensity is 0.4~0.7W/cm ² , and the slurry temperature is 50~70℃, slurry pH is 1~3.

In the step (3), the germanium-precipitating temperature of the tannins is 60-65° C., and the germanium-precipitating time is 20-40 minutes.

Further, the pH value of the germanium-precipitated liquid II is 2~3, the temperature is 55-60°C, the germanium content in the germanium-precipitated liquid II is 0.01-0.1 mg/L, and the Fe ³⁺ content is 1-5 mg/L. L, the zinc content is 99~148g/L; the zinc content of tannin germanium slag II is 14.62~34.82%, the Fe content is 0.62~1.26%, and the Ge content is 3.45~5.62%.

In the step (4), the liquid-solid mass ratio of industrial water for purification to tannin slag II is 2-4:1, the purification pH value is 1-2, the purification temperature is 40-60°C, and the zinc content in tannin slag III is 0.8~1.5%, Fe ³⁺ content 0.4~0.8%, Ge content 5.2~19.4%.

The effective tannin content in the purified liquid in the step (4) is 0.5-1%, the Zn content is 70.46-86.38g/L, the Fe ³⁺ content is 0.66-2.80mg/L, and the Ge content is 0.12-5.44mg/L L.

The beneficial effects of the present invention are:

(1) In view of the essential problem of high consumption of tannic acid - tannin solution has the property of semi-colloidal solution, and there are hydrogen bonds or dipole interactions between tannin molecules in the tannin solution, so that the tannin semi-colloid solution has an association effect , greatly reduce the germanium precipitation efficiency of tannic acid, the present invention proposes a means of synergistic strengthening of ultrasound and decoagulant, the shear force generated by sonochemistry is strong enough to destroy hydrogen bonds or dipole interactions, and reduce the colloidal concentration of tannic acid when it dissolves At the same time, the decoagulant can disperse the tannic acid micelles; the liquid microjet generated after the ultrasonic cavitation bubbles are broken is enough to break the bonds of the dispersed micelles and produce active chemical substances, which can strengthen the tannic acid under the triple action The effect of sinking germanium can greatly reduce the dosage of tannic acid;

(2) The method of the present invention can reduce the amount of tannic acid by 50%~66.67%. Calculated at 42,000/ton of tannic acid, the cost of germanium precipitation per ton of germanium is reduced by 630,000~840,000. At the same time, the amount of tannin is reduced and the adsorption of impurities is reduced , the grade of germanium concentrate increased from about 25% of the current level to 47~59%.

Description of drawings

Fig. 1 is process flow chart of the present invention.

Fig. 2 is the GPC figure of tannin germanium slag obtained under the condition of not adding ultrasonic and decoagulant;

FIG. 3 is a GPC chart of germanium tannin slag III obtained in Example 1.

Detailed ways

The present invention will be described in further detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.

Embodiment 1: A kind of method that ultrasonic synergistic tannic acid modification strengthens tannin precipitation germanium, and specific steps are as follows:

(1) Tannin dissolution: Add tannic acid and decoagulant (glycerol) into industrial water with a pH value of 1 under ultrasonic conditions at a temperature of 50°C and dissolve for 5 minutes to form a tannic acid solution; Nitric acid is 10 times the mass of germanium in the germanium-containing leaching solution, the ultrasonic power density is 0.3W/cm ² , the ultrasonic frequency is 16kHz, the concentration of tannic acid in the tannic acid solution is 10wt.%, and the concentration of decoagulant (glycerin) is 5wt .%;

(2) Tannin germanium precipitation: add tannin acid solution to the germanium-containing leaching solution for tannin germanium precipitation for 10 minutes, and liquid-solid separation to obtain germanium-precipitating liquid I and tannin slag I; the germanium content in the germanium-containing leaching solution is 50mg/ L, the content of Fe ³⁺ is 10mg/L, the content of zinc is 100g/L, the pH is 1, and the temperature ^is 60°C; The content is 99.4g/L, the pH is 1, and the temperature is 60°C; the zinc content in the germanium tannin slag I is 12.52%, the Fe content is 0.60%, and the Ge content is 3.63%;

(3) Tannin slag slurrying germanium precipitation: tannin slag I was added to industrial water with a pH value of 4, and ultrasonically slurried at a temperature of 60°C for 20 minutes to obtain a mixed slurry, in which the solid-liquid mixture of tannin slag I and industrial water The mass ratio is 1:1, the slurry ultrasonic frequency is 16kHz, and the ultrasonic intensity is 0.4W/cm ² ;

After the mixed slurry is mixed with the germanium-precipitated liquid I, the tannin-precipitated germanium is carried out at a temperature of 60°C for 20 minutes, and the liquid-solid separation is obtained to obtain the germanium-precipitated liquid II and the tannin residue II; the germanium content in the germanium-precipitated liquid II is 0.01mg/ L, the content of Fe ³⁺ is 1mg/L, the content of zinc is 99g/L, the pH is 2, and the temperature is 55°C; the content of zinc in germanium tannin slag II is 34.82%, the content of Fe is 0.62%, and the content of Ge is 3.45%;

(4) Purification and roasting of tannin slag: after germanium precipitation, the liquid II is directly neutralized and then purified and electrowinning. The tannin slag II is purified by industrial water, and the liquid and solid are separated to obtain tannin slag III and purified liquid, of which industrial water is used for purification The liquid-solid mass ratio to tannin residue II is 2:1, the purification pH is 1, the purification temperature is 40°C, the zinc content in tannin residue III is 0.8%, the Fe ³⁺ content is 0.4%, and the Ge content is 5.2%; Tannin slag III is oxidized and roasted to obtain germanium concentrate. After purification, the liquid returns to step (1) to dissolve tannic acid and decoagulant; the effective tannin content in the purified liquid is 0.5%, the Zn content is 70.46g/L, and the Fe ³⁺ The content is 1.78mg/L, and the Ge content is 0.12mg/L;

Under the condition of not adding ultrasound and decoagulant (other conditions do not change), the GPC chart of the obtained tannin germanium slag is shown in Figure 2, and the GPC chart of the tannin germanium slag III obtained in this embodiment is shown in Figure 3, as can be seen from Figure 2, The number-average molecular weight Mn of germanium tannin slag III obtained without adding ultrasound and decoagulant is 3197, and the distribution coefficient PDI is 1.45; The average molecular weight Mn is 532, and the distribution coefficient PDI is 1.36, which proves that the combined action of ultrasound and decoagulant can reduce the association of tannin colloids, and the formed tannin germanium slag has a smaller molecular weight and a more uniform molecular weight distribution;

The grade of the germanium concentrate prepared in this example is 47.02%.

Embodiment 2: A kind of method that ultrasonic synergistic tannic acid modification strengthens tannin precipitation germanium, and specific steps are as follows:

(1) Tannin dissolution: Add tannic acid and decoagulant (acetic acid) into industrial water with a pH value of 2 under ultrasonic conditions at a temperature of 60°C and dissolve for 10 minutes to form a tannic acid solution; 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 decoagulant (acetic acid) is 0.5wt.%.

(2) Tannin sinking germanium: add tannin acid solution to the germanium-containing leach solution for tannin sinking germanium for 20 minutes, and liquid-solid separation to obtain germanium sinking liquid I and tannin residue I; the tannin acid in the tannin acid solution is The quality of germanium in the germanium-containing leach solution is 12 times, the content of germanium in the leach solution containing germanium is 100mg/L, the content of Fe ³⁺ is 15mg/L, the content of zinc is 120g/L, the pH is 2, and the temperature is 65°C; The content of germanium in I is 30mg/L, the content of Fe ³⁺ is 8mg/L, the content of zinc is 118.9g/L, the pH is 1.5, and the temperature is 62°C; the content of zinc in tannin germanium slag I is 8.70%, and the content of Fe is 0.40%, Ge content is 4.08%;

(3) Tannin slag slurrying germanium precipitation: tannin slag I was added to industrial water with a pH value of 4.5, and ultrasonically slurried at a temperature of 60°C for 20 minutes to obtain a mixed slurry, in which the solid-liquid mixture of tannin slag I and industrial water The mass ratio is 1:1, the slurry ultrasonic frequency is 18kHz, and the ultrasonic intensity is 0.6 W/cm ² ;

After the mixed slurry is mixed with the germanium-precipitated solution I, tannin-precipitated germanium is carried out at a temperature of 62°C for 30 minutes, and liquid-solid separation is obtained to obtain the germanium-precipitated solution II and tannin residue II; the germanium content in the germanium-precipitated solution II is 0.05mg/ L, the content of Fe ³⁺ is 2mg/L, the content of zinc is 118.5g/L, the pH is 2.5, and the temperature is 58°C; the content of zinc in tannic germanium slag II is 21.09%, the content of Fe is 0.50%, and the content of Ge is 3.82% ;

(4) Purification and roasting of tannin slag: after germanium precipitation, the liquid II is directly neutralized and then purified and electrowinning. The tannin slag II is purified by industrial water, and the liquid and solid are separated to obtain tannin slag III and purified liquid, of which industrial water is used for purification The liquid-solid mass ratio to tannin residue II is 3:1, the purification pH is 1.5, the purification temperature is 50°C, the zinc content in tannin residue III is 1%, the Fe ³⁺ content is 0.6%, and the Ge content is 7.5%; Tannin slag III is oxidized and roasted to obtain germanium concentrate, and the purified liquid returns to step (1) to dissolve tannic acid and decoagulant; the effective tannin content in the purified liquid is 0.75%, the Zn content is 68.62g/L, and the Fe ³⁺ The content is 0.66mg/L, and the Ge content is 0.13mg/L;

The grade of the germanium concentrate prepared in this example is 50.31%.

Embodiment 3: A kind of method that ultrasonic synergistic tannic acid modification strengthens tannin precipitation germanium, specific steps are as follows:

(1) Dissolution of tannins: Add tannic acid to industrial water with a pH value of 3 and dissolve for 20 minutes under ultrasonic conditions at a temperature of 70°C to form a tannic acid solution; the ultrasonic power density is 0.6W/cm ² , and the ultrasonic frequency is 20kHz, the concentration of tannic acid in the tannic acid solution is 20wt.%;

(2) Tannin sinking germanium: add tannin acid solution to the germanium-containing leach solution for tannin sinking germanium for 30 minutes, and liquid-solid separation to obtain germanium sinking liquid I and tannin residue I; the tannin acid in the tannin acid solution is 15 times the quality of germanium in the germanium-containing leach solution, the content of germanium in the leach solution containing germanium is 200mg/L, the content of Fe ³⁺ is 50mg/L, the content of zinc is 150g/L, the pH is 3, and the temperature is 70°C; The content of germanium in I is 80mg/L, the content of Fe ³⁺ is 30mg/L, the content of zinc is 148.4g/L, the pH is 2, and the temperature is 65°C; the content of zinc in tannin germanium slag I is 12.52%, and the content of Fe is 0.77%, Ge content is 4.66%;

(3) Tannin slag slurrying germanium precipitation: tannin slag I was added to industrial water with a pH value of 5, and ultrasonically slurried at a temperature of 70°C for 15 minutes to obtain a mixed slurry, in which the solid-liquid mixture of tannin slag I and industrial water The mass ratio is 1:1, the slurry ultrasonic frequency is 20kHz, and the ultrasonic intensity is 0.7W/cm ² ;

After the mixed slurry is mixed with the germanium-precipitated liquid I, the tannin-precipitated germanium is carried out at a temperature of 65°C for 40 minutes, and the liquid-solid separation is obtained to obtain the germanium-precipitated liquid II and the tannin residue II; the germanium content in the germanium-precipitated liquid II is 0.1mg/ L, the content of Fe ³⁺ is 5mg/L, the content of zinc is 148g/L, the pH is 3, and the temperature is 60°C; the content of zinc in germanium tannin slag II is 14.62%, the content of Fe is 1.26%, and the content of Ge is 5.62%;

(4) Purification and roasting of tannin slag: after germanium precipitation, the liquid II is directly neutralized and then purified and electrowinning. The tannin slag II is purified by industrial water, and the liquid and solid are separated to obtain tannin slag III and purified liquid, of which industrial water is used for purification The liquid-solid mass ratio to tannin residue II is 4:1, the purification pH is 2, the purification temperature is 60°C, the zinc content in tannin residue III is 1.5%, the Fe ³⁺ content is 0.8%, and the Ge content is 19.4%; Tannin slag III is oxidized and roasted to obtain germanium concentrate, and the purified liquid returns to step (1) to dissolve tannic acid; the effective tannin content in the purified liquid is 1%, the Zn content is 86.38g/L, and the Fe ³⁺ content is 2.80 mg/L, Ge content is 5.44mg/L;

The grade of the germanium concentrate prepared in this example is 58.86%.

The specific embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention within the scope of knowledge possessed by those of ordinary skill 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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