CN115323179B - Method for inhibiting formation of iron silicon germanium colloid precipitate during deacidification of high-acid germanium-containing leaching solution by utilizing ultrasound - Google Patents
Method for inhibiting formation of iron silicon germanium colloid precipitate during deacidification of high-acid germanium-containing leaching solution by utilizing ultrasound Download PDFInfo
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- CN115323179B CN115323179B CN202211005105.7A CN202211005105A CN115323179B CN 115323179 B CN115323179 B CN 115323179B CN 202211005105 A CN202211005105 A CN 202211005105A CN 115323179 B CN115323179 B CN 115323179B
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- 239000002253 acid Substances 0.000 title claims abstract description 123
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 90
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002386 leaching Methods 0.000 title claims abstract description 46
- IFJPTKXSPLUPDR-UHFFFAOYSA-N [Fe].[Si].[Ge] Chemical compound [Fe].[Si].[Ge] IFJPTKXSPLUPDR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000084 colloidal system Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002244 precipitate Substances 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims description 14
- 230000002401 inhibitory effect Effects 0.000 title claims description 12
- 238000002604 ultrasonography Methods 0.000 title abstract description 6
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 32
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 43
- 239000002002 slurry Substances 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000004576 sand Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000779 smoke Substances 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 59
- 239000000243 solution Substances 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for forming iron-silicon-germanium colloid precipitate when high-acid germanium-containing leaching solution is subjected to acid reduction by utilizing ultrasound, and belongs to the technical field of germanium extraction devices. Aiming at the problem that germanium precipitation loss is easy to occur when the existing high-acid germanium-containing leaching solution is subjected to acid reduction, the high-acid germanium-containing liquid and mortar are premixed through ultrasonic collaborative mechanical stirring, and the large radial flow generated by mechanical stirring and the small diameter vortex and jet flow generated by ultrasonic are used for being subjected to synergistic effect, so that the high-acid germanium-containing liquid and mortar are quickly and uniformly mixed to form a homogeneous solution, and the problem that local pH is too high to form iron-silicon-germanium colloid precipitation when the ore mortar is subjected to acid reduction is avoided, so that adsorption and precipitation loss of germanium are avoided.
Description
Technical Field
The invention relates to a method for forming iron-silicon-germanium colloid precipitate when high-acid germanium-containing leaching solution is subjected to acid reduction by utilizing ultrasound, and belongs to the technical field of germanium extraction devices.
Background
China is the largest germanium producing country in the world, the yield reaches more than 66% of the global yield, china 63% germanium production takes zinc oxide smoke dust containing gram ton grade as a raw material, and a high acid leaching-germanium precipitation process is adopted to initially enrich the germanium to 2-30%, and then deep enrichment and purification are carried out. In order to realize efficient leaching of germanium, high-acid leaching is needed, the final acid reaches tens of grams liter, but the pH of the germanium precipitation needs to be controlled to be about 2, and the high-acid germanium-containing leaching solution is subjected to acid reduction treatment.
In conventional acid reduction, local pH too high regions are likely to occur, and high acid is formed to be difficult to dissolve iron silicon germanium colloid precipitate (figure 1), resulting in loss of leached germanium. In the method for extracting germanium from high-impurity low-grade complex zinc oxide powder, 0.5-3.5 g/L sulfite reducing agent is added to reduce Fe 3+ Adjusting the pH to 0.5-1.5, and then precipitating germanium, but the loss caused by silicon is not involved; in the process for improving the germanium recovery rate of the electrogalvanizing system, the loss of germanium in the leaching solution is reduced by controlling the concentration of iron before neutral leaching, but the effect on the loss of germanium when the actual germanium-containing leaching solution is subjected to acid reduction is smaller.
However, only those in the prior art have been reportedFe 3+ Germanium loss precipitation is caused under certain conditions, but no corresponding solution is reported or proposed for iron silicon germanium colloid coprecipitation.
Disclosure of Invention
Aiming at the problems that in the prior art of extracting germanium from smoke dust, when the acid is reduced by the high-acid germanium-containing leaching solution, a local area with too high pH value is easy to appear, and iron silicon germanium colloid precipitate is difficult to dissolve by the high-acid.
The invention adopts the technical proposal for solving the technical problems that:
a method for forming iron silicon germanium colloid sediment when high-acid germanium-containing leaching solution is deacidified by utilizing ultrasound, adopts a device for inhibiting the formation of iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified, and the device comprises an ultrasound premixing tank and an acid-reducing tank, and comprises the following specific steps:
(1) Adding slurry mixing water into ore sand to perform slurry mixing treatment to obtain ore mortar;
(2) Synchronously introducing ore mortar and high-acid germanium-containing leaching solution in equal proportion into an ultrasonic premixing tank, and rapidly and uniformly mixing to form a homogeneous premix by utilizing the synergistic effect of large radial flow generated by mechanical stirring and small-diameter vortex and jet flow generated by ultrasonic;
(3) The homogeneous premix is introduced into an acid reducing tank for neutralization and acid reduction treatment, and iron-silicon-germanium colloid precipitation is completely inhibited.
The ore sand in the step (1) is zinc oxide smoke dust, calcine or zinc oxide; the main phase of zinc in the calcine is zinc oxide, the zinc content in the ore sand is 35-80 wt%, the pH value of the slurry mixing water is 4.5-7, and the liquid-solid mass ratio in the ore mortar is 1.5-3.5:1.
The high-acid germanium-containing leaching solution in the step (2) is a germanium-containing sulfuric acid solution, and the concentration of germanium in the high-acid germanium-containing leaching solution is 50-500 mg/L, and SiO 2 The concentration is 100-400 mg/L, fe 2+ The concentration is 3-20 g/L, fe 3+ The concentration is 5-100 mg/L, and the acidity is 10-60 g/L.
The temperature of the high-acid germanium-containing leaching solution is 50-80 ℃ and the flow is 20-50 m 3 /h。
Calculated by 80% ZnO consumed by the high-acid germanium-containing solution, the solid-liquid ratio kg of the ore sand and the high-acid germanium-containing leaching solution in the step (1) is m 3 8.86-166.38:1, and the flow rate of the ore slurry is 0.26-29.12 m 3 /h。
The mechanical stirring speed in the ultrasonic premixing tank is 300-600 r/min, and the ultrasonic power is 50-300 kW.
The final acid acidity of the neutralization and deacidification treatment in the step (3) is 0.4-4 g/L, the temperature is 50-70 ℃, and the iron silicon germanium colloid precipitation is completely inhibited.
In the device for inhibiting formation of iron-silicon-germanium colloid precipitate when the high-acid germanium-containing leaching solution is subjected to acid reduction, a first mechanical stirring device is vertically arranged in an ultrasonic premixing tank 12, the tail end of the first mechanical stirring device is inserted into the bottom of the ultrasonic premixing tank 12, two rows of ultrasonic vibrators 4 which are axisymmetric relative to the first mechanical stirring device are vertically arranged in the ultrasonic premixing tank 12, an ore mortar pipe 2 and a high-acid germanium-containing liquid pipe 3 are arranged at the top end of the ultrasonic premixing tank 12, the ore mortar pipe 2 and the high-acid germanium-containing liquid pipe 3 are positioned at two sides of the first mechanical stirring device, the bottom outlet of the ultrasonic premixing tank 12 is communicated with the top inlet of an acid reduction tank 20 through a drainage tube 10, a second mechanical stirring device is vertically arranged in the acid reduction tank 20 and is positioned on the central shaft of the acid reduction tank 20, and pH meters are respectively arranged at the top and the bottom of the acid reduction tank 20.
The ultrasonic premixing tank 12 is vertically provided with a first guide column 11 which is axisymmetric relative to the first mechanical stirring device, the first guide column 11 is positioned on the side surface of the first mechanical stirring device, and the acid reducing tank 20 is vertically provided with a second guide column 24 which is axisymmetric relative to the second mechanical stirring device.
The first mechanical stirring device comprises a first motor 1, the first motor 1 is arranged right above an ultrasonic premixing groove 12, a first stirring shaft 5 is fixedly arranged on an output shaft of the first motor 1, and a turbine stirring paddle 9 is arranged at the bottom end of the first stirring shaft 5.
The second mechanical stirring device comprises a second motor 19, the second motor 19 is arranged right above the acid reducing tank 20, a second stirring shaft 21 is fixedly arranged on an output shaft of the second motor 19, an upper-layer blade type stirring blade 22 and a lower-layer blade type stirring blade 23 are arranged on the second stirring shaft 21, the upper-layer blade type stirring blade 22 is positioned in the middle of the acid reducing tank 20, and the lower-layer blade type stirring blade 23 is positioned at the bottom of the acid reducing tank 20.
Each row of ultrasonic vibrators 4 are connected in series, and the distance between every two adjacent ultrasonic vibrators 4 is 2-4 cm.
Preferably, the ultrasonic vibrator 4 is arranged on the inner groove wall of the ultrasonic premixing groove 12, and the first guide post 11 is 5 cm to 10cm away from the groove wall of the ultrasonic premixing groove 12.
Preferably, the turbine type stirring paddle 9 is 5-10 cm away from the bottom of the tank, the diameter of the turbine type stirring paddle 9 is 1/5-1/2 of the diameter of the ultrasonic premixing tank 12, and the blade width of the turbine type stirring paddle 9 is 1/3-5/6 of the diameter of the turbine type stirring paddle 9.
The length of the second stirring shaft 21 is 2/3-4/5 of the depth of the acid-reducing tank 20, the stirring diameter of the upper stirring blade 22 is smaller than that of the lower stirring blade 23, the distance between the upper stirring blade 22 and the top end of the acid-reducing tank 20 is 1/3-1/2 of the depth of the acid-reducing tank 20, the distance between the lower stirring blade 23 and the top end of the acid-reducing tank 20 is 4/5-9/10 of the depth of the acid-reducing tank 20, the stirring radius of the upper blade stirring blade 22 is 1/2-2/3 of the radius of the acid-reducing tank 20, the stirring radius of the lower stirring blade 23 is 1/2-2/3 of the radius of the acid-reducing tank 20, and the distance between the second flow guiding column 24 and the tank wall 10-20 cm of the acid-reducing tank 20.
The device for inhibiting the formation of iron-silicon-germanium colloidal precipitate when the high-acid germanium-containing leaching solution is subjected to acid reduction also comprises an ultrasonic control cabinet 18, and each row of ultrasonic vibrators 4 are respectively and electrically connected with the ultrasonic control cabinet 18.
The two rows of ultrasonic vibrators 4 are an A row ultrasonic vibrator and a B row ultrasonic vibrator respectively, an A row ultrasonic vibrator control panel 13, an A row ultrasonic vibrator starting button 17, a B row ultrasonic vibrator control panel 14, a B row ultrasonic vibrator starting button 18 and an emergency stop button 15 are arranged on the ultrasonic control cabinet 18, the A row ultrasonic vibrator control panel 13 and the A row ultrasonic vibrator starting button 17 are connected in series to form an A row ultrasonic vibrator control circuit, the B row ultrasonic vibrator control panel 14 and the B row ultrasonic vibrator starting button 18 are connected in series to form a B row ultrasonic vibrator control circuit, and the A row ultrasonic vibrator control circuit and the B row ultrasonic vibrator control circuit are connected in parallel and then are electrically connected with the emergency stop button 15.
In the device for inhibiting the formation of iron-silicon-germanium colloid precipitate when the high-acid germanium-containing leaching solution is subjected to acid reduction, turbine stirring slurry 9 of an ultrasonic premixing tank 12 generates a first large radial flow 6, an ultrasonic vibrator 4 generates a small diameter vortex 7 and a jet flow 8, and under the synergistic effect of the first large radial flow 6, the small diameter vortex 7 and the jet flow 8, mineral mortar and the high-acid germanium-containing liquid are rapidly and uniformly mixed to form uniform mixed liquid, so that a local pH over-high area is avoided; the upper stirring blade 22 and the lower stirring blade 23 of the acid reducing tank 20 generate a second large radial flow 26, and the mixed solution forms homogeneity in the acid reducing tank 20 under the action of the second large radial flow 26, so that the occurrence of a local pH too high area is avoided.
The invention has the beneficial effects that:
(1) The invention combines the pH meter with the deacidification, and can realize effective and accurate regulation and control of the acidity of the solution;
(2) According to the invention, an ultrasonic premixing tank is adopted, and uniform mixing of mortar and high-acid germanium-containing liquid can be rapidly realized in a small ultrasonic premixing tank through cooperation of conventional stirring, ultrasonic jet flow and ultrasonic vortex, namely premixing before the leaching liquid is subjected to acid reduction, so that high-acid hard to dissolve iron silicon germanium colloid precipitation caused by local pH is prevented, and high-efficiency germanium recovery is realized.
Drawings
FIG. 1 is a ferrosilicon colloid;
FIG. 2 is a schematic diagram of an apparatus for inhibiting the formation of iron-silicon-germanium colloid precipitate when the high-acid germanium-containing leachate is deacidified;
FIG. 3 is a top view of an ultrasonic premix tank;
in the figure, a 1-first motor, a 2-slurry pipe, a 3-high acid germanium-containing liquid pipe, a 4-ultrasonic vibrator, a 5-first stirring shaft, a 6-large radial flow, a 7-small diameter vortex, an 8-jet flow, a 9-turbine type stirring slurry, a 10-drainage pipe, a 11-first flow guiding column, a 12-ultrasonic premixing groove, a 13-A row vibrator control panel, a 14-B row vibrator control panel, a 15-scram button, a 16-A row ultrasonic vibrator start button, a 17-B row ultrasonic vibrator start button, a 18-ultrasonic control cabinet, a 19-second motor, a 20-acid reducing groove, a 21-second stirring shaft, a 22-upper layer blade type stirring slurry blade, a 23-lower layer blade type stirring slurry blade, a 24-second flow guiding column, a 25-pH meter and a 26-second large radial flow.
Detailed Description
The invention will be further described with reference to the following specific embodiments.
The invention suppresses the device (see figures 2 and 3) forming iron silicon germanium colloid and precipitating while the high-acid germanium-containing lixivium is reduced in acid, including supersonic premixing groove 12 and acid reducing groove 20, there is the first mechanical stirring device vertically in the supersonic premixing groove 12, the end of the first mechanical stirring device inserts to the bottom of supersonic premixing groove 12, there are two rows of supersonic vibrators 4 axisymmetric relative to the first mechanical stirring device vertically in the supersonic premixing groove 12, there are mineral mortar tube 2 and high-acid germanium-containing liquid tube 3 on the top of supersonic premixing groove 12, mineral mortar tube 2 and high-acid germanium-containing liquid tube 3 are located the both sides of the first mechanical stirring device, the bottom exit of supersonic premixing groove 12 communicates with top inlet of the acid reducing groove 20 through the drainage tube 10, there is the second mechanical stirring device vertically in the acid reducing groove 20, the second mechanical stirring device is located on central axis of the acid reducing groove 20, there are pH gauges at the top and bottom of the acid reducing groove 20;
a first flow guiding column 11 which is axisymmetric relative to the first mechanical stirring device is vertically arranged in the ultrasonic premixing tank 12, the first flow guiding column 11 is positioned on the side surface of the first mechanical stirring device, and a second flow guiding column 24 which is axisymmetric relative to the second mechanical stirring device is vertically arranged in the acid reducing tank 20;
the first mechanical stirring device comprises a first motor 1, the first motor 1 is arranged right above an ultrasonic premixing groove 12, a first stirring shaft 5 is fixedly arranged on an output shaft of the first motor 1, and a turbine stirring paddle 9 is fixedly arranged at the bottom end of the first stirring shaft 5;
the second mechanical stirring device comprises a second motor 19, the second motor 19 is arranged right above the acid reducing tank 20, a second stirring shaft 21 is fixedly arranged on an output shaft of the second motor 19, an upper-layer blade type stirring blade 22 and a lower-layer blade type stirring blade 23 are arranged on the second stirring shaft 21, the upper-layer blade type stirring blade 22 is positioned in the middle of the acid reducing tank 20, and the lower-layer blade type stirring blade 23 is positioned at the bottom of the acid reducing tank 20;
the device for inhibiting the formation of iron-silicon-germanium colloid sediment when the high-acid germanium-containing leaching solution is subjected to acid reduction also comprises an ultrasonic control cabinet 18, and each row of ultrasonic vibrators 4 are respectively and electrically connected with the ultrasonic control cabinet 18;
each row of ultrasonic vibrators 4 are connected in series, the two rows of ultrasonic vibrators 4 are respectively an A row of ultrasonic vibrators and a B row of ultrasonic vibrators, an A row of ultrasonic vibrator control panel 13, an A row of ultrasonic vibrator starting button 17, a B row of ultrasonic vibrator control panel 14, a B row of ultrasonic vibrator starting button 18 and an emergency stop button 15 are arranged on an ultrasonic control cabinet 18, the A row of ultrasonic vibrators, the A row of ultrasonic vibrator control panel 13 and the A row of ultrasonic vibrator starting button 17 are connected in series to form an A row of ultrasonic vibrator control circuit, the B row of ultrasonic vibrators, the B row of ultrasonic vibrator control panel 14 and the B row of ultrasonic vibrator starting button 18 are connected in series to form a B row of ultrasonic vibrator control circuit, and the A row of ultrasonic vibrator control circuit and the B row of ultrasonic vibrator control circuit are connected in parallel and then are electrically connected with the emergency stop button 15; the ultrasonic vibrator 4 is started and controlled by an ultrasonic control cabinet 18, the ultrasonic control cabinet 4 controls the ultrasonic power of the ultrasonic vibrator of the row A through an ultrasonic vibrator control panel 13 of the row A, controls the ultrasonic power of the ultrasonic vibrator of the row B through an ultrasonic vibrator control panel 14 of the row B, starts the ultrasonic vibrator of the row A through an ultrasonic vibrator starting button 16 of the row A, starts the ultrasonic vibrator of the row B through an ultrasonic vibrator starting button 17 of the row B, and the emergency stop button 15 can emergently stop the ultrasonic vibrator of the row A and the ultrasonic vibrator of the row B; the setting of the ultrasonic vibrator needs to be controlled at a certain interval to achieve the optimal synergistic effect; the flow guide column is separated from the ultrasonic at a certain distance, so that the ultrasonic jet flow is not blocked while the mechanical stirring is effectively enhanced; meanwhile, the height of the stirring paddle, the length and the width of the stirring paddle blade are required to be matched with the whole stirring, so that the service life of the stirring paddle is ensured while the optimal mechanical stirring effect is achieved;
the distance between every two adjacent ultrasonic vibrators 4 in each row is 2-4 cm;
the ultrasonic vibrator 4 is arranged on the inner groove wall of the ultrasonic premixing groove 12, and the distance between the first guide post 11 and the groove wall of the ultrasonic premixing groove 12 is 5-10 cm;
the turbine type stirring paddle 9 is 5-10 cm away from the bottom of the tank, the diameter of the turbine type stirring paddle 9 is 1/5-1/2 of the diameter of the ultrasonic premixing tank 12, and the blade width of the turbine type stirring paddle 9 is 1/3-5/6 of the diameter of the turbine type stirring paddle 9;
the stirring radius of the upper blade type stirring blade 22 is 1/2-2/3 of the radius of the acid reducing tank 20, the stirring radius of the lower stirring blade 23 is 1/2-2/3 of the radius of the acid reducing tank 20, and the distance between the second guide column 24 and the tank wall of the acid reducing tank 20 is 10-20 cm;
the turbine stirring slurry 9 of the ultrasonic premixing tank 12 generates a first large radial flow 6, the ultrasonic control cabinet 18 controls the ultrasonic vibrator 4 to generate a small-diameter vortex 7 and jet flow 8, and under the synergistic effect of the first large radial flow 6, the small-diameter vortex 7 and the jet flow 8, the mineral mortar and the high-acid germanium-containing liquid are rapidly and uniformly mixed to form uniform mixed liquid, so that a local pH over-high area is avoided; the upper stirring blade 22 and the lower stirring blade 23 of the acid reducing tank 20 generate a second large radial flow 26, and the mixed solution forms homogeneity in the acid reducing tank 20 under the action of the second large radial flow 26, so that the occurrence of a local pH too high area is avoided.
Example 1: a method for forming iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified by utilizing ultrasonic, adopts a device for inhibiting the formation of iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified, and comprises the following specific steps:
(1) Adding slurry mixing water (industrial production water with pH of 4.5) into ore sand (calcine) for slurry mixing treatment to obtain ore mortar, wherein the calcine contains 35wt% of zinc, and the mass ratio of liquid to solid in the ore mortar is 1.5:1;
(2) 52.07L of ore mortar and 1m 3 Synchronously introducing the high-acid germanium-containing leaching solution with the temperature of 50 ℃ into an ultrasonic premixing tank in equal proportion, and rapidly and uniformly mixing to form a homogeneous premix by utilizing the synergistic effect of large radial flow generated by mechanical stirring and small-diameter vortex and jet flow generated by ultrasonic; wherein the high acid germanium-containing leaching solution contains germanium 50mg/L, siO 2 100mg/L、Fe 2+ 3g/L、Fe 3+ 5mg/L, 10g/L sulfuric acid, and the flow rate of the high-acid germanium-containing leaching solution is 20m 3 And/h, the flow rate of the calcined mortar is 1.04m 3 The ore sand amount is 1m calculated by consuming 80% ZnO by the high-acid germanium-containing solution 3 The high-acid germanium-containing solution needs to consume 34.71kg of calcine, and the premixing volume of the ultrasonic premixing tank is 1m 3 The stirring speed of the turbine stirrer is 300r/min, and the ultrasonic power is 50kW;
(3) Introducing the homogenized premix into an acid reducing tank for neutralization and acid reduction treatment, wherein the final acid acidity is 0.4g/L, and the temperature is 50 ℃, so that iron silicon germanium colloid precipitation can be completely inhibited; the iron-silicon-germanium colloid is shown in fig. 1, and as can be seen from fig. 1, the distribution characteristics of the elements germanium, silicon and iron are consistent, and the precipitate is definitely germanium-silicon-iron copolymer.
Example 2: a method for forming iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified by utilizing ultrasonic, adopts a device for inhibiting the formation of iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified, and comprises the following specific steps:
(1) Adding slurry mixing water (pH 4.5 industrial production water) into ore sand (zinc oxide smoke dust) for slurry mixing treatment to obtain ore mortar (zinc oxide smoke dust slurry), wherein zinc content in the zinc oxide smoke dust is 50wt%, and the mass ratio of liquid to solid in the ore mortar is 2.5:1;
(2) 200L of ore mortar (zinc oxide smoke slurry) and 1m of ore mortar 3 Synchronously introducing the high-acid germanium-containing leaching solution with the temperature of 70 ℃ into an ultrasonic premixing tank in equal proportion, and rapidly and uniformly mixing to form a homogeneous premix by utilizing the synergistic effect of large radial flow generated by mechanical stirring and small-diameter vortex and jet flow generated by ultrasonic; wherein the high acid germanium-containing leaching solution contains 150mg/L, siO of germanium 2 200mg/L、Fe 2+ 6g/L、Fe 3+ 50mg/L, 30g/L sulfuric acid, and 30m of high-acid germanium-containing leaching solution flow 3 And/h, the flow rate of ore mortar (zinc oxide smoke slurry) is 6m 3 The ore sand amount is 1m calculated by consuming 80% ZnO by the high-acid germanium-containing solution 3 62.12kg of calcine is consumed by the high-acid germanium-containing solution, and the premixing volume of the ultrasonic premixing tank is 1m 3 The stirring speed of the turbine stirrer is 400r/min, and the ultrasonic power is 100kW;
(3) The homogenized premix is introduced into an acid reducing tank for neutralization and acid reduction treatment, the final acid acidity is 2g/L, the temperature is 60 ℃, and the precipitation of iron-silicon-germanium colloid can be completely inhibited.
Example 3: a method for forming iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified by utilizing ultrasonic, adopts a device for inhibiting the formation of iron silicon germanium colloid sediment when the high-acid germanium-containing leaching solution is deacidified, and comprises the following specific steps:
(1) Adding slurry mixing water (pH 5.5 industrial production water) into ore sand (pure zinc oxide) for slurry mixing treatment to obtain ore mortar (pure zinc oxide slurry), wherein the mass ratio of liquid to solid in the ore mortar is 3.5:1;
(2) 271.79L mineral mortar (pure zinc oxide slurry) and 1m 3 Synchronously introducing the high-acid germanium-containing leaching solution with the temperature of 80 ℃ into an ultrasonic premixing tank in equal proportion, and rapidly and uniformly mixing to form a homogeneous premix by utilizing the synergistic effect of large radial flow generated by mechanical stirring and small-diameter vortex and jet flow generated by ultrasonic; wherein the high acid germanium-containing leaching solution contains 500mg/L, siO of germanium 2 400mg/L、Fe 2+ 20g/L、Fe 3+ 50mg/L, sulfuric acid 60g/L, and the flow rate of the high-acid germanium-containing leaching solution is 50m 3 And/h, the flow rate of the ore mortar (pure zinc oxide mortar) is 13.59m 3 The ore sand amount is 1m calculated by consuming 80% ZnO by the high-acid germanium-containing solution 3 The high-acid germanium-containing solution needs to consume 77.66kg of pure zinc oxide, and the premixing volume of the ultrasonic premixing tank is 1m 3 The stirring speed of the turbine stirrer is 400r/min, and the ultrasonic power is 300kW;
(3) The homogenized premix is introduced into an acid reducing tank for neutralization and acid reduction treatment, the final acid acidity is 4g/L, the temperature is 70 ℃, and the precipitation of iron-silicon-germanium colloid can be completely inhibited.
The specific embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (3)
1. A method for forming iron silicon germanium colloid sediment when high-acid germanium-containing leaching solution is subjected to deacidification by utilizing ultrasonic inhibition is characterized in that: the device for inhibiting the formation of iron-silicon-germanium colloid precipitate during the deacidification of the high-acid germanium-containing leaching solution comprises an ultrasonic premixing tank and an deacidification tank, and comprises the following specific steps:
(1) Adding slurry mixing water into ore sand to perform slurry mixing treatment to obtain ore mortar; the ore sand is zinc oxide smoke dust, calcine or zinc oxide; the main phase of zinc in the calcine is zinc oxide, the zinc in the ore sand is 35-80 wt%, the pH value of the slurry mixing water is 4.5-7, and the liquid-solid mass ratio in the ore mortar is 1.5-3.5:1;
(2) Synchronously introducing ore mortar and high-acid germanium-containing leaching solution into an ultrasonic premixing tank in equal proportion, and utilizing large radial flow generated by mechanical stirring and small ultrasonic flowThe radial vortex and jet flow cooperate to quickly and uniformly mix to form a homogeneous premix; the high-acid germanium-containing leaching solution is a germanium-containing sulfuric acid solution; the germanium concentration in the high-acid germanium-containing leaching solution is 50-500 mg/L, siO 2 The concentration is 100-400 mg/L, fe 2+ The concentration is 3-20 g/L, fe 3+ The concentration is 5-100 mg/L, and the acidity is 10-60 g/L; the temperature of the high-acid germanium-containing leaching solution is 50-80 ℃, and the flow is 20-50 m 3 /h; calculated by using 80% ZnO consumed by the high-acid germanium-containing solution, the solid-liquid ratio kg of the ore sand and the high-acid germanium-containing leaching solution in the step (1) is m 3 8.86-166.38:1, and the flow rate of the ore slurry is 0.26-29.12 m 3 /h；
(3) The homogeneous premix is introduced into an acid reducing tank for neutralization and acid reduction treatment, and iron-silicon-germanium colloid precipitation is completely inhibited.
2. The method for suppressing the formation of iron silicon germanium colloid precipitate when the high-acid germanium-containing leachate is deacidified by utilizing ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps of: the mechanical stirring speed in the ultrasonic premixing tank is 300-600 r/min, and the ultrasonic power is 50-300 kW.
3. The method for suppressing the formation of iron silicon germanium colloid precipitate when the high-acid germanium-containing leachate is deacidified by utilizing ultrasonic waves as claimed in claim 1, wherein the method comprises the following steps of: and (3) the final acid acidity of the neutralization and acid reduction treatment is 0.4-4 g/L, and the temperature is 50-70 ℃.
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| CN114574706A (en) * | 2022-03-09 | 2022-06-03 | 昆明理工大学 | Method for ultrasonically enhancing germanium leaching in zinc oxide smoke |
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| US3367394A (en) * | 1964-11-12 | 1968-02-06 | Consortium Elektrochem Ind | Process for manufacturing homogeneous bodies of germanium-silicon |
| CN106011470A (en) * | 2016-07-04 | 2016-10-12 | 中南大学 | Method of recovering gallium and germanium from oxalate solution containing gallium and germanium |
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