CN106480475A - High-purity copper electrorefining additive and the manufacture method of high-purity copper - Google Patents
High-purity copper electrorefining additive and the manufacture method of high-purity copper Download PDFInfo
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- CN106480475A CN106480475A CN201610751052.1A CN201610751052A CN106480475A CN 106480475 A CN106480475 A CN 106480475A CN 201610751052 A CN201610751052 A CN 201610751052A CN 106480475 A CN106480475 A CN 106480475A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
The present invention provides high-purity copper electrorefining additive and the manufacture method of the high-purity copper using this additive.A kind of high-purity copper electrorefining additive, it is added in the copper electrolyte manufacturing high-purity electrolytic copper refining, and it includes：Host, is made up of nonionic surfactant, and described nonionic surfactant has the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes；And stress relaxation agent, it is made up of polyvinyl alcohol or derivatives thereof.
Description
Technical field
The present invention relates to the high-purity copper electrorefining of high-purity copper that the impurity manufacturing sulfur and silver etc. is greatly reduced is with adding
Plus the manufacture method of agent and the high-purity copper using this additive.
The application is for Japanese patent application the 2015-169881st and May 28 in 2016 filed in August in 2015 29 days
Japanese patent application 2016-106862 CLAIM OF PRIORITY filed in day, and here quotes its content.
Background technology
As the manufacture method of high-purity copper, it is known to enter as described in Japanese Patent Publication 08-990 publication
The method of following two one-step electrolysis of row：After copper sulfate solution is electrolysed, using the copper separating out on negative electrode as anode, enter one
Step is in copper nitrate aqueous solution with 100A/m2Following low current density is electrolysed again.
In addition, as described in Japanese Unexamined Patent Publication 2001-123289 publication it is known to by containing chloride from
Add the polyoxyethylene system surfactants such as PEG (Polyethylene Glycol) in son, glue class etc. and the copper sulfate electrolyte of active sulfur components
To improve mechanical characteristic and the manufacture method with the electrolytic copper foil of the stickiness of negative electrode.Additionally, as Japanese Unexamined Patent Publication 2005-
It is known to pass through and use the mucus of levelling agent and the PEG of PVA (polyvinyl alcohol) etc. etc. as described in No. 307343 publications
(ス ラ イ system) accelerator come to manufacture copper surface smooth and the silver as impurity and sulfur poor high-purity electrolytic copper side
Method.
As shown in the manufacture method of Japanese Patent Publication 08-990 publication, in the electrolysis carrying out copper sulfate bath and copper nitrate bath
This two one-step preparation method of electrolysis in there is a problem of electrolysis bothersome.In addition, with regard to the use of nitric acid, there is carrying capacity of environment high
And drainage sunk well becomes numerous and diverse problem.
If using existing additive (PVA, PEG etc.), it is difficult to improve electric current density, if close in order to improve electric current
Degree and carry out solution stirring then mucus dance in the air, it is attached to and leads to the purity of cathode copper to reduce on negative electrode.It is additionally, since interpolation
The dissolving of agent strong inhibition anode, thus the voltage overshoot of anode rises and produces a large amount of mucus in anodic solution, negative electrode
The mucus quantitative change that yield is attached on negative electrode while decline is many.Further, since existing additive suppresses the precipitation of negative electrode anti-
Should, thus there is a problem of that the sulphur concentration that electrolyte contains cathode copper during sulfate radical rises and leads to purity to decline.
Further, since existing additive (PEG etc.) in the same manner as anode also can strong effect in negative electrode, thus exist because
In electrolysis in negative electrode produce stress and lead to negative electrode warpage and in electrorefining negative electrode from asking that SUS motherboard comes off
Topic.
In addition, the hydrophilic of the additive of the water soluble polymer such as PEG and PVA is high, and ultraviolet-absorbing is not enough,
Thus using the quantitative analysis difficult of high performance liquid chromatography (HPLC), and decomposition rate is rapid, therefore, it is difficult to carrying out accurately
Concentration management.If additionally, using PEG, there is the dendritic processes being easy to produce cathode copper surface, and, be
Solve this problem and use cathode copper during PVA surface smoothened, but the silver as impurity will not fully reduce.In addition,
And then the cathode copper of the manufacture method of surfactant such as the use PEG described in Japanese Unexamined Patent Publication 2001-123289 publication
Sulfur content contour it is difficult to obtain highly purified cathode copper.
Content of the invention
It is an object of the invention to, a kind of manufacture with regard to high-purity copper is provided, can eliminate in existing manufacture method
The problems referred to above, the generation of mucus can be suppressed in electrorefining, can manufacture silver and that the impurity such as sulfur is greatly reduced is high-purity
The high-purity copper with additive and using this high-purity copper electrorefining additive for the high-purity copper electrorefining of degree copper
Manufacture method.
By the present invention in that sending out of suppression mucus can be produced with the additive including host and stress relaxation agent
High-purity copper raw and that the impurity such as silver and sulfur is greatly reduced, provides above-mentioned additive and the manufacture method using this additive, institute
State host to be made up of surfactant, described surfactant has specific hydrophobic group and hydrophilic group.
The present invention relates to having the high-purity copper electrorefining additive of following structure and the manufacture method of high-purity copper.
[1] a kind of high-purity copper electrorefining additive, it is added to the copper manufacturing high-purity electrolytic copper refining
It is characterised in that including in electrolyte：Host, is made up of nonionic surfactant, described nonionic surfactant
There is the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes；And stress relaxation agent, by polyvinyl alcohol or its
Derivant is constituted.
[2] the high-purity copper electrorefining additive according to above-mentioned [1], wherein, described host described hydrophilic
Base comprises at least one of polyoxyethylene groups and polyoxypropylene base, and the described hydrophobic group of described host comprises phenyl or naphthyl.
[3] the high-purity copper electrorefining additive according to above-mentioned [1] or [2], wherein, described host described
The addition molal quantity of the polyoxyalkylenes of hydrophilic group is 2～20.
[4] the high-purity copper electrorefining additive according to any one of above-mentioned [1]～[3], wherein, described should
Power relaxant is 70～99 moles of % of saponification rate and the polyvinyl alcohol of average degree of polymerization 200～2500 or derivatives thereof.
[5] the high-purity copper electrorefining additive according to above-mentioned [4], wherein, described polyvinyl alcohol derivative
Thing is carboxy-modified polyvinyl alcohol, ethylene modified polyvinyl alcohol or polyoxyethylene-modified polyvinyl alcohol.
[6] a kind of manufacture method of high-purity copper, wherein, adds by nonionic surfactant structure in copper electrolyte
The host and the stress relaxation agent that is made up of polyvinyl alcohol or derivatives thereof that become and carry out cupric electrolysis, described non-ionic surface is lived
Property agent there is the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes.
[7] manufacture method of the high-purity copper according to above-mentioned [6], wherein, with the described master in described copper electrolyte
The concentration of agent is 2～500mg/L and described host (X) is 0.01～1.0 with the concentration ratio (Y/X) of described stress relaxation agent (Y)
The mode of scope carry out cupric electrolysis.
[8] manufacture method of the high-purity copper according to above-mentioned [6] or [7], wherein, described copper electrolyte is copper sulfate
Solution, copper nitrate solution or copper chloride solution.
[9] manufacture method of the high-purity copper according to any one of above-mentioned [6]～[8], wherein, using copper concentration be
5～90g/L and sulfuric acid concentration are the copper-bath of 10～300g/L, copper concentration is 5～90g/L and concentration of nitric acid be 0.1～
The copper nitrate solution of 100g/L or copper concentration is 5～90g/L and concentration of hydrochloric acid is the copper chloride solution of 10～300g/L as institute
State copper electrolyte.
[10] manufacture method of the high-purity copper according to any one of above-mentioned [6]～[9], wherein, manufactures sulphur concentration
The glossiness being below 1 mass ppm and cathode copper surface with silver concentration is more than 1 high-purity copper.
In high-purity electrolytic copper refining, by using the additive of the present invention, the electrolysis of manufacture can be greatly reduced
The silver concentration of copper and sulphur concentration.Further, since cathode copper surface is smoothened, thus anode mucus and copper electrolyte are difficult to remain
On cathode copper surface, the few highly purified cathode copper of impurity can be obtained.For example, using copper-bath as copper electrolyte
Cupric electrolysis in, the considerably less cathode copper of sulphur concentration can be obtained.For instance, it is possible to obtain sulphur concentration, silver concentration is 1 mass
The glossiness on below ppm and cathode copper surface is more than 1 high-purity copper.Preferably, sulphur concentration can be manufactured and silver concentration is equal
For below 0.5 mass ppm and cathode copper surface glossiness be more than 2 high-purity electrolytic copper.
The additive of the present invention is attached on copper anode surface due to excessive, thus copper anode can appropriateness dissolve, with
Compare anode mucus during using PEG etc. to reduce, it is possible to increase the yield of cathode copper.The yield of cathode copper is to represent that real income arrives
Cathode weight with respect to the ratio of the anode weight being used, and represent that yield is higher, productivity ratio is better.Anode mucus send out
Raw amount is fewer, and yield is higher, and it is less than 30% that the additive of the present invention can make the incidence rate of anode mucus.Further, since with
Compare during using PEG etc. anode mucus few it is thus possible to carry out solution stirring while carrying out high speed electrolytic.Further, since
Polyoxyethylene list phenyl ether, polyoxyethylene naphthyl ether etc. do not contain sulfur in molecular skeleton, thus if using by this chemical combination
The additive of the present invention that thing is constituted, then can obtain the extremely low cathode copper of sulphur concentration, therefore preferably.In addition, polyoxyethylene groups
Deng addition molal quantity be 2～20 additive compared with glue class strand short, therefore excellent in stability, the management of electrobath is held
Easily, therefore preferably.
The electricity being made the cathode copper separating out on negative electrode by the stress relaxation agent included in the additive of the present invention is sunk
Long-pending stress is relaxed, thus will not produce warpage on cathode copper, therefore cathode copper is kept long-term and stably by negative electrode, can get
The smooth cathode copper of fine and close precipitation and surface.
Specific embodiment
Below, embodiments of the present invention are specifically described.
The additive of present embodiment is high-purity copper electrorefining additive, and it is added to and manufactures high-purity copper
In the copper electrolyte of electrorefining, including：Host, is made up of nonionic surfactant, described non-ionic surfactant
Agent has the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes；And stress relaxation agent, by polyvinyl alcohol or
Its derivant is constituted, in addition, the manufacture method of present embodiment is the manufacture method of the high-purity copper using above-mentioned additive.
The additive of present embodiment includes host, is made up of nonionic surfactant, described non-ionic surface
Activating agent has the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes.The aromatic nucleus of the hydrophobic group of this host
As for phenyl or naphthyl etc., can enumerate single phenyl, naphthyl, cumyl, alkyl phenyl, styrenyl benzene base mono-phemyol, naphthyl,
Cumyl, alkyl phenyl, styrenyl phenyl, distyrenated phenyl, triphenylethylene base phenyl, tribenzyl phenyl etc.
Deng.The polyoxyalkylenes of the hydrophilic group of this host are, for example, polyoxyethylene groups, polyoxypropylene base etc., can also be and comprise polyoxy second
Both groups of thiazolinyl and polyoxypropylene base.
The specific compound of the host included in the additive of present embodiment is, for example, polyoxyethylene list phenyl
Ether, polyoxyethylene methyl phenyl ether, NONIN HS 240, polyoxyethylene lauryl base phenyl ether, polyoxyethylene naphthyl
Ether, polyoxyethylene styrene base phenyl ether, the distyrenated phenyl ether of polyoxyethylene, polyoxyethylene tri-styryl base benzene
Base ether, polyoxyethylene cumyl phenyl ether, polyoxypropylene list phenyl ether, polyoxypropylene methyl phenyl ether, polyoxypropylene octyl phenyl
Ether, polyoxypropylene dodecylphenyl ether, polyoxypropylene naphthyl ether, polyoxypropylene styrenyl phenyl ether, polyoxypropylene two
Styrenyl phenyl ether, polyoxypropylene triphenylethylene base phenyl ether, polyoxypropylene cumyl phenyl ether etc..
The additive of present embodiment is added in the copper electrolyte of copper electrolyzing refining and uses.In this copper electrolyzing refining
In, the host included in the additive of present embodiment is due to having the hydrophobic group of aromatic rings and the hydrophilic of polyoxyalkylenes
Base, it is thus possible to the silver ion in suppression copper electrolyte and sulphion precipitate into cathode base, can be greatly reduced cathode copper
Silver concentration and sulphur concentration.Additionally, the additive of present embodiment is few with using anode mucus compared with during PEG etc..Specifically, originally
The host of the additive of embodiment comprises the hydrophilic group of hydrophobic group and polyoxyalkylenes, is excessively attached to cathode base
On surface, the dissolving of therefore not extra-inhibitory copper anode.Therefore, because copper anode appropriateness dissolving, anode mucus with use PEG
Deng when compare few, thus the anode mucus amount being attached on the surface of the cathode copper precipitateing into cathode base reduces, and can obtain
Highly purified cathode copper.
Additionally, on the surface making precipitate into cathode base by the host included in the additive of present embodiment
Cathode copper becomes fine and close, and the flatness on therefore cathode copper surface improves.Therefore, the sulfur in copper electrolyte and anode mucus be difficult to attached
And remain on cathode copper surface, thus they are difficult to enter cathode copper, the highly purified electrolysis few therefore, it is possible to obtain impurity
Copper.
Existing surfactant used in copper electrolyte, such as PEG due to not comprising aromatic rings in hydrophobic group,
Hence without this effect.On the contrary, existing PEG etc. is because strong adhesion is on copper anode surface, thus the dissolving of copper anode
It is overly hindered.Therefore, the generation of anode mucus is many, and it enters the cathode copper surface of cathode base, thus existing under copper quality
The problem of fall.Specifically, add PEG etc. and carry out the sulphur concentration of cathode copper and the adding using present embodiment of electrorefining
Plus compare very many during agent.On the other hand, compared with the additive of present embodiment and existing PEG etc., electricity can be significantly reduced
The sulphur concentration of solution copper.
The aromatic rings of the hydrophobic group of above-mentioned host are preferably single phenyl or naphthyl.In addition, the hydrophilic group of above-mentioned host is poly-
Oxyalkylene group for example has polyoxyethylene groups, mixing of polyoxypropylene base, polyoxyethylene groups and polyoxypropylene base etc., particularly preferably
For polyoxyethylene groups.Host included in the additive of present embodiment, preferably addition molal quantity are 2～20 polyoxy
Ethylene list phenyl ether or polyoxyethylene naphthyl ether that addition molal quantity is 2～20 etc..
With regard to above-mentioned host, preferred concrete example described below.Formula 1 is polyoxyethylene list phenyl ether, and formula 2 is polyoxyethylene
Naphthyl ether.Formula 1, the n of formula 2 are the addition molal quantity of polyoxyethylene groups.
[changing 1]
[changing 2]
In above-mentioned host, the addition molal quantity preferably 2～20 of the polyoxyalkylenes of hydrophilic group, and, this addition rubs
You are more preferably 2～15 by number.If this addition molal quantity is less than 2, above-mentioned host is not dissolved in copper electrolyte.If should add
Molal quantity is become to be more than 20, then this additive becomes overstocked to the attachment of anode surface, the dissolving reaction of anode is over-constrained, because
There is more, the yield decline of cathode copper in this anode mucus.If additionally, above-mentioned addition molal quantity is more than 20, precipitate into
It is easy on the cathode copper surface of cathode base ingotism (デ Application ト ラ イ ト), flatness declines.Therefore, because anode
Sulfur in mucus and copper electrolyte is easy to attachment and remains on cathode copper surface, thus the purity of cathode copper can decline.If on
State host polyoxyalkylenes addition molal quantity be 2～20, then the dissolving appropriateness of anode carry out, therefore with during using PEG etc.
Compare anode mucus to reduce, highly purified cathode copper can be obtained.Additionally, having the polyoxy that above-mentioned addition molal quantity is 2～15
The additive changing thiazolinyl can be greatly reduced the sulphur concentration of cathode copper.
Further, since electrolysis reaction is affected by the bath temperature of copper electrolyte, thus the addition of above-mentioned polyoxyethylene groups rubs
The preferred scope of your number is different because bath temperature is different, and such as bath temperature is that addition molal quantity when 20～55 DEG C is preferably 2～15, copper
The bath temperature of electrolyte is that addition molal quantity when 55 DEG C～75 DEG C is preferably 9～20.
There is no phenyl or naphthyl and only there is the electricity making cathode base of the compound of the polyoxyethylene groups of hydrophilic group etc.
It is not sufficiently effective that analysis smooths.For example, the Polyethylene Glycol of addition molal quantity 8 with by the addition molal quantity 8 of same polyoxyethylene groups
Polyoxyethylene list phenyl ether is used in be compared during additive, such as in electric current density 200A/m2When, the surface of cathode copper, especially
It is that end is thicker.
Stress relaxation agent included in the additive of present embodiment is made up of polyvinyl alcohol or derivatives thereof.Should
Power relaxant is relaxed to the electro-deposition stress of the cathode copper precipitateing into cathode base and is prevented this cathode copper from cathode base
Come off.It is relaxed by electro-deposition stress, cathode copper is held in cathode base by long-time stable, therefore can get copper densely
The smooth cathode copper of electrolysis and surface.On the other hand, if electro-deposition stress is not relaxed and accumulates, cathode copper produces warpage
And peel off from cathode base and come off.
Polyvinyl alcohol of above-mentioned stress relaxation agent or derivatives thereof is, for example, carboxy-modified polyvinyl alcohol, ethylene modified poly- second
Enol or polyoxyethylene-modified polyvinyl alcohol.
The saponification rate of above-mentioned polyvinyl alcohol or derivatives thereof is preferably 70～99 moles of %.If saponification rate rubs less than 70
You are %, then relax the not sufficiently effective of electro-deposition stress.On the other hand, fully saponified material (100 moles of % of saponification rate) is molten
Solution property is remarkably decreased it is impossible to dissolve in polyvinyl alcohol or derivatives thereof in copper electrolyte.More preferably by polyvinyl alcohol or its
The saponification rate of derivant is set to 70～90 moles of %, but is not limited to this.Saponification rate is according to JIS K 6726:1994 poly- second
Enol test method is obtained.
The average degree of polymerization of the polyvinyl alcohol of above-mentioned stress relaxation agent or derivatives thereof is preferably 200～2500.Polyethylene
The essential structure of alcohol and its derivant is made up of with the partly-hydrolysed type with acetate the fully saponified type of hydroxyl, polyvinyl alcohol
And its degree of polymerization of derivant is the sum of both, average degree of polymerization is the meansigma methodss of the degree of polymerization.Average degree of polymerization being capable of root
According to JIS K 6726:1994 polyvinyl alcohol test method is measured.
Average degree of polymerization as pectin/polyvinyl alcohol or derivatives thereof is less than 200, then relax the not sufficiently effective of electro-deposition stress.
In addition, average degree of polymerization is less than 200 polyvinyl alcohol or derivatives thereof there is also difficulty on manufacturing, and generally do not use,
Therefore, it is difficult to obtaining.In addition, when above-mentioned average degree of polymerization is more than 2500, the effect of lax electro-deposition stress fades away, separate out
There is warpage in the cathode copper to cathode base.And, if above-mentioned average degree of polymerization is more than 2500, produce electro-deposition suppression effect
Really, there is the tendency declining in the yield of cathode copper.More preferably the average degree of polymerization of polyvinyl alcohol or derivatives thereof is set to 200
～2000, but it is not limited to this.
With regard to host and stress relaxation agent, copper electrolyte can be added to after being pre-mixed in the way of becoming normal concentration
Middle as additive, or can also be respectively added in copper electrolyte in the way of becoming normal concentration.
The additive of present embodiment is added in copper electrolyte and uses.In copper electrolyte, above-mentioned host dense
Degree is preferably the scope of 2～500mg/L, the more preferably scope of 10～300mg/L.If the concentration of this host is less than 2mg/L,
The inhibition deficiency then brought due to host, thus the flatness on cathode copper surface declines.If cathode copper surface is smooth
Property decline, then copper electrolyte is easy to be attached to cathode copper surface and enters in cathode copper, the therefore sulphur concentration in cathode copper and silver
Concentration can rise.On the other hand, if the concentration of this host is more than 500mg/L, the attachment of anode surface is too strong, the generation of mucus
Amount can increase, and it enters the cathode copper of cathode base, the therefore sulphur concentration in cathode copper and silver together with the additive of surpluses
Concentration can improve.
Concentration (mg/L) with regard to stress relaxation agent, is preferably this stress relaxation agent (Y) dense with respect to above-mentioned host (X)
The concentration ratio (Y/X) of degree is 0.01～1.0 scope.If the concentration of stress relaxation agent is higher than the concentration of host, Y/X ratio is more than
1.0, then cathode copper can somewhat produce warpage on the contrary.On the other hand, if the concentration of stress relaxation agent is low, Y/X ratio less than 0.01,
Then stress relaxation agent is not sufficiently effective.More preferably above-mentioned Y/X ratio is set to 0.01～0.5, but is not limited to this.Additionally,
In the additive of present embodiment it is preferable that becoming above-mentioned with concentration ratio when this additive is added in copper electrolyte
The mode of scope mix host and stress relaxation agent.
The copper electrolyte that the additive of present embodiment is used is copper-bath, copper nitrate solution or copper chloride solution
Copper compound solution Deng mineral acid.When using copper-bath as copper electrolyte, sulfuric acid concentration is preferably 10～300g/L.
When sulfuric acid concentration is less than 10g/L, in cathode copper surface, produce Copper hydrate, precipitation state can deteriorate.On the other hand, if sulphuric acid
Concentration is more than 300g/L, then the sulphuric acid inlet in cathode copper increases, and sulphur concentration can rise.Sulfuric acid concentration more preferably 10～
100g/L, but it is not limited to this.When copper electrolyte is for copper nitrate solution, concentration of nitric acid is preferably 0.1～100g/L, more excellent
Elect 0.1～50g/L as, but be not limited to this.When copper electrolyte is for copper chloride solution, concentration of hydrochloric acid be preferably 10～
300g/L, more preferably 10～200g/L, but it is not limited to this.
Copper electrolyte for copper-bath, copper nitrate solution or copper chloride solution any one when, the copper of copper electrolyte
Concentration is both preferably 5～90g/L and (is calculated as 20～350g/L with copper sulfate pentahydrate concentration, with cupric nitrate trihydrate concentration
It is calculated as 19～342g/L, 13～241g/L is calculated as with copper chloride dihydrate concentration).Copper concentration be less than 5g/L when, cathode copper with
Powder separates out, and therefore purity can decline.On the other hand, if copper concentration is more than 90g/L, copper electrolyte easily enters electrolysis
In copper, therefore purity can decline.More preferably the copper concentration of copper electrolyte is set to 20～70g/L, but is not limited to this.
It is copper electrolyte when copper sulfate or copper nitrate with regard to copper electrolyte, chloride ion concentration is preferably 200mg/L
Below.If chloride ion concentration is more than 200mg/L, chloride easily enters in cathode copper, the purity of cathode copper can under
Fall.Furthermore it is preferred that the lower limit of chloride ion concentration is set to 5mg/L, more preferably chloride ion concentration is set to 5～
150mg/L, but it is not limited to this.
The additive of present embodiment includes：Host, is made up of nonionic surfactant, described non-ionic surface
Activating agent has the hydrophobic group of hydrophilic group and the phenyl or naphthyl of polyoxyethylene groups etc. etc., inhales because this host has intensive ultraviolet
The property received and hydrophobicity are it is thus possible to carry out the quantitative analyses using high performance liquid chromatography (HPLC).Therefore, surveyed by HPLC
Determine the concentration of this host in copper electrolyte, maintain the scope of 2～500mg/L with the concentration of this host, more preferably maintain 10～
The mode of the scope of 300mg/L, supplements the minimizing part of this host and carries out copper electrolyzing refining.In addition, with host and answering
The concentration ratio (Y/X) of power relaxant maintains the mode of 0.01～1.0 scope, supplements host and stress relaxation agent (or additive)
Minimizing part and carry out copper electrolyzing refining and also may be used.
[embodiment]
Examples and comparative examples of the present invention described below.The cathode copper manufacturing in below example and comparative example
Sulphur concentration and silver concentration are to be measured by GD-MS (glow discharge mass analysis).In addition, measuring the central part of cathode copper
Sulphur concentration and silver concentration.The glossiness on cathode copper surface is based on JIS Z 8741:1997 (corresponding to ISO 2813:1994、
ISO 7668:1986), existed using Grossmeters (electricity Se Industrial Co., Ltd of Japan system makes HANDY GLOSSMETERPG-1M)
The central authorities of cathode copper are measured under conditions of 60 ° of angle (angle of incidence).If glossiness is less than 1, it is difficult to fully be cleaned with water
It is attached to the electrolyte on cupric electrolysis copper surface, therefore copper electrolyte is easy to remain on cathode copper surface, the purity of cathode copper
Can decline.Observe by visual observation to judge the warpage of cathode copper.No being represented with zero symbol of warpage, slightly warpage with △ symbol
Represent, warpage is very big and can be clearly visible cathode copper and is represented with × symbol from what cathode base was peeled off.Specifically, by cathode copper
The cathode copper do not peeled off from cathode base is judged as no warpage mark zero symbol, by the area of cathode copper more than half from the moon
The cathode copper that electrode substrate is peeled off is judged as that warpage is very big and marks × symbol, and judgement in addition is to have warpage and mark △
Symbol.Mucus incidence rate is obtained by following formula.Additionally, the meltage of the anode of following formula is the weight of the anode before and after electrorefining
Variable quantity.
Mucus incidence rate (%)=100- (weight of the cathode copper of precipitation)/(meltage of anode) × 100
[embodiment 1]
Copper-bath, copper nitrate solution or copper chloride solution are used as copper electrolyte.Will be dense for the acid of this copper electrolyte
Degree be set to 50g/L, copper concentration is set to 50g/L, except copper chloride bathe (copper chloride solution) in addition to chloride ion concentration is set to
100mg/L.In this copper electrolyte add 30mg/L host (A～B), by stress relaxation agent (D～G) with stress relaxation agent/
The amount that the ratio (Y/X) of the concentration (mg/L) of host becomes the value shown in table 1 is added in above-mentioned copper electrolyte.Table 1 illustrates host
Species, addition molal quantity (n) of ethylene oxide and concentration (mg/L) and the species of stress relaxation agent, saponification rate (rub
Your %), average degree of polymerization and concentration (mg/L).In the anode using the electrolysis of sulphur concentration 5 mass ppm and silver concentration 8 mass ppm
Copper, uses SUS316 as cathode base.Electric current density is set to 200A/m2, it is electrolysed at 30 DEG C of bath temperature.Little every 12
When, measure host and the concentration of stress relaxation agent by using the HPLC of ODS chromatographic column and GPC chromatographic column, by host
Concentration is maintained at 30mg/L and the concentration of stress relaxation agent is maintained at the mode of the concentration ratio (Y/X) of table 1 and feeds minimizing part
And manufacture cathode copper.Table 1 illustrates its result (No.1～No.14).
[comparative example 1]
It is used copper-bath similarly to Example 1 as copper electrolyte, add 30mg/L's in this copper electrolyte
Host (A～C, PEG), without stress relaxation agent, No.18 adds stress relaxation agent D to No.15～No.17, in addition with reality
Apply example 1 similarly to carry out electrorefining and manufacture cathode copper.Table 1 illustrates its result (No.15～No.18).In addition, using and reality
Apply the same copper-bath of example 1 as copper electrolyte, host and stress relaxation agent are all without (No.19), or add poly-
Ethylene glycol (PEG) (No.20), carries out electrorefining similarly to Example 1 in addition and manufactures cathode copper.Table 1 illustrates it
Result.
As shown in table 1, the sulphur concentration of the cathode copper of the No.1～No.14 of embodiment 1 is considerably less, and silver concentration is also few.In addition,
Mucus incidence rate is less than 29%, and the glossiness on cathode copper surface is more than 2.
On the other hand, do not use the sticking up of the cathode copper of comparative sample No.15～No.17 of the comparative example 1 of stress relaxation agent
Qu Jun great, the glossiness on cathode copper surface is also low.In addition, the electricity using host C and the comparative sample No.18 of stress relaxation agent D
The concentration of the sulfur of solution copper and silver is many, and mucus incidence rate is also high, and the glossiness on cathode copper surface is also greatly reduced.Host C and enforcement
Used in example 1, host A, B is different, does not have the hydrophobic group of aromatic rings, therefore confirms the effect not suppressing mucus to occur.And
And, and if with this host C and stress relaxation agent D, the concentration of the sulfur of cathode copper and silver and mucus incidence rate significantly uprise,
Confirm host C and stress relaxation agent and with not preferred.
As shown in the No.1～No.14 of embodiment 1, preferably lived by non-ionic surface with the host of stress relaxation agent
Property agent constitute, described nonionic surfactant has the hydrophobic group comprising aromatic rings and comprise the hydrophilic of polyoxyalkylenes
Base, is identified through and with this host with the stress relaxation agent that is made up of polyvinyl alcohol or derivatives thereof, can obtain cathode copper
The concentration of sulfur and silver is few, mucus incidence rate is low, no warpage and the high cathode copper of glossiness.
All not using host and stress relaxation agent comparative example 1 comparative sample No.19 by not having additive to be brought
Anodic solution inhibition, thus mucus generating capacity is low, but the concentration of the sulfur of cathode copper and silver is high, and cathode copper surface is non-
Often coarse.Therefore, it is impossible to glossiness is measured by Grossmeters.With regard to the No.20 using existing PEG, mucus incidence rate is high,
The concentration of the sulfur of cathode copper and silver is also many than the No.1～No.14 of embodiment 1.Further, since cathode copper surface is easy to generation tree
Branch projection, thus glossiness cannot be measured.In addition, No.19 and No.20 of comparative example 1 all sees warpage in cathode copper.
[table 1]
[embodiment 2]
As copper electrolyte, using copper-bath (sulfuric acid concentration 100g/L, copper concentration 40g/L) or copper nitrate solution
(concentration of nitric acid 10g/L, copper concentration 40g/L), using by host A (addition molal quantity 5) of embodiment 1 and stress relaxation agent D (soap
88 moles of % of rate, average degree of polymerization 200) additive that constitutes, or using host B (addition molal quantity 7) by embodiment 1
The additive constituting with stress relaxation agent E (78 moles of % of saponification rate, average degree of polymerization 620), by these additives with host and
The amount that the concentration of stress relaxation agent becomes the scope shown in table 2 is added in copper electrolyte, in addition similarly to Example 1
Cathode copper is manufactured by electrorefining.Table 2 illustrates its result.As shown in table 2, confirm that the concentration of host under any circumstance is all excellent
Select the scope of 2～50mg/L.
[table 2]
[embodiment 3]
As copper electrolyte, using copper-bath or copper nitrate solution, adjustment acid concentration and copper concentration as shown in table 2.
Add and be included in host A used in embodiment 1 (addition molal quantity 15) and stress relaxation agent D (88 moles of % of saponification rate, averagely
The degree of polymerization 200) the present invention additive, or add comprise host B (addition molal quantity 7) and stress relaxation agent G (saponification rate
98 moles of %, averages degree of polymerization 700) the present invention additive, in addition carry out electrorefining similarly to Example 1,
Manufacture cathode copper.Table 3 illustrates its result.As shown in table 3, confirm to be preferably sulphuric acid as the copper-bath that copper electrolyte uses
Concentration 10～300g/L and the scope of copper concentration 5～90g/L, copper nitrate solution is preferably concentration of nitric acid 0.1～100g/L and copper
The scope of concentration 5～90g/L.
[table 3]
Above preferred embodiments of the present invention have been disclosed for illustrative, but the present invention is not limited to these embodiments.Not
Depart from the range of spirit of the invention, adding, omit, replacing and other changes of structure can be carried out.The present invention not by
Aforesaid explanation is limited, and the claims being only attached limit.
Industrial applicability
High-purity copper electrorefining additive according to the present invention and using this high-purity copper electrorefining additive
Manufacture method, high-purity electrolytic copper refining can suppress the generation of mucus, sulphur concentration can be manufactured and silver concentration is big
The high-purity copper that width reduces.
Claims (10)
1. a kind of high-purity copper electrorefining additive, it is added to the copper electrolyte manufacturing high-purity electrolytic copper refining
In it is characterised in that include：Host, is made up of nonionic surfactant, and described nonionic surfactant has bag
Hydrophobic group containing aromatic rings and the hydrophilic group comprising polyoxyalkylenes；And stress relaxation agent, by polyvinyl alcohol or derivatives thereof
Constitute.
2. high-purity copper electrorefining additive according to claim 1, wherein, the described hydrophilic group bag of described host
Containing at least one of polyoxyethylene groups and polyoxypropylene base, the described hydrophobic group of described host comprises phenyl or naphthyl.
3. high-purity copper electrorefining additive according to claim 1 and 2, wherein, described host described hydrophilic
The addition molal quantity of the polyoxyalkylenes of base is 2～20.
4. the high-purity copper electrorefining additive according to any one of claims 1 to 3, wherein, described stress pine
Relaxation agent is 70～99 moles of % of saponification rate and the polyvinyl alcohol of average degree of polymerization 200～2500 or derivatives thereof.
5. high-purity copper electrorefining additive according to claim 4, wherein, the derivant of described polyvinyl alcohol is
Carboxy-modified polyvinyl alcohol, ethylene modified polyvinyl alcohol or polyoxyethylene-modified polyvinyl alcohol.
6. a kind of manufacture method of high-purity copper is it is characterised in that add by nonionic surfactant in copper electrolyte
The host and the stress relaxation agent that is made up of polyvinyl alcohol or derivatives thereof that constitute and carry out cupric electrolysis, described non-ionic surface
Activating agent has the hydrophobic group comprising aromatic rings and the hydrophilic group comprising polyoxyalkylenes.
7. the manufacture method of high-purity copper according to claim 6, wherein, with the described host in described copper electrolyte
Concentration be 2～500mg/L and concentration ratio Y/X of described host X and described stress relaxation agent Y be 0.01～1.0 scope side
Formula carries out cupric electrolysis.
8. the manufacture method of the high-purity copper according to claim 6 or 7, wherein, described copper electrolyte be copper-bath,
Copper nitrate solution or copper chloride solution.
9. the manufacture method of the high-purity copper according to any one of claim 6～8, wherein, using copper concentration be 5～
90g/L and sulfuric acid concentration are the copper-bath of 10～300g/L, copper concentration is 5～90g/L and concentration of nitric acid be 0.1～
The copper nitrate solution of 100g/L or copper concentration is 5～90g/L and concentration of hydrochloric acid is the copper chloride solution of 10～300g/L as institute
State copper electrolyte.
10. the manufacture method of the high-purity copper according to any one of claim 6～9, wherein, manufactures sulphur concentration and silver is dense
The glossiness that degree is below 1 mass ppm and cathode copper surface is more than 1 high-purity copper.
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| JP2016-106862 | 2016-05-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110678582A (en) * | 2017-06-01 | 2020-01-10 | 三菱综合材料株式会社 | Method for producing high-purity electrolytic copper |
| CN111304694A (en) * | 2019-11-13 | 2020-06-19 | 铜陵有色金属集团股份有限公司 | Method for directly electrolyzing scrap copper |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018221724A1 (en) | 2017-06-01 | 2018-12-06 | 三菱マテリアル株式会社 | High-purity electrolytic copper |
| JP7172131B2 (en) * | 2017-06-02 | 2022-11-16 | 三菱マテリアル株式会社 | Manufacturing method of high-purity electrolytic copper |
| CN114457390B (en) * | 2022-02-24 | 2024-06-04 | 阳谷祥光铜业有限公司 | Preparation method of ultra-high purity copper foil |
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| TW201726979A (en) | 2017-08-01 |
| JP2017043834A (en) | 2017-03-02 |
| CN106480475B (en) | 2021-01-15 |
| TWI691618B (en) | 2020-04-21 |
| JP6733313B2 (en) | 2020-07-29 |
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