CN102220493B - Method and device for purifying zinc sulfate solution based on action of cavitation effect - Google Patents
Method and device for purifying zinc sulfate solution based on action of cavitation effect Download PDFInfo
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Abstract
The invention relates to a method and a device for purifying a zinc sulfate solution based on action of a cavitation effect. The method comprises the following steps: adding zinc powder into a solution before purifying the zinc sulfate, and conveying the solution to a partition plate in a purifying container or forming cavitation effect bubbles through the periodic oscillation action of a vibration device for stripping impurities which are displaced out from the surface of the zinc powder, thereby keeping the reaction surface of the zinc powder exposed at any time, being capable of participating in displacement, purification and removal of the impurities and reducing the consumption amount of the zinc powder; and filtering the solution which passes through a 1-3 grade cavitation effect generation device for acting for 20-50 minutes, and obtaining filtrate which is a new qualified electrolysis solution and filter residue which is high-grade copper-cadmium slag or nickel-cobalt slag. When in purification and removal of cobalt and nickel, the zinc powder, copper sulfate and antimony white powder are further added into the purifying container, the energy consumption is low and the using quantity of the zinc powder is reduced from 100-200 times of the content in traditional displacement of the cobalt by using the zinc powder to 20-50 times of the content.
Description
Technical field
The invention belongs to the purifying method of solution of zinc sulfate in zinc hydrometallurgy, be specifically related to a kind of Purification of zinc sulfate solution method and device based under the cavitation effect effect.
Background technology
Zinc is important non-ferrous raw material.At present, zinc is only second to copper and aluminium in the consumption of non-ferrous metal, and the zinc metal has good calenderability, wear resistance and corrosion-resistant, can make physics and the better alloy of chemical property with various metals.Main products by zinc production has: metallic zinc, zinc base alloy, zinc oxide, and these end-uses are very extensive, mainly contain the following aspects:
1. for zinc-plated aspect, account for 46% of zinc consumption.2. manufactured copper alloy material aspect, account for 15% of zinc consumption.3. for the zinc alloy aspect, account for 15% of zinc consumption.4. Zinc-oxide-based product accounts for 11% of zinc consumption.5. manufacture drying battery aspect zinc used and account for 13% of zinc consumption.
In recent years, the zinc production and consumption in the world increases substantially year by year, produces a little less than consumption.The market value of zinc is also to increase year by year, in 2007, peaks.Table 1 is the whole world and Chinese zinc production and consumption in recent years.
Table 1 is the whole world and Chinese zinc production and consumption in recent years
| Time | 1999 | 2000 | 2001 | 2002 | 2003 | 2004 | 2005 | 2006 | 2007 |
| World's zinc output (ten thousand tons) | 810.9 | 836.8 | 920.0 | 940.0 | 979.0 | 1022 | 1031.5 | 1084.0 | 1141 |
| World's zinc consumption (ten thousand tons) | 816.6 | 840.0 | 879.0 | 900.0 | 926.1 | 1044 | 1062.4 | 1108.0 | 1157 |
| World's zinc price ($/t) | 1077 | 1150 | 886 | 779 | 828 | 1381 | 3275 | 3236 | |
| China's zinc output (ten thousand tons) | 169.50 | 192.00 | 204.00 | 204.00 | 222.7 | 251.9 | 286.5 | 322.5 | |
| China's zinc consumption (ten thousand tons) | 109.90 | 113.00 | 149.00 | 162.00 | 190.0 | 281.7 | 315.0 | ||
| China's zinc price (unit/t) | 9781 | 10905 | 9167 | 7945 | 8547 | 10100 | 13509 | 27187 | 27490 |
As can be seen here, zinc plays an important role in national product, but along with the scarcity day by day of zinc metals resources and the increase of zinc consumption, and the second stage employ that how to reduce the cost of zinc in smelting and zinc metal seems and is even more important.
Due to the Zinc Hydrometallurgy Technology development, adopt in the world the zinc amount of metal of zinc hydrometallurgy output to surpass 80% at present, the current zinc hydrometallurgy of China accounts for more than 90% of total capacity.Therefore, the production cost that how to reduce zinc hydrometallurgy plays vital effect to whole zinc metallurgy industry.
Solution of zinc sulfate is the intermediate raw material of producing electrolytic zinc, because the solution of zinc sulfate after leaching often contains a large amount of impurity, as Cu, Cd, Ni, Co, Ge, Sb etc., has greatly affected current efficiency in follow-up electrowinning process and the quality of electrolytic zinc.Because the space of power consumption and personnel cost saving is very limited, the cost control that zinc is smelted depends primarily on the degree of purification of solution of zinc sulfate impurity, the i.e. consumption of zinc powder.
In the zinc metallurgical process, various starting material, energy consumption etc. consume as table 2.By existing market value, cost structure and proportion are also as table 2.
Table 2 ton zinc tooling cost
As can be seen from result of Table 2, in the tooling cost of zinc metallurgy, be up to power consumption, accounting for 54% of zinc metallurgical processing cost, is secondly zinc consumption, accounts for 21% of zinc metallurgical processing cost, be pole plate consumption again, account for 5% of total cost, artificial, manage and keep in repair approximately 9%, other is 11%.
Although power consumption is tooling cost 54%, Zong about 3790 degree of power consumption also are on advanced level in modern zinc hydrometallurgy, it is little that power consumption continues to fall space again, even save 5% power consumption, energy-conservation expense accounts for 2.7% of total processing charges.
Because zinc consumption accounts for 21% in zinc metallurgical processing cost, and several 10 times to more than 100 times of zinc consumption theoretical consumption, the zinc powder of every saving 10%, can reduce costs 2%, for zinc is metallurgical, has important effect.
In Purification of zinc sulfate solution, impurity is mainly two classes, and the first kind is for the impurity that affects quality product as Cu, Cd, Fe, and Equations of The Second Kind is for to affect electrolytic deposition process impurity as As, Sb, Ni, Co, Ge, F and Cl etc.
For first kind impurity, can adopt ion-exchange, extraction, displacement, the precipitator method etc.For the solution of zinc sulfate purified, wherein Fe generally reaches the purification requirement, is no longer purified; For Cu and Cd, generally adopt zinc powder to be replaced easily and be removed; For Equations of The Second Kind impurity, because liquid before purifying adopts the Fe neutralizing hydrolysis, As and Sb basically are hydrolyzed, adsorb and remove, and Ge and In etc. also major part are hydrolyzed and remove, and in solution, Ni and Co, the especially Co of residual difficult hydrolysis are difficult to remove.Zinc powder accounts for more than 80% of zinc powder total burn-off at the consumption except in Ni, Co, and the zinc powder consumption in removing the Co process accounts for 60% left and right of total zinc powder consumption.Therefore, how to reduce and the zinc powder purifying zinc sulfate solution is played an important role except the zinc powder consumption in Ni, Co.
In solution of zinc sulfate, adopt in the zinc dust precipitation scavenging process, the displacement signal is as Fig. 1.After zinc particle 1 enters solution of zinc sulfate 3, with the Ni in solution, with the Co ion, contact, on the zinc particle surface, replacement(metathesis)reaction occurs, the impurity 2 such as the metallic nickel displaced and cobalt remain on zinc particle with solid-state form.Along with zinc particle moves in solution, with other Ni in solution, with the Co ion, further contact, further be reduced, whole zinc particle surface is covered by Ni and Co metal.
In replacement process, according to the displacement step of following order, carry out:
(1) in solution, Ni and Co ion are diffused into the zinc particle surface;
(2) be diffused into Ni and the Co ion desolvation on zinc particle surface;
(3) desolvated Ni and Co ion and zinc powder generation replacement(metathesis)reaction;
(4) the Zn ion that replacement(metathesis)reaction forms diffuses in solution.
Due to Ni and Co that substitution product is solid, it is deposited in the surface of zinc particle, and after forming precipitation, in its obstruction solution, Ni and Co ion, to the zinc powder surface diffusion, make the zinc dust precipitation reaction be converted into diffusion control by the control of replacement(metathesis)reaction.If accelerate carrying out or the speed of replacement(metathesis)reaction, must make the Ni and the Co metal that are deposited on the zinc powder surface break away from zinc particle.
If the Ni of replacement deposition and Co metal level parcel zinc particle, the inside zinc powder of parcel is because the speed that Ni and Co ion diffuse into the zinc powder surface is slow, cause the inside zinc powder of parcel effectively not utilize, the zinc powder utilization ratio is not high, thereby in the displacement purge process, zinc consumption is large, cause the purification cost of zinc solution high.
In sum, improve the speed of replacement(metathesis)reaction, just need to improve the displacement temperature and enough zinc powders are provided; Reduce the zinc powder consumption, just must make to precipitate Ni and Co and break away from the zinc powder surface.
The cobalt method of removing adopted both at home and abroad at present mainly contains: Beta Naphthol 99MIN method, xanthate are except cobalt method, zinc replacement.Adopt xanthate, Beta Naphthol 99MIN can effectively remove cobalt, but cause serious environmental pollution while adopting xanthate, Beta Naphthol 99MIN; And while adopting traditional zinc dust precipitation, needing comparatively high temps, energy consumption high, the clarification time reaches that 180min is above and the zinc powder consumption is large (except cobalt zinc powder consumption up to cobalt contents 100～200 times).
Summary of the invention
The invention provides a kind of production cost than Purification of zinc sulfate solution method and device under the cavitation effect effect low, that environmental pollution is little, operation is comparatively simple, energy consumption is lower, overcome above-mentioned the deficiencies in the prior art.The present invention is achieved through the following technical solutions:
A kind of Purification of zinc sulfate solution method based under the cavitation effect effect, it is characterized in that: before the zinc sulfate in the container of sizing mixing purifies, in liquid, add zinc powder to be sized mixing, delivered solution is to purifying vessel, injection forms the cavitation effect bubble to the dividing plate in purifying vessel or the periodic swinging effect by vibrating device, the cavitation effect bubble collapses and produces high temperature in uphill process, high pressure, the effects such as ripple impulse, the impurity cemented out is got off from the zinc powder sur-face peeling, thereby make zinc powder keep at any time exposed reaction surface, can participate in the displacement purge removal of impurities, thereby reduce the consumption of zinc powder, described solution filters after by 1～3 grade of cavitation effect generation device effect 20～50min, and filtrate is that the new liquid of qualified electrolysis, filter residue are higher-grade copper-cadmium slag or nickel cobalt slag.
Liquid before described zinc sulfate purifies, be that the zinc sulfate of impure cadmium, cobalt, nickel, copper leaches rear liquid, supernatant liquor in claiming again, and its impurity level is: Cd≤1500mg/L, Cu≤200mg/L, Ni≤100mg/L, Co≤100mg/L; Purification temperature is controlled at 55～85 ℃.
Described zinc powder joins in the front liquid of zinc sulfate purification with the form of slurries or powder, and while purifying copper removal, cadmium, the zinc powder consumption is 1.0～1.4 times of Cu+Cd foreign matter content sum in the front solution of zinc sulfate of purification.
When 1～3 grade of cavitation effect generation device of described employing carries out Cobalt Purification, nickel to solution of zinc sulfate, also in purifying vessel, add zinc powder, copper sulfate and stibium trioxide powder, the zinc powder consumption is 20～50 times of liquid cobalt, nickel content sum before purifying, the copper sulfate consumption is 20mg/L, and stibium trioxide powder consumption is 4mg/L.
The pressure of described cavitation effect effect generation device delivered solution is 3.8～6.5MPa, and feed flow is 3.0～6.0m
3/ h, power are 25～35KW.
The described purification device of zinc sulfate solution based under the cavitation effect effect is characterized in that: at least comprise size mixing container and the purifying vessel that dispose respectively whipping appts, for the barrier effect that plays arranged in the interchanger to each container heating, transferpump, spray gun and purifying vessel for delivery of solution, make sprayed solution produce fierce the backflow and form the dividing plate of cavitation effect bubble or generation periodic swinging effect and form the vibrating device of cavitation effect bubble.
Described whipping appts adopts mechanical type, magnetic-type or hydraulic stirring mechanism.
The solution that described cavitation effect generation device transports out produces the cavitation effect bubble from the container of sizing mixing by the dividing plate spray gun directive purifying vessel and around it.
The solution that described cavitation effect generation device transports out pumps into corresponding purifying vessel by transferpump and the spacer function in it forms the cavitation effect bubble in purifying vessel.
The solution that described cavitation effect generation device transports out pumps into the periodic swinging effect of corresponding purifying vessel by vibrating device by transferpump and forms the cavitation effect bubble.
Cleaning principle of the present invention is: the cavitation effect generation device, in the zinc powder scavenging process, can produce a large amount of small bubbles while acting on solution of zinc sulfate.Said these small bubbles: the one, in liquid, part tensile stress occurs and forms negative pressure, the reduction of pressure makes originally to be dissolved in gas overflowing or the solution vaporization of liquid, becomes small bubbles.Another reason is that powerful tensile stress " is torn liquid " and become a cavity, in cavity, is liquid vapors or the another kind of gas that is dissolved in liquid, may be even vacuum.The small bubbles that form because of cavatition can constantly move, grow up or vanish suddenly with the vibration of surrounding medium.While vanishing, surrounding liquid pours bubble suddenly and produces high temperature, high pressure, produces shock wave simultaneously.The internal friction accompanied with cavatition can form electric charge, and produces luminescence phenomenon in the electric discharge of bubble internal cause.Be present in the microbubble in liquid, the partial Pressure peak value of cavitation nucleus can reach hundreds of jets of even going up kilo-atmospheric pressure and speed per hour 400km/h, produces upper 1000K temperature of moment simultaneously.
Owing to producing upper 1000K temperature of moment, zinc dust precipitation speed is accelerated, the approximately 373K displacement temperature during for traditional zinc dust precipitation can not be compared; Secondly the partial Pressure peak value can reach hundreds of jets of even going up kilo-atmospheric pressure and speed per hour 400km/h, makes the Ni and the Co that are deposited on the zinc powder surface break away from the zinc powder surface, makes wrapped zinc powder exposed, can participate in displacement, thereby reduce the consumption of zinc powder.It is very identical that this and zinc dust precipitation purify the kinetics required.
The advantage of Purification of zinc sulfate solution impurity-removing method of the present invention:
The cavitation effect produced by the effect of cavitation effect generating unit, make in solution to form the cavitation bubble collapse and produce the effects such as high temperature, high pressure, the ripple that impulses, reduced the integument that zinc powder produces in the substitutional impurity process, effectively improve the surfactivity of zinc powder, thereby reached Reaction time shorten in the Purification of zinc sulfate solution process, reduction energy consumption, reduction zinc powder consumption etc.Concrete advantage is as follows:
1, purifying total time is 20～60min, than 180～240min of conventional wet zinc metallurgy purification process, time shorten more than 2/3, technical process is shortened greatly, maximum temperature is compared and is reduced by 10～15 ℃ than traditional technology, and total energy consumption reduces more than 50%, and device is produced continuously.
2, remove 20～50 times that cobalt zinc powder consumption is cobalt contents under the cavitation effect effect, compare for 100～200 times that are cobalt contents than zinc powder consumption in conventional wet Cobalt Purification technique, zinc powder consumption reduces greatly.
3, lower by the new liquid foreign matter content of the electrolysis after the cavitation effect effect, can reach the new liquid standard of electrolysis of most manufacturing enterprises, the raising of current efficiency in follow-up zinc electrolytic deposition process is also had to certain help.
4, under the cavitation effect effect, can process solution of zinc sulfate and zinc powder consumption that foreign matter content is higher lower, make the adaptability to raw material of factory obtain larger raising, this is that traditional technology is incomparable.
The accompanying drawing explanation
Fig. 1 adopts the principle schematic of zinc dust precipitation in solution of zinc sulfate.
Fig. 2 is the Purification of zinc sulfate solution schema under the cavitation effect effect proposed according to the present invention.
Fig. 3 is the purification device of zinc sulfate solution schematic diagram under the cavitation effect effect proposed according to the present invention.
Fig. 4 is for realizing another kind of purification device of zinc sulfate solution schematic diagram of the present invention.
Fig. 5 is for realizing the third purification device of zinc sulfate solution schematic diagram of the present invention.
Embodiment
Fig. 2 is the purification process that adopts three sections cavitation effect effects.Realize that refining plant of the present invention describes in detail by following three kinds of structures:
One, as shown in Figure 3: by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing by 1.0～1.4 times of Cu+Cd foreign matter content in solution of zinc sulfate, then slurries are injected to one section purification tank 6 by transferpump 3 through a spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, cavitation bubble collapses the environment gone out at its high pressure of very low range formation on every side, high temperature in uphill process.Solution is filtered after 1～3 grade of cavitation effect generation device effect 20～50min by two sections purification tanks 7 and three sections purification tanks 8 again, and filtrate is that the new liquid power transmission solution of qualified electrolysis workshop, filter residue are higher-grade copper-cadmium slag or nickel cobalt slag.All dispose whipping appts 2 in surge tank and purification tank.
Two, as shown in Figure 4: by interchanger 15, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter contents, and by transferpump 3, the solution after sizing mixing is sent into to one section purification tank 5 and produce eddy current with dividing plate 4 effect form cavitation bubble after the high-speed stirring of screw blade whipping appts 6 in groove, cavitation bubble collapses the environment that around it very low range of going out forms high pressure, high temperature in uphill process.Make solution pass through to filter after 1～3 grade of cavitation effect generation device effect 20～50min, filtrate is that the new liquid power transmission solution of qualified electrolysis workshop, filter residue are higher-grade copper-cadmium slag or nickel cobalt slag.
Three, as shown in Figure 5: by interchanger 15, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter contents, then the periodic swinging effect generation mechanical wave of solution being sent into to one section purification tank 4 vibrating device 6 in groove by transferpump 3 forms cavitation bubble, and cavitation bubble collapses the environment gone out at its high pressure of very low range formation on every side, high temperature in uphill process.Make solution pass through to filter after 1～3 grade of cavitation effect generation device effect 20～50min, filtrate is that the new liquid power transmission solution of qualified electrolysis workshop, filter residue are higher-grade copper-cadmium slag or nickel cobalt slag.
The transferpump power adopted in following embodiment is 25～35KW.
Embodiment 1: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd642.48mg/L, Cu18.33mg/L, Ni23.96mg/L, Co32.05mg/L.Adopt the new liquid of the qualified electrolysis of purification process output of three sections cavitation effect effects, as shown in Figure 3.
At first by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter content in solution of zinc sulfate, then adopt the transferpump 3 rear solution of zinc sulfate of sizing mixing to inject one section purification tank 6 through a spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, in one section purification tank, the reaction times is 10min.Transferpump pressure is 3.8～4.5MPa, and the transferpump flow is 6.0m
3/ h; After production fluid filters, filtrate is advanced two sections purification tanks 7.One section cleaning section is copper removal cadmium operation, and temperature is 55～85 ℃, and the zinc powder consumption is 1.0～1.4 times of Cu+Cd foreign matter content in solution of zinc sulfate before purifying, and zinc powder is for being routinely added to mode;
Two sections purifications are for removing cadmium, cobalt, nickel operation, temperature is 55～85 ℃, and the zinc powder consumption is one section except liquid impurity Co+Ni content after Cu, Cd 20～50 times, and the copper sulfate consumption is 20mg/L, stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with conventionally form; Adopt transferpump 3 that liquid after one section purification is injected to two sections purification tanks 7 through spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, in two sections purification tanks, the reaction times is 20min, and transferpump pressure is 4.5～6.5MPa, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced three sections cleaning sections.
Three sections purifications are for removing residual cadmium cobalt operation, and temperature is 55～85 ℃, and the zinc powder consumption is 0.6～1.4g/L, and zinc powder is for being routinely added to mode; Adopt transferpump 3 that liquid after two sections purifications is injected to three sections purification tanks 8 through spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, in three sections purification tanks, the reaction times is 20min, and transferpump pressure is 4.5～6.5MPa, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid composition: Cu0.062mg/L after removal of impurities, Cd0.27mg/L, Co0.9mg/L, Ni0.2mg/L.
Embodiment 2: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd454.55mg/L, Cu162.5mg/L, Ni12.5mg/L, Co37.5mg/L.Adopt the new liquid of the qualified electrolysis of cleaning section output of two sections cavitation effect effects, zinc powder adds with the form of slurries.As shown in Figure 3.
At first by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter content in solution, then adopts the transferpump 3 rear solution of zinc sulfate of sizing mixing to inject one section purification tank 6 through a spray gun 4 and carry out one section purification.One section cleaning section is copper removal cadmium operation, and temperature is 55～85 ℃; In one section purification tank, dividing plate is not set, the reaction times is 20min.After production fluid filters, filtrate is advanced two sections purification tanks 7.
Two sections cleaning sections are for removing cadmium, cobalt, nickel operation, temperature is 55～85 ℃, and the zinc powder consumption is one section except liquid impurity Co+Ni content after Cu, Cd 20～50 times, and the copper sulfate consumption is 20mg/L, stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with the form of slurries; Adopt transferpump 3 that liquid after one section purification is injected to two sections purification tanks 7 through spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, in two sections purification tanks, the reaction times is 20min, and transferpump pressure is 4.5～6.5MPa, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced three sections cleaning sections.
Three sections is that temperature is 55～85 ℃ except residual cadmium cobalt operation, and the zinc powder consumption is 0.5～1.0g/L, and zinc powder adds with the form of slurries; Adopt transferpump 13 that liquid after two sections purifications is injected to three sections purification tanks 8 through spray gun 4, because the dividing plate 5 in groove stops that producing fierce backflow effect forms cavitation bubble, in three sections purification tanks, the reaction times is 10min, and transferpump pressure is 4.5～6.5MPa, and the transferpump flow is 6.0m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid impurity component: Cu0.2mg/L after removal of impurities, Cd0.3mg/L, Co0.87mg/L, Ni0.14mg/L.
Embodiment 3: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd636.36mg/L, Cu62.5mg/L, Ni14.02mg/L, Co58mg/L.Adopt two sections new liquid of the qualified electrolysis of purification process output.As shown in Figure 4.
At first before by interchanger 9, zinc sulfate being purified, liquid is warming up to 55～85 ℃, zinc powder is pressed 1.0～1.4 times of Cu+Cd foreign matter content in solution, 20～40 times of Co+Ni content add in surge tank 1 and are sized mixing with solution of zinc sulfate, add in a usual manner, after the high-speed stirring of screw blade whipping appts 2 in groove 1, adopt the transferpump 3 one section purification tank 6 of rear solution of zinc sulfate input of sizing mixing, produce eddy current with dividing plate 5 effects after the high-speed stirring of screw blade whipping appts 2 in groove 2, reaction times is 20min, one section cleaning section is copper removal cadmium cobalt nickel operation, temperature is 55～85 ℃, the rotating speed of screw blade whipping appts 2 is 2500～4500r/min, the transferpump flow velocity is 3.6m
3/ h.After production fluid filters, filtrate is advanced two sections cleaning sections.
Two sections cleaning sections are for removing residual cadmium, cobalt operation, and temperature is 55～85 ℃, and adding the zinc powder consumption is 0.5～1.0g/L, and the copper sulfate consumption is 20mg/L, and stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with conventionally form; Adopt transferpump 3 that two sections purification tanks 7 of liquid input after one section purification are produced to eddy current with dividing plate 5 effects after the high-speed stirring of screw blade whipping appts 2 in groove, the reaction times is 20min, and rotating speed is 2500～4500r/min, and flow is 4m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid impurity component: Cu0.042mg/L after removal of impurities, Cd0.38mg/L, Co0.98mg/L, Ni0.14mg/L.
Embodiment 4: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd637.93mg/L, Cu 105.83mg/L, Ni34.24mg/L, Co 54.29mg/L.Adopt the new liquid of the qualified electrolysis of purification process output of three sections cavitation effect effects, as shown in Figure 5.
At first by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter content in solution, then send one section cleaning section.
One section is copper removal cadmium cobalt nickel operation, and temperature is 55～85 ℃, and the zinc powder consumption is 10～30 times of 1.0～1.4 times of impurity Cu+Cd content, Co+Ni content in liquid before purifying, and zinc powder is for being routinely added to mode; Adopt will the size mixing periodic swinging effect of the vibrating devices 10 of one section purification tank of rear solution of zinc sulfate input 6 by substituting dividing plate of transferpump 3 to produce the cavitation effect bubble, the reaction times is 20min, and vibrating device power is 25～35KW, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced two sections cleaning sections.
Two sections for except cadmium, cobalt, nickel operation, and temperature is 55～85 ℃, and the zinc powder consumption is 10～30 times of liquid impurity Co+Ni content after one section purification, and the copper sulfate consumption is 20mg/L, and stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with conventionally form; Adopt transferpump 3 that the periodic swinging effect of two sections purification tanks of liquid input, 7 vibrating devices 10 by alternative dividing plate after one section purification is produced to the cavitation effect bubble, the reaction times is 20min, and vibrating device power is 25～35KW, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced three sections cleaning sections.
Three sections is that temperature is 55～85 ℃ except residual cadmium cobalt operation, and the zinc powder consumption is 0.6～1.4g/L, and zinc powder is for being routinely added to mode; Adopt transferpump 3 by the periodic swinging effect cavitation effect bubble of three sections purification tanks of liquid input, 8 vibrating devices 10 by alternative dividing plate after two sections purifications, the reaction times is 10min, and vibrating device power is 25～35KW, and the transferpump flow is 6.0m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid impurity component: Cu0.26mg/L after removal of impurities, Cd0.26mg/L, Co0.84mg/L, Ni0.14mg/L.
Embodiment 5: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd636.36mg/L, Cu62.5mg/L, Ni14.02mg/L, Co58mg/L.Adopt the new liquid of the qualified electrolysis of purification process output of one section cavitation effect effect.As shown in Figure 5.
At first by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter content in solution, then send one section cleaning section.
One section is copper removal cadmium cobalt nickel operation, temperature is 55～85 ℃, and the zinc powder consumption is 20～50 times of 1.0～1.4 times of impurity Cu+Cd content, Co+Ni content in liquid before purifying, and the copper sulfate consumption is 20mg/L, stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with conventionally form; Adopt will the size mixing periodic swinging effect of the vibrating devices 10 of one section purification tank of rear solution of zinc sulfate input 5 by substituting dividing plate of transferpump 3 to produce the cavitation effect bubble, the reaction times is 30min, and vibrating device power is 25～35KW, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid impurity component: Cu0.083mg/L after removal of impurities, Cd0.5mg/L, Co0.69mg/L, Ni0.16mg/L.
Embodiment 6: solution before the zinc sulfate of impure cadmium, cobalt, nickel, copper purifies, its impurity level is: Cd1000mg/L, Cu29.17mg/L, Ni17.65mg/L, Co52.78mg/L.Adopt the new liquid of three sections cleaning sections (one section does not adopt cavitation effect) qualified electrolysis of output.As shown in Figure 5.
At first by interchanger 9, solution of zinc sulfate is warming up to 55～85 ℃, zinc powder adds in a usual manner in surge tank 1 and is sized mixing with solution of zinc sulfate by 1.0～1.4 times of Cu+Cd foreign matter contents, then send one section cleaning section.
One section is copper removal cadmium operation, and temperature is 55～85 ℃, and the zinc powder consumption is 1.0～1.4 times of Cu+Cd foreign matter contents in liquid before purifying, and zinc powder is for being routinely added to mode; Cavitation effect is not set in one section purification tank 6 and produces dividing plate, reaction times 20min.After production fluid filters, filtrate is advanced two sections cleaning sections.
Two sections for removing cadmium, cobalt, nickel operation, temperature is 55～85 ℃, and the zinc powder consumption is one section except liquid impurity Co+Ni content after Cu, Cd 20～50 times, and the copper sulfate consumption is 20mg/L, stibium trioxide powder consumption is 4mg/L, and zinc powder, copper sulfate and stibium trioxide powder all add with conventionally form; Adopt transferpump 3 by two sections purification tanks 6 of liquid input after one section purification, the periodic swinging effect of the vibrating device 10 by purification tank 6 interior settings produces the cavitation effect bubble, and the reaction times is 20min, and vibrating device power is 25～35KW, and the transferpump flow is 3.0m
3/ h.After production fluid filters, filtrate is advanced three sections cleaning sections.
Three sections is that temperature is 55～85 ℃ except residual cadmium cobalt operation, and the zinc powder consumption is 0.6～1.4g/L, and zinc powder is for being routinely added to mode; Adopt transferpump 3 that the periodic swinging effect that after two sections purifications, three sections purification tanks of liquid input 7 pass through vibrating device 10 is produced to the cavitation effect bubble, the reaction times is 10min, and vibrating device power is 25～35KW, and the transferpump flow is 6.0m
3/ h.After production fluid filters, filtrate is advanced the electrolytic zinc system.
Liquid impurity component after removal of impurities: Cu 0.063mg/L, Cd 0.094mg/L, Co0.76mg/L, Ni0.08mg/L.
Claims (8)
1. the Purification of zinc sulfate solution method based under the cavitation effect effect, it is characterized in that: before the zinc sulfate in the container of sizing mixing purifies, in liquid, add zinc powder to be sized mixing, delivered solution is to purifying vessel, injection forms the cavitation effect bubble to the dividing plate in purifying vessel or the periodic swinging effect by vibrating device, the cavitation effect bubble collapses and produces high temperature in uphill process, high pressure, the ripple effect impulses, the impurity cemented out is got off from the zinc powder sur-face peeling, thereby make zinc powder keep at any time exposed reaction surface, can participate in the displacement purge removal of impurities, thereby reduce the consumption of zinc powder, described solution filters after by 1～3 grade of cavitation effect generation device effect 20～50min, and filtrate is that the new liquid of qualified electrolysis, filter residue are higher-grade copper-cadmium slag or nickel cobalt slag,
Liquid before described zinc sulfate purifies, be that the zinc sulfate of impure cadmium, cobalt, nickel, copper leaches rear liquid, supernatant liquor in claiming again, and its impurity level is: Cd≤1500mg/L, Cu≤200mg/L, Ni≤100mg/L, Co≤100mg/L; Purification temperature is controlled at 55～85 ℃;
The pressure of described cavitation effect effect generation device delivered solution is 3.8～6.5MPa, and feed flow is 3.0～6.0m
3/ h, power are 25～35kW.
2.
purification of zinc sulfate solution method based under the cavitation effect effect according to claim 1, it is characterized in that: described zinc powder joins in the front liquid of zinc sulfate purification with the form of slurries or powder, while purifying copper removal, cadmium, the zinc powder consumption is 1.0～1.4 times of Cu+Cd foreign matter content sum in solution of zinc sulfate before purifying.
3. the Purification of zinc sulfate solution method based under the cavitation effect effect according to claim 1, it is characterized in that: while adopting 1～3 grade of cavitation effect generation device to carry out Cobalt Purification, nickel to solution of zinc sulfate, also in purifying vessel, add zinc powder, copper sulfate and stibium trioxide powder, the zinc powder consumption is 20～50 times of liquid cobalt, nickel content sum before purifying, the copper sulfate consumption is 20mg/L, and stibium trioxide powder consumption is 4mg/L.
4. a device that is applied to the Purification of zinc sulfate solution method based under the cavitation effect effect claimed in claim 1 is characterized in that: at least comprise size mixing container and the purifying vessel that dispose respectively whipping appts, for the barrier effect that plays arranged in the interchanger to each container heating, transferpump, spray gun and purifying vessel for delivery of solution, make sprayed solution produce fierce the backflow and form the dividing plate of cavitation effect bubble or generation periodic swinging effect and form the vibrating device of cavitation effect bubble.
5. the device of the Purification of zinc sulfate solution method based under the cavitation effect effect according to claim 4 is characterized in that: described whipping appts adopts mechanical type, magnetic-type or hydraulic stirring mechanism.
6. according to the device of the described Purification of zinc sulfate solution method based under the cavitation effect effect of claim 4 or 5, it is characterized in that the solution that described cavitation effect generation device transports out produces the cavitation effect bubble from the container of sizing mixing by the dividing plate spray gun directive purifying vessel and around it.
7. according to the device of the described Purification of zinc sulfate solution method based under the cavitation effect effect of claim 4 or 5, it is characterized in that solution that described cavitation effect generation device transports out pumps into corresponding purifying vessel by transferpump and the spacer function in it forms the cavitation effect bubble in purifying vessel.
8. according to the device of the described Purification of zinc sulfate solution method based under the cavitation effect effect of claim 4 or 5, it is characterized in that solution that described cavitation effect generation device transports out pumps into the periodic swinging effect of corresponding purifying vessel by vibrating device by transferpump and forms the cavitation effect bubble.
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| CN110804695B (en) * | 2018-08-06 | 2021-01-22 | 昆明理工大学 | Method for purifying zinc sulfate solution by using pressurized zinc powder |
| CN110819801B (en) * | 2018-08-07 | 2021-01-22 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
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| CN110819802B (en) * | 2018-08-08 | 2021-01-22 | 昆明理工大学 | Method for strengthening and purifying zinc sulfate solution by microwave heating of zinc powder |
| 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 |
| CN115382241A (en) * | 2022-08-15 | 2022-11-25 | 衡阳百赛化工实业有限公司 | Zinc sulfate evaporation crystallization drying equipment |
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