CN104005049A - Insoluble anodic electrodeposition production process for nickel - Google Patents
Insoluble anodic electrodeposition production process for nickel Download PDFInfo
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- CN104005049A CN104005049A CN201410240461.6A CN201410240461A CN104005049A CN 104005049 A CN104005049 A CN 104005049A CN 201410240461 A CN201410240461 A CN 201410240461A CN 104005049 A CN104005049 A CN 104005049A
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Abstract
The invention discloses an insoluble anodic electrodeposition production process for nickel, and the process can be used for obviously improving the quality of electro-nickel and reducing the power consumption in comparison with existing processes. The insoluble anodic electrodeposition production process for nickel disclosed by the invention is characterized by feeding a pre-nickel-electrodeposition liquid into a membrane filtration device to carry out precision membrane filtration firstly, wherein a porous membrane filter element with the average pore diameter of 2-8 mu m is selected, the filter differential pressure is 0.02-0.1 MPa, and the filtration temperature is 60-80 DEG C; then, discharging the filtered pre-nickel-electrodeposition liquid at a temperature of 60-80 DEG C to an electrodeposition cell and electrodepositing; under the conditions that the pH value of the pre-nickel-electrodeposition liquid discharged to the electrodeposition cell is controlled at 3-3.5, the cathode current density in the process of electrodeposition is 200-230 A/m<2>, and the e average cell voltage is 3-3.9 V, separating out electrodeposited nickel from a cathode. Compared with existing insoluble anodic electrodeposition production processes, the process disclosed by the invention has the advantages that the electro-nickel qualified rate and first-grade product pass rate of the insoluble anodic electrodeposition production process for nickel disclosed by the invention are greatly improved, the average cell voltage is reduced by about 0.3-0.4 V, and the power consumption is effectively reduced.
Description
Technical field
The present invention relates to the electrochemical preparation process of metallic nickel, be specifically related to a kind of electrowinning with insoluble anode production technique of nickel.
Background technology
The preparation technology of metallic nickel mainly contains two kinds of soluble anode electrolysis and electrowinning with insoluble anode.In electrolysis (electrodeposition) process, in order to prevent that impurity thing from separating out at negative electrode, all adopt diaphragm electrolysis (electrodeposition) technique, to ensure electric nickel quality.In addition, the front liquid of electrolysis (electrodeposition) is entering before electrolysis (electrodeposition) groove, also need to purify through the solid-liquid separation of plate-and-frame filter press, pipe filter, in the front liquid of electrolysis (electrodeposition) after purification, solid content is lower, and naked eyes cannot be observed substantially.But after current electrolysis (electrodeposition), the surface of negative plate is generally more black, and surperficial pimple is more.The concrete reason that produces this problem is not quite clear.
Summary of the invention
Technical problem to be solved by this invention is that a kind of electrowinning with insoluble anode production technique of nickel and the soluble anode electrolysis production technique of nickel are provided respectively, compares existing technique and can obviously improve electric nickel quality and reduce power consumption.
The electrowinning with insoluble anode production technique of nickel of the present invention, is characterized in that first liquid before nickel electrodeposition being passed into membrane filter appts carries out accurate membrane filtration, and selecting mean pore size is the porous-film filter core of 2～8 μ m, filtration pressure difference 0.02～0.1MPa, 60～80 DEG C of filtration temperatures; Again liquid before the nickel electrodeposition after filtering is entered to Winning cell with 60～80 DEG C and carries out electrodeposition, enter the pH value of liquid before the nickel electrodeposition of Winning cell and be controlled in 3～3.5 scope, when electrodeposition, cathode current density is 200～230A/m
2, average cell voltage is 3～3.9V, obtains electro deposited nickel thereby separate out on negative electrode.
In the electrowinning with insoluble anode production technique of above-mentioned nickel, can be further preferably controlled in 3.2～3.4 scope entering the pH value of liquid before the nickel electrodeposition of Winning cell.Separate out at negative electrode like this that to obtain electric nickel void content low, and electric nickel chemical purity is also higher.
Before nickel electrodeposition, the pH value of liquid can regulate before accurate membrane filtration, but suggestion is after accurate membrane filtration, first liquid before the nickel electrodeposition after above-mentioned filtration to be carried out to acid to be adjusted to and again liquid before this nickel electrodeposition to be entered to Winning cell after pH value 3.2～3.4 and carry out electrodeposition, more accurate to the control meeting of pH value like this.
Even adopt non-diaphragm electrodeposition in the electrowinning with insoluble anode production technique of above-mentioned nickel, still can ensure preferably electric nickel quality.But described electrodeposition preferably adopts diaphragm electrodeposition, at this moment, the poor 10～50mm that is set as of the anode and cathode liquid level of diaphragm electrodeposition, average cell voltage is 3.6～3.9V.The anode and cathode liquid level of diaphragm electrodeposition is poor can be preferably set to 10～30mm again.
As the further improvement of the electrowinning with insoluble anode production technique to above-mentioned any one nickel, porous-film filter core is selected sintering Ti-Al base alloy porous material membrane cartridge; The operation steps of membrane filter appts has: a, the start preparatory stage to pass in membrane filter appts displacement liquid fully replace in membrane filter appts air, and pass into pre-hydrothermal solution to membrane filter appts and will in membrane filter appts, be preheated to more than 40 DEG C; After b, preheating, discharge pre-hydrothermal solution, then passing into temperature to membrane filter appts is liquid before the nickel electrodeposition of 60～80 DEG C, when reaching 0.02～0.03MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrodeposition after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to 0.8～1.2t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing, using liquid before the nickel electrodeposition after filtering is backwash liquid, and kickback pressure is set as 0.2～0.25MPa; D, liquid before remaining nickel electrodeposition in membrane filter appts is discharged after filtering, thereby then to passing into scavenging solution in membrane filter appts, it is cleaned.After above-mentioned improvement, sintering Ti-Al base alloy porous material membrane cartridge has shown excellent erosion resistance, and after long-time running, filtering accuracy is without impact; Exhaust and the preheating of start preparatory stage, further reduced corrosion and destruction to filter core; Clear liquid flux stabilized when filtration, slowly, backwashing period can reach 20～25 minutes in decay, and after back flushing, clear liquid flux can recover rapidly.
In addition, further, if sintering Ti-Al base alloy porous material membrane cartridge is carried out to still < 0.8t/m of clear liquid flux after back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode with liquid before the nickel electrodeposition in the hot water displacement membrane filter appts of 60～80 DEG C of temperature, and the maintenance filtration pressure difference identical with normal filtration pattern filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts pass into mass concentration be 4～6g/l NaOH solution and keep the filtration pressure difference identical with normal filtration pattern NaOH solution is filtered, treat clear liquid flux no longer rise backward membrane filter appts pass into clear water replace clean to clear water pH≤8; B, discharge after clear water again that to pass into pH be 1.5～2 aqueous sulfuric acid and keep the filtration pressure difference identical with normal filtration pattern to filter aqueous sulfuric acid to membrane filter appts, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.Aforesaid method can effectively extend the irreversible membrane fouling of porous-film filter core, keeps the long-term efficient operation of membrane filter appts.
The soluble anode electrolysis production technique of nickel of the present invention, is characterized in that first liquid before nickel electrowinning being passed into membrane filter appts carries out accurate membrane filtration, and selecting mean pore size is the porous-film filter core of 2～8 μ m, filtration pressure difference 0.02～0.1MPa, 60～80 DEG C of filtration temperatures; Again liquid before the nickel electrowinning after filtering is entered to electrolyzer with 60～80 DEG C and carry out electrolysis, entering the pH value of liquid before the nickel electrowinning of electrolyzer is controlled in 4.5～5.1 scope, described electrolysis adopts diaphragm electrolysis, poor 30～the 60mm that is set as of anode and cathode liquid level of diaphragm electrolysis, when electrolysis, cathode current density is 200～230A/m
2, average cell voltage is 3.2～3.5V, obtains electrolytic nickel thereby separate out on negative electrode.The anode and cathode liquid level of diaphragm electrolysis is poor can be preferably set to 30～50mm again.
In the soluble anode electrolysis production technique of above-mentioned nickel, can be further preferably just enter the pH value of liquid before the nickel electrowinning of electrolyzer and be controlled in 4.6～4.8 scope.At this moment can separate out and obtain the low electric nickel of void content at negative electrode, and electric nickel chemical purity be also higher.Same suggestion is first carried out acid to liquid before the nickel electrowinning after above-mentioned filtration and is adjusted to and again liquid before this nickel electrowinning is entered to electrolyzer after pH value 4.6～4.8 and carry out electrolysis.
As the further improvement of the soluble anode electrolysis production technique to above-mentioned any one nickel, select sintering Ti-Al base alloy porous material membrane cartridge; The operation steps of membrane filter appts has: a, the start preparatory stage to pass in membrane filter appts displacement liquid fully replace in membrane filter appts air, and pass into pre-hydrothermal solution to membrane filter appts and will in membrane filter appts, be preheated to more than 40 DEG C; After b, preheating, discharge pre-hydrothermal solution, then passing into temperature to membrane filter appts is liquid before the nickel electrowinning of 60～80 DEG C, when reaching 0.02～0.03MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrowinning after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to 0.8～1.2t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing, using liquid before the nickel electrowinning after filtering is backwash liquid, and kickback pressure is set as 0.2～0.25MPa; D, liquid before remaining nickel electrowinning in membrane filter appts is discharged after filtering, thereby then to passing into scavenging solution in membrane filter appts, it is cleaned.After above-mentioned improvement, sintering Ti-Al base alloy porous material membrane cartridge has shown excellent erosion resistance, and after long-time running, filtering accuracy is without impact; Exhaust and the preheating of start preparatory stage, further reduced corrosion and destruction to filter core; Clear liquid flux stabilized when filtration, slowly, backwashing period can reach 20～25 minutes in decay, and after back flushing, clear liquid flux can recover rapidly.
Further, if sintering Ti-Al base alloy porous material membrane cartridge is carried out to still < 0.8t/m of clear liquid flux after back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode with liquid before the nickel electrowinning in the hot water displacement membrane filter appts of 60～80 DEG C of temperature, and the maintenance filtration pressure difference identical with normal filtration pattern filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts pass into mass concentration be 4～6g/l NaOH solution and keep the filtration pressure difference identical with normal filtration pattern NaOH solution is filtered, treat clear liquid flux no longer rise backward membrane filter appts pass into clear water replace clean to clear water pH≤8; B, discharge after clear water again that to pass into pH be 1.5～2 aqueous sulfuric acid and keep the filtration pressure difference identical with normal filtration pattern to filter aqueous sulfuric acid to membrane filter appts, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.Aforesaid method can effectively extend the irreversible membrane fouling of porous-film filter core, keeps the long-term efficient operation of membrane filter appts.
The no matter electrowinning with insoluble anode production technique of above-mentioned nickel or the soluble anode electrolysis production technique of nickel, has all adopted the technique means of the front liquid of electrodeposition (electrolysis) being carried out to accurate membrane filtration, and limits particular filter parameter.Wherein, " filtration pressure difference " refers to the pressure difference of porous-film filter core both sides.Test is found, by above-mentioned accurate membrane filtration process, has held back unexpectedly a lot of black molecules from electrodeposition (electrolysis) in liquid, analyzes and shows to contain in these particles more C, SiO
2deng material, and after follow-up electrodeposition (electrolysis), the electric nickel visual appearance of producing obviously improves, and negative plate face is smooth, pimple is few, judges that the materials such as C that these are retained down are exactly probably the more major cause of surface blackening, pimple of former negative plate.In addition, in above-mentioned accurate membrane filtration process process, the operation exception of membrane filter appts is stable, and clear liquid flux decline is slow.The soluble anode electrolysis production technique of the electrowinning with insoluble anode production technique of nickel of the present invention and nickel, the electric nickel qualification rate of producing and first grade qualification rate all more current electrowinning with insoluble anode production technique and soluble anode electrolysis production technique have raising by a relatively large margin, the average cell voltage approximately 0.3～0.4V that declines, effectively reduces power consumption.
Embodiment
The 1st group of embodiment > of <
The electrowinning with insoluble anode technique of nickel is carried out to three periodic duties continuously, and be 144 hours the working time in each cycle.Adopt without diaphragm electrodeposition.Concrete technology thes contents are as follows:
1) parameter of liquid before electrodeposition
Ni content: 75～85g/l
Co content: 0.0022～0.0045g/l
Fe content: 0.0001～0.0005g/l
Na
2sO4 content: 90～110g/l
Proportion: 1.1g/cm
3
Temperature: 70～80 DEG C
Solid content :≤500mg/l
pH：3～3.5
2) accurate membrane filtration
Select sintering Ti-Al base alloy porous material membrane cartridge, measuring its mean pore size by bubble-tube method is 4.6 μ m.The operation steps of membrane filter appts is: a, fully replace the air in membrane filter appts in the start preparatory stage to passing into clear water in membrane filter appts, and pass into 70 DEG C of hot water to membrane filter appts and will in membrane filter appts, be preheated to 50 DEG C of left and right; After b, preheating, discharge hot water, then passing into temperature to membrane filter appts is liquid (establishing steam jacket insulation on the shell of membrane filter appts) before the above-mentioned electrodeposition of 70～80 DEG C, when reaching 0.025MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrodeposition after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to about 1t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing (back flushing average period is 22 minutes), using the front liquid of nickel electrodeposition after filtering is backwash liquid, and kickback pressure is set as 0.25MPa; D, liquid before remaining nickel electrodeposition in membrane filter appts is discharged after filtering, then to passing into clear water in membrane filter appts, it is cleaned.
Still < 0.8t/m of clear liquid flux after sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode, with liquid before the nickel electrodeposition in the hot water displacement membrane filter appts of 60～80 DEG C of temperature, and keep the filtration pressure difference of 0.01MPa to filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts, to pass into mass concentration be the NaOH solution of 5g/l and keep the filtration pressure difference of 0.01MPa to filter NaOH solution, treats that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH≤8; After b, discharge clear water, pass into the aqueous sulfuric acid of pH=2 and keep the filtration pressure difference of 0.01MPa to filter aqueous sulfuric acid to membrane filter appts again, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.
3) acid is adjusted
Liquid before electrodeposition after above-mentioned filtration is carried out to acid and be adjusted to pH value 3.2.
4) liquid before above-mentioned electrodeposition is entered to Winning cell with 70～80 DEG C and carry out without diaphragm electrodeposition, when electrodeposition, cathode current density is 210A/m
2.On negative electrode, separate out and obtain electro deposited nickel.
5) test-results (referring to table 1)
Table 1
Note: " first grade " refers to that the weight percent of nickel+cobalt in electric nickel is not less than 99.96%.Lower same.
The 2nd group of embodiment > of <
The electrowinning with insoluble anode technique of nickel is carried out to three periodic duties continuously, and be 144 hours the working time in each cycle.Adopt diaphragm electrodeposition.Concrete technology thes contents are as follows:
1) parameter of liquid before electrodeposition
Ni content: 75～85g/l
Co content: 0.0022～0.0045g/l
Fe content: 0.0001～0.0005g/l
Na
2sO4 content: 90～110g/l
Proportion: 1.1g/cm
3
Temperature: 70～80 DEG C
Solid content :≤500mg/l
pH：3～3.5
2) accurate membrane filtration
Select sintering Ti-Al base alloy porous material membrane cartridge, measuring its mean pore size by bubble-tube method is 4.6 μ m.The operation steps of membrane filter appts is: a, fully replace the air in membrane filter appts in the start preparatory stage to passing into clear water in membrane filter appts, and pass into 70 DEG C of hot water to membrane filter appts and will in membrane filter appts, be preheated to 50 DEG C of left and right; After b, preheating, discharge hot water, then passing into temperature to membrane filter appts is liquid (establishing steam jacket insulation on the shell of membrane filter appts) before the above-mentioned electrodeposition of 70～80 DEG C, when reaching 0.025MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrodeposition after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to about 1t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing (back flushing average period is 22 minutes), using the front liquid of nickel electrodeposition after filtering is backwash liquid, and kickback pressure is set as 0.25MPa; D, liquid before remaining nickel electrodeposition in membrane filter appts is discharged after filtering, then to passing into clear water in membrane filter appts, it is cleaned.
Still < 0.8t/m of clear liquid flux after sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode, with liquid before the nickel electrodeposition in the hot water displacement membrane filter appts of 60～80 DEG C of temperature, and keep the filtration pressure difference of 0.01MPa to filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts, to pass into mass concentration be the NaOH solution of 5g/l and keep the filtration pressure difference of 0.01MPa to filter NaOH solution, treats that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH≤8; After b, discharge clear water, pass into the aqueous sulfuric acid of pH=2 and keep the filtration pressure difference of 0.01MPa to filter aqueous sulfuric acid to membrane filter appts again, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.
3) acid is adjusted
Liquid before electrodeposition after above-mentioned filtration is carried out to acid and be adjusted to pH value 3.4.
4) liquid before above-mentioned electrodeposition is entered to Winning cell with 70～80 DEG C and carry out diaphragm electrodeposition, when electrodeposition, cathode current density is 230A/m
2, the poor 25mm that is set as of anode and cathode liquid level of diaphragm electrodeposition.On negative electrode, separate out and obtain electro deposited nickel.
5) test-results (referring to table 2)
Table 2
The 3rd group of embodiment > of <
The soluble anode electrolysis process of nickel is carried out to three periodic duties continuously, and be 144 hours the working time in each cycle.Adopt diaphragm electrolysis.Concrete technology thes contents are as follows:
1) parameter of liquid before electrolysis
Ni content: 70～75g/l
Co content: 0.02g/l
Fe content: 0.004g/l
Na content: 40g/l
Cl content: 60～80g/l
Proportion: 1.1g/cm
3
Temperature: 60～70 DEG C
Solid content :≤500mg/l
pH：4.5～5.1
2) accurate membrane filtration
Select sintering Ti-Al base alloy porous material membrane cartridge, measuring its mean pore size by bubble-tube method is 4.6 μ m.The operation steps of membrane filter appts is: a, fully replace the air in membrane filter appts in the start preparatory stage to passing into clear water in membrane filter appts, and pass into 70 DEG C of hot water to membrane filter appts and will in membrane filter appts, be preheated to 50 DEG C of left and right; After b, preheating, discharge hot water, then passing into temperature to membrane filter appts is liquid (establishing steam jacket insulation on the shell of membrane filter appts) before the above-mentioned electrolysis of 60～70 DEG C, when reaching 0.02MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrowinning after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to about 1t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing (back flushing average period is 22 minutes), using liquid before the nickel electrowinning after filtering is backwash liquid, and kickback pressure is set as 0.2MPa; D, liquid before remaining nickel electrowinning in membrane filter appts is discharged after filtering, then to passing into clear water in membrane filter appts, it is cleaned.
Still < 0.8t/m of clear liquid flux after sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode, with liquid before the nickel electrowinning in the hot water displacement membrane filter appts of 60～70 DEG C of temperature, and keep the filtration pressure difference of 0.01MPa to filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts, to pass into mass concentration be the NaOH solution of 5g/l and keep the filtration pressure difference of 0.01MPa to filter NaOH solution, treats that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH≤8; After b, discharge clear water, pass into the aqueous sulfuric acid of pH=2 and keep the filtration pressure difference of 0.01MPa to filter aqueous sulfuric acid to membrane filter appts again, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.
3) acid is adjusted
Liquid before electrolysis after above-mentioned filtration is carried out to acid and be adjusted to pH value 4.7.
4) liquid before above-mentioned electrolysis is entered to electrolyzer with 60～70 DEG C and carry out diaphragm electrolysis, when electrolysis, cathode current density is 230A/m
2, the poor 40mm that is set as of anode and cathode liquid level of diaphragm electrolysis.On negative electrode, separate out and obtain electrolytic nickel.
5) test-results (referring to table 3)
Table 3
Claims (7)
1. the electrowinning with insoluble anode production technique of nickel, is characterized in that: first liquid before nickel electrodeposition is passed into membrane filter appts and carry out accurate membrane filtration, selecting mean pore size is the porous-film filter core of 2～8 μ m, filtration pressure difference 0.02～0.1MPa, 60～80 DEG C of filtration temperatures; Again liquid before the nickel electrodeposition after filtering is entered to Winning cell with 60～80 DEG C and carries out electrodeposition, enter the pH value of liquid before the nickel electrodeposition of Winning cell and be controlled in 3～3.5 scope, when electrodeposition, cathode current density is 200～230A/m
2, average cell voltage is 3～3.9V, obtains electro deposited nickel thereby separate out on negative electrode.
2. the electrowinning with insoluble anode production technique of nickel as claimed in claim 1, is characterized in that: be controlled in 3.2～3.4 scope entering the pH value of liquid before the nickel electrodeposition of Winning cell.
3. the electrowinning with insoluble anode production technique of nickel as claimed in claim 2, is characterized in that: first liquid before the nickel electrodeposition after above-mentioned filtration is carried out to acid and be adjusted to and again liquid before this nickel electrodeposition entered to Winning cell after pH value 3.2～3.4 and carry out electrodeposition.
4. the electrowinning with insoluble anode production technique of nickel as claimed in claim 1, is characterized in that: described electrodeposition adopts diaphragm electrodeposition, the poor 10～50mm that is set as of anode and cathode liquid level of diaphragm electrodeposition, and average cell voltage is 3.6～3.9V.
5. the electrowinning with insoluble anode production technique of nickel as claimed in claim 4, is characterized in that: the poor 10～30mm that is set as of anode and cathode liquid level of diaphragm electrodeposition.
6. the electrowinning with insoluble anode production technique of the nickel as described in any one claim in claim 1 to 5, is characterized in that: select sintering Ti-Al base alloy porous material membrane cartridge; The operation steps of membrane filter appts has: a, the start preparatory stage to pass in membrane filter appts displacement liquid fully replace in membrane filter appts air, and pass into pre-hydrothermal solution to membrane filter appts and will in membrane filter appts, be preheated to more than 40 DEG C; After b, preheating, discharge pre-hydrothermal solution, then passing into temperature to membrane filter appts is liquid before the nickel electrodeposition of 60～80 DEG C, when reaching 0.02～0.03MPa, opens the filtration pressure difference of Ti-Al base alloy porous material membrane cartridge to be sintered both sides clear liquid valve, before nickel electrodeposition after filtration, liquid starts to discharge from clear liquid valve, and clear liquid flux is controlled to 0.8～1.2t/m
2h; C, in the time that filtration pressure difference reaches 0.08～0.1MPa, sintering Ti-Al base alloy porous material membrane cartridge is carried out to back flushing, using liquid before the nickel electrodeposition after filtering is backwash liquid, and kickback pressure is set as 0.2～0.25MPa; D, liquid before remaining nickel electrodeposition in membrane filter appts is discharged after filtering, thereby then to passing into scavenging solution in membrane filter appts, it is cleaned.
7. the electrowinning with insoluble anode production technique of nickel as claimed in claim 6, is characterized in that: if sintering Ti-Al base alloy porous material membrane cartridge is carried out to still < 0.8t/m of clear liquid flux after back flushing
2h, membrane filter appts is switched to the first regeneration mode from normal filtration pattern, under the first regeneration mode with liquid before the nickel electrodeposition in the hot water displacement membrane filter appts of 60～80 DEG C of temperature, and the maintenance filtration pressure difference identical with normal filtration pattern filter hot water, if clear liquid flux recovery is to 0.8t/m
2clear liquid flux more than h, membrane filter appts switched back to normal filtration pattern from the first regeneration mode, if cannot return to 0.8t/m
2more than h, membrane filter appts is switched to the second regeneration mode from the first regeneration mode, the operation steps of the second regeneration mode has: a, to membrane filter appts pass into mass concentration be 4～6g/l NaOH solution and keep the filtration pressure difference identical with normal filtration pattern NaOH solution is filtered, treat clear liquid flux no longer rise backward membrane filter appts pass into clear water replace clean to clear water pH≤8; B, discharge after clear water again that to pass into pH be 1.5～2 aqueous sulfuric acid and keep the filtration pressure difference identical with normal filtration pattern to filter aqueous sulfuric acid to membrane filter appts, treat that the clear liquid flux backward membrane filter appts that no longer rises passes into clear water displacement and cleans to clear water pH>=5, finally switches back normal filtration pattern by membrane filter appts from the second regeneration mode.
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| CN201410240461.6A CN104005049B (en) | 2014-05-30 | 2014-05-30 | The electrowinning with insoluble anode production technology of nickel |
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| CN201410240461.6A Active CN104005049B (en) | 2014-05-30 | 2014-05-30 | The electrowinning with insoluble anode production technology of nickel |
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| CN110127729A (en) * | 2019-05-27 | 2019-08-16 | 四川思达能环保科技有限公司 | Lithium hydroxide production technology |
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