CN101274262B - Method and device for improving zinc powder activity with ultrasonic, and application thereof - Google Patents
Method and device for improving zinc powder activity with ultrasonic, and application thereof Download PDFInfo
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- CN101274262B CN101274262B CN2008100311289A CN200810031128A CN101274262B CN 101274262 B CN101274262 B CN 101274262B CN 2008100311289 A CN2008100311289 A CN 2008100311289A CN 200810031128 A CN200810031128 A CN 200810031128A CN 101274262 B CN101274262 B CN 101274262B
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Abstract
The invention provides a method for improving the activity of zinc powders with supersonic and a devide as well as applications thereof, wherein, the method leads the zinc powder to always keep fresh and active surface under solution environment condition that the zinc powder is taken as reducing agent, the alkali-typed zinc salt passivation film on the surface of the zinc powder can be removed by the supersonic. The supersonic has the frequency of 15-60 kHz and the sound intensity of 1-1000w/cm2; the ultrasonic cavitation reaction time on the zinc powder is 1-45 minutes. Under the effect of supersonic, common ZnSO4 solution containing 100mg/L of cobalt can reduce the cobalt content to 0.8mg/L within 30 minutes. The device provided by the method of the invention improves the zinc powder activativity with the supersonic and comprises at least a reaction chamber where ZnSO4 solution is fully filled; at least a supersonic emitter and at least one mixing device are dipped and arranged in the reaction chamber. The applications of the method at least comprise a technique of cobalt removal with antimony salt and a technique of cobalt removal with antimony trioxide.
Description
Affiliated technical field
The present invention relates to a kind of method and device of solution of zinc sulfate removal of impurities, be a kind of method and device that adopts zinc powder to remove impurity in the solution as reducing agent specifically, especially in Zinc hydrometallurgy process, use the method and the device of improving zinc powder activity with ultrasonic, belong to the purification techniques field.
Background technology
Comprise plurality of impurities compositions such as copper, cadmium, cobalt, nickel owing to leach the solution of zinc sulfate of zinc ore powder output in the zinc hydrometallurgy, so need handle to the solution of zinc sulfate that leaches the zinc ore powder.The at present general zinc powder that adopts removes plurality of impurities in the solution of zinc sulfate as reducing agent, and this is a kind of general process for purifying in the Zinc hydrometallurgy process.Antimonic salt removes cobalt technology, is under the condition of zinc powder as reducing agent, utilizes antimonic salt (comprising antimonials such as potassium antimony tartrate, stibium trioxide) to remove cobalt, belongs to a kind of general cobalt technology of removing that removes cobalt ions in the solution of zinc sulfate.
Antimonic salt removes cobalt technology, by zinc powder generation displacement reaction, the solution of zinc sulfate current potential is reduced and maintains negative voltage belt, makes the reaction of cobalt ions and antimonic salt, generation CoSb compound.The stable state voltage belt of CoSb is-0.4～-1.0V, when solution was in this voltage belt, cobalt ions and antimonic salt generated CoSb, and can stable existence; When the zinc dust precipitation underaction when keeping the stable state current potential of CoSb, CoSb redissolves again.Therefore, the activity of zinc powder or zinc powder participate in the validity of reaction, are directly connected to the zinc consumption that antimonic salt removes cobalt technology.Studies show that the zinc dust precipitation reaction is reduced into hydrogen with the hydrogen ion in the solution, pH value of solution value trend rises, and impels basic zinc salt (to comprise Zn (OH)
2) generate; Basic zinc salt can form passivating film on zinc powder surface, zinc powder is wrapped up layer by layer, makes its reduction or loses activity, and serious situation is that zinc powder is covered by basic zinc salt passivating film fully, becomes invalid zinc powder.For weakening or eliminate the negative effect of basic zinc salt passivating film, antimonic salt removes cobalt process using high-strength mechanical and stirs, 75 ℃ of control pH value of solution 5.2 below, liquid temperature are with first-class technical measures, but zinc consumption accounts for the 3-4% of electric zinc output still up to 150-200 times of theoretical requirement.Reach 40mg/L when above when solution of zinc sulfate contains cobalt concentration, zinc consumption and energy consumption roll up, and need to adopt multistage to remove cobalt technology, and therefore the solution of zinc sulfate of high cobalt concentration purifies, and becomes the technical bottleneck that the restriction antimonic salt removes cobalt technology again.
Remove the high problem of cobalt technology zinc consumption at antimonic salt, EP134644 proposes to improve the metal impurities stalling characteristic with flocculant, to reduce zinc consumption; US4252622 proposes to add by monitoring oxidation one reduction potential regulation and control zinc powder, prevents that zinc powder is excessive.The method that EP134644, US4252622 propose does not solve the problem that zinc powder activity reduces with reaction process, and zinc consumption is still higher.Therefore necessary this is further studied.
Summary of the invention
The objective of the invention is to: adopt zinc powder as the impurity in the reducing agent removal solution at having now, zinc powder activity is low or be easy to lose efficacy, the low or problem that is easy to lose efficacy of zinc powder activity in the Zinc hydrometallurgy process especially, a kind of method that can improve zinc powder reduction agent activity is provided.
Another object of the present invention is to: a kind of device that can improve zinc powder reduction agent activity is provided.
Another object of the present invention is to: a kind of purposes of improving zinc powder reduction agent activity methods with ultrasonic wave is provided.
The technical solution used in the present invention is: a kind of method of utilizing ultrasonic wave to improve zinc powder activity under the solution environmental condition, adopt zinc powder as reducing agent, and solution is shone with ultrasonic wave, utilize hyperacoustic ultrasonic cavitation to remove the basic zinc salt passivating film on parcel zinc powder surface, make zinc powder remain fresh active surface.
Described ultrasonic wave, frequency are 15-60kHz, and the sound intensity is 1-1000w/cm2, to ultrasonic wave action time of zinc powder be 1-45 minute.
Described solution is for containing the conventional solution of zinc sulfate of the Zinc hydrometallurgy process below the concentration of cobalt ions 100mg/L.
Described ultrasonic cavitation is to utilize ultrasonic wave that solution of zinc sulfate is carried out ultrasonic irradiation, make ultrasonic wave inject solution of zinc sulfate, in solution, produce a large amount of cavitation bubbles, cause the ultrasonic cavitation effect: when cavitation bubble collapses, minimum space forms up to the high temperature of 5000K, several thousand atmospheric high pressure around cavitation bubble in the extremely short time, and supervene at a high speed jet and remove in the solution of zinc sulfate parcel and the surface particle film of the zinc powder activity of passivation, make zinc powder remain fresh active surface, thereby strengthen the mechanism of zinc powder reaction.This kind cavitation is under the stable condition of compound between foreign metal at solution, ultrasonic wave applies vibration to impurity crystal grain again and cleans, make it remain fresh active surface, thereby strengthen the crystal seed graining effect of crystal grain, further promote the reaction of formation of compound between foreign metal, quicken the removal of impurities reaction.
The described main application of using the method for improving zinc powder activity with ultrasonic comprises that the antimonic salt that is applied in the Zinc hydrometallurgy process removes cobalt technology and arsenic salt removes in the cobalt technology.
A kind of device with improving zinc powder activity with ultrasonic that proposes according to described method is: a kind of device with improving zinc powder activity with ultrasonic, comprise that at least one fills with the reaction chamber of solution of zinc sulfate, described reaction chamber can be rectangle reaction chamber or tubular reaction chamber, and is provided with at least one inlet, a liquid outlet; In the reaction chamber at least submergence be provided with a ultrasonic transmitter; Described ultrasonic transmitter can be board-like ultrasonic transmitter, cartridge type ultrasonic transmitter or bar type ultrasonic transmitter; In reaction chamber, also be provided with at least one agitating device; Described agitating device can be mechanical stirring device, magnetic stirring apparatus or waterpower agitating device; The device that at least one eliminates the hydrogen negative effect can also be set in the reaction chamber, and the device of described elimination hydrogen negative effect is to be used for impedance hydrogen becomes the hydrogen film at the ultrasonic transmitter surface aggregation mechanical device.
Device as shown in Figure 1 with improving zinc powder activity with ultrasonic, comprise the rectangle reaction chamber, waterpower agitating device and the board-like ultrasonic transmitter more than that fill with solution of zinc sulfate, it is characterized in that: the gap between adjacent two board-like ultrasonic transmitters, it is unique passage of solution of zinc sulfate, and be provided with at least one corrugated sheet, corrugated sheet can be the waterpower stirring action, can also be the effect of eliminating the hydrogen negative effect.
Device as shown in Figure 2 with improving zinc powder activity with ultrasonic, comprise the tubular reaction chamber, mechanical stirring device and the board-like ultrasonic transmitter more than that fill with solution of zinc sulfate, it is characterized in that: board-like ultrasonic transmitter can be that the flow direction emission of reverse solution of zinc sulfate is hyperacoustic, and the flow direction emission that also can be perpendicular to solution of zinc sulfate is hyperacoustic.
Device as shown in Figure 3 with improving zinc powder activity with ultrasonic, comprise the tubular reaction chamber, mechanical stirring device and at least one the cartridge type ultrasonic transmitter that fill with solution of zinc sulfate, it is characterized in that: cartridge type ultrasonic transmitter and tubular reaction chamber have same vertical axis, and are hyperacoustic towards the emission of tubular reaction chamber circumference.
Device as shown in Figure 4 with improving zinc powder activity with ultrasonic, comprise rectangle reaction chamber, magnetic stirring apparatus and an above bar type ultrasonic transmitter of filling with solution of zinc sulfate, it is characterized in that: the flow direction of solution of zinc sulfate, with hyperacoustic transmit direction can be in the same way, also can be in opposite directions or reverse, can also be vertical.
The present invention is applied to the know-why that antimonic salt removes cobalt technology: fill with in the reaction chamber that contains the following conventional solution of zinc sulfate of cobalt 100mg/L frequency 15-60kHz, sound intensity 1-1000w/cm
2At least one ultrasonic transmitter and at least one agitating device move continuously; PH value of solution, liquid temperature, antimonic salt and addition and zinc powder are that antimonic salt removes the common usefulness of cobalt technology.Ultrasonic wave is injected solution of zinc sulfate, in solution, produce a large amount of cavitation bubbles, cause the ultrasonic cavitation effect: when cavitation bubble collapsed, minimum space formed up to the high temperature of 5000K, several thousand atmospheric high pressure around cavitation bubble in the extremely short time, and supervened jet at a high speed.Hyperacoustic this cavitation, can efficiently remove the basic zinc salt passivating film on zinc powder surface, make zinc powder remain fresh active surface, thereby make zinc powder effectively participate in course of reaction, reducing also fast, the stable maintenance solution potential accelerates the reaction of formation of CoSb in negative voltage belt greatly.Through 1-45 minute cavitation of ultrasonic wave, cobalt ions is converted into the CoSb compound crystal grain, reaches the zinc electrolyte quality requirement except that liquid behind the cobalt contains cobalt concentration.Realize process thus with improving zinc powder activity with ultrasonic.
Description of drawings
Fig. 1 is the structural representation of one embodiment of the invention;
Fig. 2 is the structural representation of another embodiment of the present invention;
Fig. 3 is the structural representation of another embodiment of the present invention;
Fig. 4 is the structural representation of another embodiment of the present invention.
Among the figure, 1, reaction chamber; 2, ultrasonic transmitter, 3, agitating device; 4, inlet; 5, solution of zinc sulfate; 6, slag-drip opening; 7, liquid outlet; 8, except that solution behind the cobalt; 9, board-like ultrasonic transmitter; 10, mechanical stirring device; 11, tubular reaction chamber; 12, solution of zinc sulfate flow direction; 13, tubular reaction chamber; 14, cartridge type ultrasonic transmitter; 15, vertical axis; 16, mechanical stirring device; 17, remove the outlet of solution of zinc sulfate behind the cobalt; 18, remove the outlet of cobalt slag; 19, the inlet of solution of zinc sulfate; 20, magnetic stirring apparatus; 21 bar type ultrasonic transmitters; 22, division board; 23, rectangle reaction chamber.
The specific embodiment
The invention will be further described below in conjunction with drawings and Examples, but protection scope of the present invention is not limited to the described scope of embodiment.
Embodiment one
Fig. 1 is one embodiment of the present of invention, from accompanying drawing 1 as can be seen, the present invention is a kind of device with improving zinc powder activity with ultrasonic, described method with improving zinc powder activity with ultrasonic, be to adopt under the solution environmental condition of zinc powder as reducing agent, remove the basic zinc salt passivating film on zinc powder surface with ultrasonic wave, make zinc powder remain the method for fresh active surface.Described ultrasonic wave, frequency 15-60kHz, sound intensity 1-1000w/cm
2, to the ultrasonic cavitation time of zinc powder be 1-45 minute.Described employing zinc powder comprises the conventional solution of zinc sulfate that contains the following Zinc hydrometallurgy process of concentration of cobalt ions 100mg/L at least as the solution environmental of reducing agent.
Device as shown in Figure 1 with improving zinc powder activity with ultrasonic, shown ultrasound-enhanced zinc dust precipitation removes the cobalt device, comprise a reaction chamber 1 that fills with solution of zinc sulfate 5, described reaction chamber is the rectangle reaction chamber, and is provided with an inlet 4, a liquid outlet 7 and a slag-drip opening 6; Submergence is provided with 10 ultrasonic transmitters 2 in the reaction chamber 1, and described ultrasonic transmitter 2 is board-like ultrasonic transmitter, takes to flow to hierarchal arrangement by solution of zinc sulfate 5; Also be provided with agitating device 3 in reaction chamber 1, described agitating device 3 is waterpower agitating devices.And the gap between adjacent two board-like ultrasonic transmitters is unique passage of solution of zinc sulfate, except that solution behind the cobalt 8 is discharged by liquid outlet 7; And be provided with at least one corrugated sheet that plays the waterpower stirring action.At least one dehydrogenation film device can also be set in the reaction chamber, and described dehydrogenation film device can be an at least one corrugated sheet.
The operation principle of described device for carrying out said is: in filling with the rectangle reaction chamber of the conventional solution of zinc sulfate that contains below the cobalt 100mg/L, 10 frequency 15-60kHz, sound intensity 1-1000w/cm are arranged
2Board-like ultrasonic transmitter and a waterpower agitating device move continuously; PH value of solution, liquid temperature, antimonic salt and addition and zinc powder are that antimonic salt removes the common usefulness of cobalt technology.Ultrasonic wave is injected solution of zinc sulfate, in solution, produce a large amount of cavitation bubbles, cause the ultrasonic cavitation effect: when cavitation bubble collapsed, minimum space formed up to the high temperature of 5000K, several thousand atmospheric high pressure around cavitation bubble in the extremely short time, and supervened jet at a high speed.Hyperacoustic this cavitation can efficiently be removed the basic zinc salt passivating film on trend parcel zinc powder surface, makes zinc powder remain fresh active surface, thereby makes zinc powder effectively participate in the displacement reaction process.Effective participation displacement reaction of zinc powder, reducing also fast, the stable maintenance solution potential accelerates the reaction of formation of CoSb in negative voltage belt greatly.Through ultrasonic wave 1-45 minute cavitation, most of zinc consumption totally, cobalt ions is converted into the CoSb compound crystal grain, removes behind the cobalt solution and contains cobalt concentration and reach the zinc electrolyte quality requirement.Realize process thus with improving zinc powder activity with ultrasonic.
Embodiment two
Accompanying drawing 2 is an alternative embodiment of the invention.The principle of its removal of impurities is the same with embodiment one, mainly is that apparatus structure is different.Device as shown in Figure 2 with improving zinc powder activity with ultrasonic, comprise the tubular reaction chamber 11 that fills with solution of zinc sulfate 5, mechanical stirring device 10 and along tubular reaction chamber 11 periphery, board-like ultrasonic transmitter 9 more than one, board-like ultrasonic transmitter 9 can be that reverse solution of zinc sulfate flow direction 12 emissions are hyperacoustic, also can be that vertical solution of zinc sulfate flow direction emission is hyperacoustic.
The advantage of this device for carrying out said is, utilizes the solution eddy flow to impact ultrasonic transmitter surface hydrogen film, and the ultrasonic wave EFFECTIVE RANGE is longer, and convenient user removes the cobalt groove and transforms existing the purification.
Embodiment three
Accompanying drawing 3 is an alternative embodiment of the invention.The principle of its removal of impurities is the same with embodiment one, mainly is that apparatus structure is different.Cartridge type ultrasonic transmitter and tubular reaction chamber have same vertical axis 15, and are hyperacoustic towards the emission of tubular reaction chamber circumference.Ultrasound-enhanced zinc dust precipitation as shown in Figure 3 removes the device of cobalt, comprise the tubular reaction chamber 13, mechanical stirring device 16 and the cartridge type ultrasonic transmitter 14 that fill with solution of zinc sulfate 5, and cartridge type ultrasonic transmitter 14 has same vertical axis with tubular reaction chamber 13, and cartridge type ultrasonic transmitter 14 is hyperacoustic towards the emission of tubular reaction chamber circumference.Be provided with the inlet 19 of solution of zinc sulfate 5 in the lower side of tubular reaction chamber 13, be provided with outlet 18 in the centre of tubular reaction chamber 13 bottom surfaces, the outlet 17 of solution of zinc sulfate after the side on tubular reaction chamber 13 tops is provided with except that cobalt except that the cobalt slag.
The advantage of this device for carrying out said is that facility weakens hydrogen film negative effect.
Embodiment four
Accompanying drawing 4 is an alternative embodiment of the invention.Device as shown in Figure 4 with improving zinc powder activity with ultrasonic, comprise the rectangle reaction chamber 23 that fills with solution of zinc sulfate 5, in rectangle reaction chamber 23, rectangle reaction chamber 23 is divided into 5 layers from top to bottom, is provided with 1 magnetic stirring apparatus 20 and 1 bar type ultrasonic transmitter 21 at each layer by division board 22.The flow direction of solution of zinc sulfate 5, with hyperacoustic transmit direction can be in the same way, also can be in opposite directions or reverse, can also be vertical.
The advantage of this device for carrying out said is, the convenient high sound intensity improving zinc powder activity with ultrasonic of use removes cobalt efficient height, and the time is short, help except that cobalt, filtering technique and equipment integrated.
The present invention's method of improving zinc powder activity with ultrasonic, the effect of using ultrasound cavitation is strengthened zinc powder and is cleaned, and prevents the zinc powder surface passivation, keeps zinc powder activity, thereby strengthens antimonic salt except that the cobalt process, and effect is remarkable.
During the removing the cobalt temperature and be controlled at 85～95 ℃ of the inventive method, the higher cobalt efficient of removing will be obtained; At a lower temperature, as 60 ℃ of the liquid temperature behind the copper removal cadmium, it also is very high removing cobalt efficient, except that can saving the heating expense, also can obviously reduce the redissolution of cobalt salt, also becomes comparatively serious but zinc hydroxide hinders the problem of filtering.
The inventive method will produce maximized economic benefit as being used for the cleaning process technology transformation that one section purification removes cobalt nickel.
The inventive method is 1 ~ 45 minute with the ultrasonic cavitation time of improving zinc powder activity with ultrasonic, compares in commonly used 90 ~ 150 minutes with zinc hydrometallurgy factory, and except that the cobalt time significantly shortens, cobalt salt redissolves and significantly reduces, and energy consumption significantly reduces, and equipment investment also significantly reduces.
The antimonic salt that the inventive method is used can be a stibium trioxide, also can be tartar emetic.Addition determines that according to the content of cobalt and nickel of solution of zinc sulfate the antimony ion mole addition that antimonial is brought into is selected in 0.5 ~ 9 scope with the ratio of the integral molar quantity of the cobalt nickel ion of solution of zinc sulfate.
The zinc powder that the present invention adds can be simple zinc powder, also can be that zinc antimony alloy powder and other are generally used for removing the zinc-base granular material of cobalt nickel.If solution of zinc sulfate passes through the copper removal cadmium in advance, then be used for removing the zinc powder addition of cobalt nickel generally between 0.2 ~ 2.0g/L.
The present invention is used for the removal of conventional solution of zinc sulfate nickel ion impurity with the method for improving zinc powder activity with ultrasonic, also is obvious results.Test two, experiment three and test four result have all fully confirmed this point.
Test one
Experimental condition: zinc powder 3.5g/L; Stibium trioxide is an amount of; 60～65 ℃ of temperature; 60 minutes clarification times; No ultrasonic irradiation.
| The neutral supernatant of zinc ore powder | Co | Cd | Cu | Ni | Sb |
| Mg/L before purifying | 9 | 500 | 175 | 5 | 4.2 |
| Purify back mg/L | 4.7 | 0.1 | 0.1 | 1.5 | 4 |
Test two
Experimental condition: zinc powder 4g/L; Stibium trioxide is an amount of; 60～65 ℃ of temperature; 60 minutes clarification times; The 25kHz ultrasonic irradiation.
| The neutral supernatant of zinc ore powder | Co | Cd | Cu | Ni | Sb |
| Mg/L before purifying | 9 | 500 | 175 | 5 | 4.2 |
| Purify back mg/L | 0.2 | 1.2 | 0.6 | 0.9 | 0.1 |
Test three
Experimental condition: zinc powder 3g/L; Stibium trioxide is an amount of; 60～70 ℃ of temperature; 60 minutes clarification times; The 28kHz ultrasonic irradiation.
| The neutral supernatant of zinc ore powder | Co | Cd | Cu | Ni | Sb |
| Mg/L before purifying | 9 | 500 | 175 | 5 | 4.2 |
| Purify back mg/L | 0.01 | 3.52 | 1.43 | 0.1 | 0.01 |
Test four
Experimental condition: zinc powder 2.5g/L; Potassium antimony tartrate 8mg/L; 78～85 ℃ of temperature; 20 minutes clarification times; The 20kHz ultrasonic irradiation.
| The neutral supernatant of zinc ore powder | Co | Cd | Cu | Ni | Sb |
| Mg/L before purifying | 9 | 500 | 175 | 5 | 4.2 |
| Purify back mg/L | 0.48 | 0.84 | 0.52 | 0.31 | 0.12 |
Test shows, cavitation effect of ultrasonic waves can also promote CoSb crystal grain anti-molten fast.Zinc consumption is when a certain amount of, and solution potential rises, and when solution potential exceeds CoSb stable state critical potential, ultrasonic wave can quicken CoSb crystal grain conversely and redissolve.Therefore, the zinc powder in the described solution of zinc sulfate being applied ultrasonic cavitation in limited time, is to guarantee to improve zinc powder activity to remove cobalt technology efficiently except that cobalt and the minimum sufficient and necessary condition of zinc consumption with the application antimonic salt.
Test shows, the device of making according to the method described above with improving zinc powder activity with ultrasonic removes the cobalt process application in conjunction with antimonic salt, and effect is remarkable: the conventional solution of zinc sulfate that contains cobalt 9.5mg/L, during zinc consumption 2.5g/L, will contain cobalt concentration and be reduced to 0.4mg/L in 15 minutes; The conventional solution of zinc sulfate that contains cobalt 50mg/L during zinc consumption 4g/L, will contain cobalt concentration and be reduced to below the 0.8mg/L in 20 minutes; The conventional solution of zinc sulfate that contains cobalt 100mg/L during zinc consumption 5.2g/L, will contain cobalt concentration and be reduced to 0.8mg/L in 25 minutes.
Test shows that under ultrasonic cavitation, the zinc dust precipitation reaction is significantly accelerated, hydrogen yield enlarges markedly, near the ultrasonic wave surface of emission displacement reaction is particularly violent, so that the bubble hydrogen that generates the fast trend ultrasonic wave surface of emission forms the hydrogen film, thereby seriously hinders the transmission of ultrasonic energy.Measure confirmation, use sound intensity 1w/cm
2, frequency 28kHz ultrasonic wave inject conventional solution of zinc sulfate, only in the several seconds, promptly form the hydrogen film at the ultrasonic wave surface of emission, make the effective transmitting range of ultrasonic energy be reduced to initial transmissions tens thousand of/one constantly.Therefore, weakening or eliminate the resistance of hydrogen film to ultrasonic energy emission, is very important for the activity of improving zinc powder in the conventional solution of zinc sulfate with ultrasonic wave.
Test shows that under ultrasonic cavitation, before most of zinc powder dissolving, the generating rate of CoSb is far longer than the anti-molten speed of CoSb; After to a certain degree, or the zinc powder quantity not sufficient continues to apply the ultrasonic wave effect to keep solution potential-0.4V when following, then oppositely promotes CoSb crystal grain anti-molten fast at zinc consumption.
Test shows that also the control of liquid temperature also is very important: when the liquid temperature is reduced to 57 ℃, gluey basic zinc salt can occur in the solution.This to zinc dust precipitation reaction carry out fast with high-rate fitration all be disadvantageous.Therefore, conventional solution of zinc sulfate must reach more than 60 ℃ except that the liquid temperature control of cobalt.
Test shows that also the control of pH value of solution also is very important: under pH value of solution 5.5 above conditions, it is muddy sticky that the basic zinc salt in the solution can make solution becomes get.Although experiment confirm is not too responsive with the effect of improving zinc powder activity with ultrasonic to the variation of pH value of solution, decrease for filter efficiency, cobalt slag zinc, especially zinc electrolyte contains the assurance of zinc concentration, also is necessary below the control solution reaction terminal pH5.5.
Experiment shows that also stirring intensity also is very important: to static state, eddy flow inject ultrasonic wave with fluidised solution of zinc sulfate, what antimonic salt removed cobalt technology removes cobalt efficient, difference also is bigger.The actual utility that stirs except reinforcement zinc powder, antimonic salt evenly mix with solution of zinc sulfate, especially stops outside the zinc powder reunion layering, can not efficiently remove the basic zinc salt passivating film that trend zinc powder surface generates.
Experiment also shows, injects the conventional solution of zinc sulfate that contains 70 ℃ of cobalt 100mg/L, liquid temperature with ultrasonic wave, press 5.2g/L concentration adding zinc powder after, the liquid temperature has been brought up to 80 ℃ rapidly.Therefore, antimonic salt can carry out under lower liquid temperature condition except that cobalt technology.
Claims (8)
1. method with improving zinc powder activity with ultrasonic, it is characterized in that: adopt zinc powder as reducing agent, and with ultrasonic wave solution is shone, utilize hyperacoustic ultrasonic cavitation to remove the basic zinc salt passivating film on parcel zinc powder surface, make zinc powder remain fresh active surface; Described ultrasonic wave, frequency are 15-60kHz, and the sound intensity is 1-1000w/cm
2, to ultrasonic wave action time of zinc powder be 1-45 minute.
2. the method with improving zinc powder activity with ultrasonic as claimed in claim 1 is characterized in that: described solution, and for containing the conventional solution of zinc sulfate of the Zinc hydrometallurgy process below the concentration of cobalt ions 100mg/L.
3. the method with improving zinc powder activity with ultrasonic as claimed in claim 1, it is characterized in that: described ultrasonic cavitation is to utilize ultrasonic wave that solution of zinc sulfate is carried out ultrasonic irradiation, make ultrasonic wave inject solution of zinc sulfate, in solution, produce a large amount of cavitation bubbles, cause the ultrasonic cavitation effect: when cavitation bubble collapses, minimum space forms high temperature up to 5000K around cavitation bubble in the extremely short time, several thousand atmospheric high pressure, and supervene at a high speed jet and remove in the solution of zinc sulfate parcel and the surface particle film of the zinc powder activity of passivation, make zinc powder remain fresh active surface, thereby strengthen the mechanism of zinc powder reaction.
4. realize the described device of claim 1 for one kind with improving zinc powder activity with ultrasonic, it is characterized in that: described device with improving zinc powder activity with ultrasonic, comprise that at least one fills with the reaction chamber of solution of zinc sulfate, described reaction chamber can be rectangle reaction chamber or tubular reaction chamber, and is provided with at least one inlet, a liquid outlet; In the reaction chamber at least submergence be provided with a ultrasonic transmitter; Described ultrasonic transmitter can be board-like ultrasonic transmitter, cartridge type ultrasonic transmitter or bar type ultrasonic transmitter; In reaction chamber, also be provided with at least one agitating device; Described agitating device can be mechanical stirring device, magnetic stirring apparatus or waterpower agitating device.
5. the device with improving zinc powder activity with ultrasonic as claimed in claim 4, it is characterized in that: the device that at least one eliminates the hydrogen negative effect is set in reaction chamber, and the device of described elimination hydrogen negative effect is to be used for impedance hydrogen becomes the hydrogen film at the ultrasonic transmitter surface aggregation mechanical device.
6. realize the described device of claim 1 for one kind with improving zinc powder activity with ultrasonic, it is characterized in that: described device with improving zinc powder activity with ultrasonic comprises rectangle reaction chamber, waterpower agitating device and the board-like ultrasonic transmitter more than that fills with solution of zinc sulfate, gap between adjacent two board-like ultrasonic transmitters, be unique passage of solution of zinc sulfate, and be provided with at least one corrugated sheet.
7. realize the described device of claim 1 for one kind with improving zinc powder activity with ultrasonic, it is characterized in that: described device with improving zinc powder activity with ultrasonic comprises the tubular reaction chamber that fills with solution of zinc sulfate, mechanical stirring device and board-like ultrasonic transmitter more than, and board-like ultrasonic transmitter is that reverse solution of zinc sulfate flow direction emission is hyperacoustic or hyperacoustic perpendicular to the emission of solution of zinc sulfate flow direction.
8. purposes with the improving zinc powder activity with ultrasonic method as claimed in claim 1 is characterized in that: described method with improving zinc powder activity with ultrasonic is applied to antimonic salt in the Zinc hydrometallurgy process and removes cobalt technology and arsenic salt except that in the cobalt technology.
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| CN102220493B (en) * | 2011-07-27 | 2013-06-19 | 昆明冶金研究院 | Method and device for purifying zinc sulfate solution based on action of cavitation effect |
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| CN105836779A (en) * | 2016-03-28 | 2016-08-10 | 余国礼 | Apparatus of converting celestite into strontium carbonate under cavitation effect |
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| CN106929677B (en) * | 2017-04-03 | 2019-01-08 | 张华� | A kind of method and device improving zinc powder utilization rate in zinc sulfate fluid purification |
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| CN110819821B (en) * | 2018-08-07 | 2021-05-11 | 昆明理工大学 | Method for intensively purifying zinc sulfate solution |
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| CN111705213A (en) * | 2020-07-13 | 2020-09-25 | 昆明冶金高等专科学校 | Method and device for purifying zinc sulfate solution by using ultrasonic waves |
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|---|---|---|---|---|
| CN1262678C (en) * | 2003-02-28 | 2006-07-05 | 西安建筑科技大学 | Method for removing zinc and cobalt in cobalt dregs generated in zinc hydrometallurgy by using ultrasonic separation |
| CN1530452A (en) * | 2003-03-14 | 2004-09-22 | 中国有色工程设计研究总院 | Method and apparatus for removing copper, cadmium and cobalt from zinc sulfate solution |
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| CN101274262A (en) | 2008-10-01 |
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