CN103668419B - A kind of devices and methods therefor for reducing tin mud generation in tin plating electrolyte preparation process - Google Patents
A kind of devices and methods therefor for reducing tin mud generation in tin plating electrolyte preparation process Download PDFInfo
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- CN103668419B CN103668419B CN201210315873.2A CN201210315873A CN103668419B CN 103668419 B CN103668419 B CN 103668419B CN 201210315873 A CN201210315873 A CN 201210315873A CN 103668419 B CN103668419 B CN 103668419B
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Abstract
The present invention relates to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process, and a kind of method applying tin mud generation in described device reduction tin plating electrolyte preparation process, when not increasing extras, there is provided the design of a porous web plate to ensure that the tin particles in tin dissolving vessel can be in desirable fluidized state, namely tin particles is in a kind of free-pouring state in dissolving vessel, fully mix with the tin plating electrolyte containing dissolved oxygen, avoid the generation of local excess of oxygen.Increase the amount of tin particles in mixing section in addition, with excessive tin particles, under ensureing maximum molten tin rate behavior, oxygen also can not be excessive simultaneously, meanwhile, by the proportioning of rational tin plating electrolyte component, makes tin mud generation be reduced to a lower level.
Description
Technical field
The present invention relates to a kind of device, particularly, a kind of device for reducing tin mud generation in tin plating electrolyte preparation process is related to, simultaneously, the invention still further relates to a kind of method applying tin mud generation in described device reduction tin plating electrolyte preparation process, be applied to the plating solution preparation of insoluble anode.
Background technology
The mode of production of commodity electrolytic tinplate is divided into two kinds: one uses insoluble anode to carry out eleetrotinplate, and one uses solubility tin anode to carry out eleetrotinplate.Adopt insoluble anode, because anode electrode does not dissolve, the distance of anode and plated steel band can be made to remain unchanged, thus coating thickness evenly.Simultaneously the life-span of insoluble anode was at about 10 months, and doing so avoids soluble anode must the impact of the open severe operating environments of the heavy manual work changed of every class and the scene of bearing.
The method of insoluble anode eleetrotinplate and the maximum of soluble anode is adopted not to be both the zinc-plated device that must be had to carry out tin plating electrolyte and prepare of insoluble anode.This is the process of a chemical dissolution tin, accelerates tin be oxidized to Sn by oxygen blast
2+, but unavoidably will produce Sn
4+, i.e. tin mud.
Device prepared by tin plating electrolyte is that an inner filling has metallic tin particle, has plating solution flow at high speed and be blown into oxygen to make tin that the metallic tin dissolving vessel dissolved occur.When metallic tin particle runs into oxygen, its surface will generate tin protoxide, the H in tin protoxide and tin plating electrolyte
+reaction just generates the divalent tin ion that we need.Excessive dissolved oxygen can react with tin protoxide again and generate stannic oxide, and because stannic oxide is insoluble, so just become the mud in tin plating electrolyte, its existence not only can affect the quality of plating, is also the manifestation of a kind of tin resource loss simultaneously.
Soluble anode eleetrotinplate contacts with the mandatory of oxygen owing to not having this tin particle, in the tin mud that it produces, the content of tin generally accounts for 0.5 ~ 1.5% (tin contained in tin mud/dissolving tin) of the usage quantity of total tin metal, and insoluble anode is 4 ~ 12%.Therefore, the tin mud loss reducing insoluble anode eleetrotinplate just becomes the one pursuit of this technology.Also be the reason that current insoluble anode eleetrotinplate technology is not used widely.
In fact, the source of tin mud is caused by the reason of two aspects, and one is that in the exclusive tin process processed that faces of insoluble anode technique, tin ion contacts with the mandatory of purity oxygen; Be on the other hand these two kinds of techniques all will faced by eleetrotinplate process, the process of plating can produce oxygen, and simultaneously because tin plating electrolyte runs in the groove tank of opening, will certainly contact with air in the process of plating, the process of therefore electroplating also can produce tin mud.The per-cent that in the tin wastage rate that produce of all its soluble anode eleetrotinplates of business-like zinc-plated production line and tin mud, the content of tin accounts for the usage quantity (consumption of the tin ÷ metallic tin contained in tin mud) of total tin metal is in the world 0.5 ~ 1.5%, and insoluble anode eleetrotinplate is owing to also having a tin process processed, in all tin mud, the content of tin accounts for the per-cent of the usage quantity of total tin metal 4 ~ 12%.Therefore, the tin mud loss reducing insoluble anode eleetrotinplate just becomes the one pursuit of this technology.Also be the reason that current insoluble anode eleetrotinplate technology is not used widely.
Generating tin mud in the plating solution to suppress the tin protoxide in tin dissolving vessel to be oxidized to stannic oxide precipitation further, mainly there is following patent documentation at present:
Patent documentation 1: Unexamined Patent 3-No. 180493 publications propose and carry out mechanical stirring to accelerate the dissolution rate of tin to metal ion, thus the generating capacity reducing tin mud.In fact, churned mechanically Main Function is the tin plating electrolyte Homogeneous phase mixing more fully making tin particles and the oxygen be blown into and flowing.This method increase facility investment, meanwhile, when tin particles dissolving vessel have very large pressure, agitator turning axle just seems very important through the dynamic seal at dissolving vessel position, and under continuous duty, the reliability of normal work is difficult to ensure.The agitator increased too increases the extra consumption of the energy.
Patent documentation 2: it is the electroplate liquid of below 300ppm that Unexamined Patent-No. 131399 publication proposes to the metallic tin particle supply dissolved oxygen in mixing section, reduces the generating capacity reducing tin mud of excess of oxygen situation.Patent documentation 3:CN1993502A provides one and is controlled between target bound by tin ion concentration, thus makes tin ion formation speed close to the average predetermined spending rate of tin ion, thus can reduce the method for the generation of tin mud.The method is when the amount of being blown into of adjustment oxygen, calculate the predetermined spending rate of tin ion according to the travelling speed of steel band to measure over time, every the scheduled time, described tin ion formation speed is divided, by the interval in each division the tin ion formation speed of equalization be set as on average measuring over time, adjust the amount of being blown into of oxygen with this, making on average to measure the tin ion concentration adapted over time becomes the tin ion formation speed being no more than control objectives bound.Above-mentioned two patent documentations are all start with reduce the generation of tin mud from how reducing the excessive oxygen amount of being blown into, but method is loaded down with trivial details and control method complicated, require higher, implement difficulty larger to control accuracy.
Summary of the invention
For solving above-mentioned Problems existing, the object of the present invention is to provide a kind of device for reducing tin mud generation in tin plating electrolyte preparation process, and a kind of method applying tin mud generation in described device reduction tin plating electrolyte preparation process, when not increasing extras, there is provided the design of a porous web plate to ensure that the tin particles in tin dissolving vessel can be in desirable fluidized state, namely tin particles is in a kind of free-pouring state in dissolving vessel, fully mix with the tin plating electrolyte containing dissolved oxygen, avoid the generation of local excess of oxygen.Increase the amount of tin particles in mixing section in addition, with excessive tin particles, under ensureing maximum molten tin rate behavior, oxygen also can not be excessive simultaneously, meanwhile, by the proportioning of rational tin plating electrolyte component, makes tin mud generation be reduced to a lower level.
For achieving the above object, the present invention mainly adopts following technical scheme:
For reducing a device for tin mud generation in tin plating electrolyte preparation process, described device comprises eleetrotinplate unit and tin dissolves unit,
Described eleetrotinplate unit comprises plating tank, and described plating tank one end is connected with the second recycle pump and the 3rd valve respectively by pipeline;
Described tin dissolves unit and comprises tin dissolving vessel, described tin dissolving vessel forms closed connection by pipeline and oxygen supply device, the first recycle pump, plating solution storage tanks and the first valve, described tin dissolving vessel comprise set gradually separate chamber, mixing section and distributing chamber;
Described plating tank is connected with plating solution storage tanks by pipeline, and described second recycle pump is connected with plating solution storage tanks by the 4th valve with after the 3rd valve in parallel, it is characterized in that:
Be provided with porous web plate between described mixing section and distributing chamber, described porous web plate comprises the first web plate and the second web plate.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is provided with the 3rd tensimeter between described distributing chamber and oxygen supply device.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described mixing section is connected with the first pressure warning unit, be provided with the second pressure warning unit between described separate chamber and the first valve, between described separate chamber and the first valve, be also provided with under meter.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is also provided with the second valve between described oxygen supply device and plating solution storage tanks, and described second valve and the first recycle pump are formed and be connected in parallel.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described second web plate is arranged at above the first web plate, described first web plate thickness is 20 ~ 30mm, aperture is 6 ~ 8mm, percentage of open area is 28 ~ 32%, and described second web plate thickness is 2 ~ 5mm, and aperture is greater than 0 and is less than 2.5mm.
According to a kind of device for reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, is bolted between described first web plate and the second web plate.
Meanwhile, the present invention also provides a kind of device applying tin mud generation in described reduction tin plating electrolyte preparation process to reduce the method for tin mud generation in tin plating electrolyte preparation process, it is characterized in that: described method comprises the steps:
(A), in mixing section (102) add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is 300 ~ 1000Nl/min, and oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted tin dissolving vessel (1), oxygen is blown in distributing chamber (103) according to the oxygen amount of being blown in step (A) and oxygen blast intensity and mixes with plating solution, the plating solution being mixed with oxygen enters mixing section (102) through porous web plate (11), dissolve the tin particles in mixing section (102), form tin plating electrolyte, finally, the tin plating electrolyte of generation discharges tin dissolving vessel (1) from separate chamber (101) top exit;
(C) the numerical value P in the first pressure warning unit (5), is observed
1, numerical value P in the second pressure warning unit (6)
2and the flow velocity numerical value under meter (13), according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate (1101) constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate (1102), making the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally making tin particles and plating solution reach Homogeneous phase mixing state.
According to a kind of method reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, adopt, the diameter of described tin particles is 2.5 ~ 3mm, and described Critical Stability percentage of open area is 4 ~ 15%, the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.
According to a kind of method reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, what adopt is, described plating solution is metilsulfate plating solution, described metilsulfate plating solution comprises following component: methylsulphonic acid salt concn 65 ~ 75ml/l, additive concentration 25 ~ 35ml/l, antioxidant concentration 15 ~ 25ml/l.
According to a kind of method reducing tin mud generation in tin plating electrolyte preparation process provided by the present invention, employing, in described mixing section, tin particles add-on scope is 5 ~ 8 tons.
Beneficial effect of the present invention is:
1), a porous web plate is set between the distributing chamber and mixing section of tin dissolving vessel, thus ensure that the tin particles in tin dissolving vessel can be in desirable good Homogeneous phase mixing state, thus make tin particles in dissolving vessel, be in a kind of free-pouring state, fully mix with the plating solution containing dissolved oxygen, avoid the oxygen excess of regional area, reduce tin mud generation;
2), introduce the index of " oxygen blast intensity " and instruct control to tin particles add-on in mixing section, thus by using excessive tin particles, under ensureing maximum molten tin rate behavior, oxygen can not be excessive;
3), by the metilsulfate plating solution of specific proportioning and component, the generation of tin mud is effectively suppressed further.
Accompanying drawing explanation
Fig. 1 is that plating solution is by the total pressure drop of tin particles layer during different percentage of open area web plate and the relation schematic diagram of apparent velocity.
Fig. 2 is a kind of structural representation for reducing the device of tin mud generation in tin plating electrolyte preparation process provided by the present invention.
Fig. 3 is a kind of structural representation for reducing porous web plate in the device of tin mud generation in tin plating electrolyte preparation process provided by the present invention.
In Fig. 1, A, the fixing tin particles layer in local, B, local fluidization tin particles layer, gush tin particles layer in C, local, α, in real time percentage of open area, α
cS, Critical Stability percentage of open area, U
mf, critical fluidized speed.
In Fig. 2,1, tin dissolving vessel, 101, separate chamber, 102, mixing section, 103, distributing chamber, the 2, first recycle pump, 3, oxygen supply device, the 4, the 3rd pressure warning unit, 5, the first pressure warning unit, the 6, second pressure warning unit, the 701, first valve, 702, the second valve, the 703, the 3rd valve, the 704, the 4th valve, 8, plating solution storage tanks, the 9, second recycle pump, 10, plating tank, 11, porous web plate, 12, pipeline, 13, under meter.
In Fig. 3, the 1101, first web plate, the 1102, second web plate.
Embodiment
A kind ofly to be further explained for reducing the devices and methods therefor of tin mud generation in tin plating electrolyte preparation process provided by the present invention below in conjunction with accompanying drawing.
Provided by the present invention a kind of as follows for reducing the structure of the device of tin mud generation in tin plating electrolyte preparation process:
As shown in Figure 2, described device comprises eleetrotinplate unit and tin dissolves unit, described eleetrotinplate unit comprises plating tank 10, described plating tank 10 one end is connected with the second recycle pump 9 and the 3rd valve 704 respectively by pipeline 12, described tin dissolves unit and comprises tin dissolving vessel 1, described tin dissolving vessel 1 is by pipeline 12 and oxygen supply device 3, first recycle pump 2, plating solution storage tanks 8 and the first valve 701 form closed connection, described tin dissolving vessel 1 comprises the separate chamber 101 set gradually, mixing section 102 and distributing chamber 103, the 3rd pressure warning unit 4 is provided with between described distributing chamber 103 and oxygen supply device 3, the second valve 702 is also provided with between described oxygen supply device 3 and plating solution storage tanks 8, described second valve 702 and the first recycle pump 2 are formed and are connected in parallel, under meter 13 is also provided with between described separate chamber 101 and the first valve 701.
Described plating tank 10 is connected with plating solution storage tanks 8 by pipeline 12, described second recycle pump 9 is connected with plating solution storage tanks 8 by the 4th valve 704 with after the 3rd valve 703 parallel connection, described mixing section 102 is connected with the first pressure warning unit 5, the second pressure warning unit 6 is provided with between described separate chamber 101 and the first valve 701, porous web plate 11 is provided with between described mixing section 102 and distributing chamber 103, described porous web plate 11 comprises the first web plate 1101 and the second web plate 1102, be bolted between described first web plate 1101 and the second web plate 1102, a holding bolt is established at the center of the first web plate 1101 and the second web plate 1102, 6 holding bolts are on average established by 60 ° of angles in the mid-way at web plate center to edge, so namely, ensure that compound is tight, convenient disassembly again.The installation at the second web plate 1102 edge can utilize the mounting means of original Stainless Steel Cloth.
Wherein, described second web plate 1102 is arranged at above the first web plate 1101, and described first web plate 1101 thickness is 20 ~ 30mm, and aperture is 6 ~ 8mm, and percentage of open area is 28 ~ 32%, and described second web plate 1102 thickness is 2 ~ 5mm, and aperture is greater than 0 and is less than 2.5mm.
First web plate 1101 used in the present invention and the second web plate 1102 are applied on industrial production device.
The invention provides most important parts in tin dissolving vessel 1---the design of porous web plate 11 is to ensure the tin plating electrolyte Homogeneous phase mixing more fully of tin particles in tin dissolving vessel and the oxygen be blown into and flowing, avoid the excess of oxygen of local, make tin mud generating capacity lower.Porous web plate 11 is wherein a kind of knockdown composite structures, it by two pieces independently porous web plate form.
Wherein one block of web plate, namely the first web plate 1101, is referred to as basic web plate, and its function is tin particles in carrying dissolving vessel and the weight of plating solution and high tank internal pressure.Therefore this web plate must have certain thickness.Experience tells us, its thickness at 20 ~ 30mm, in order to easy to process hole can be opened larger, the diameter in hole is generally at 6 ~ 8mm, and its percentage of open area is inevitable very large, generally 28 ~ 32%, be the porous web plate belonging to low pressure drop.
Other one piece, i.e. the second web plate 1102, can be referred to as " stable and uniform mixing web plate ", owing to not needing load capacity, the thickness of plate can be thinner, and its function is the requirement that the percentage of open area formed after it and basic web plate (i.e. the first web plate 1101) compound should reach Critical Stability percentage of open area.Because the diameter of tin particles is generally at about 3mm, therefore the aperture of the second web plate 1102 must be less than 2.5mm, drains in distributing chamber 103 to prevent tin particles.Hole due to this web plate is smaller and intensive, and add and web plate can be caused man-hour to be out of shape warpage, therefore this web plate again can not be too thin, thickness of slab generally at 2 ~ 5mm, to machine rear to be indeformablely as the criterion.
Wherein above-mentioned two blocks of web plates must closely be combined with each other in tin dissolving vessel.If because have space therebetween, percentage of open area will change, and the good Homogeneous phase mixing state of whole tank will change.Meanwhile, the space between two blocks of plates can be blocked by tin mud.The realization of the Critical Stability percentage of open area of the porous web plate 11 after compound ensures tin particles unrestricted flow in tin dissolving vessel, key well-mixed with the plating solution containing dissolved oxygen.The present invention is through verification experimental verification, and when tin particles diameter is 2.5 ~ 3mm, its Critical Stability percentage of open area is 4 ~ 15%.
Reach low tin mud amount, the porous web plate only had is inadequate, good porous web plate can only avoid the oxygen excess of regional area, it also needs to be coordinated by the inexcessive of overall oxygen, therefore, the invention provides the method that another prevents oxygen excessive, it does not need loaded down with trivial details control method, different from the method for patent documentation 2,3, the present invention ensures the inexcessive of oxygen with the excessive of tin particles amount.The amount that the present invention introduces one " oxygen blast intensity " instructs the control to tin particles weight, described " oxygen blast intensity ", namely 1 ton of metallic tin grain correspondence is blown into how many amount of oxygen (unit is mark Nl/min, i.e. Standard Liters per Minute), when tin particles weight is greater than the tin particles weight that use " oxygen blast intensity " value calculates, the generating capacity of tin mud is minimum.For MSA plating solution, at molten tin pressure 0.6 ~ 0.8MPa, bath flow rate 100 ~ 150mm/s in mixing section, the tin particles weight in mixing section should control by being greater than the tin particles amount that 50 ~ 100Nl/min.t calculates.Namely
The tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in mixing section
Meanwhile, the present invention is the control method of the low tin mud loss based on insoluble anode MSA plating solution, prepares in tin plating electrolyte process, and the generation of proportioning on tin mud of the various components of MSA plating solution (i.e. metilsulfate plating solution) plays very large impact.The solution additive that the present invention adopts is commodity TP-G7, must meet following component proportion condition and can obtain the loss of low tin mud in tin process processed.
| Item controlled | Span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
In upper table, total acid (with MSA content meter), actual is exactly the content of MSA, the saying of " with MSA content meter " is the expression method in electroplating industry, methylsulphonic acid in plating solution occurs with two kinds of forms, be the tin methane sulfonate combined with tin ion, a kind of is free methylsulphonic acid in the plating solution, so what emphasize here to control is total acid.
Provided by the present invention a kind of reduce the method for tin mud generation in tin plating electrolyte preparation process step and principle as follows:
(A), in mixing section 102 add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is 300 ~ 1000Nl/min, and oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted tin dissolving vessel 1, oxygen is blown in distributing chamber 103 according to the oxygen amount of being blown in step (A) and oxygen blast intensity and mixes with plating solution, the plating solution being mixed with oxygen enters mixing section 102 through porous web plate 11, dissolve the tin particles in mixing section 102, form tin plating electrolyte, finally, the tin plating electrolyte of generation discharges tin dissolving vessel 1 from separate chamber 101 top exit;
(C) the numerical value P in the first pressure warning unit 5, is observed
1, numerical value P in the second pressure warning unit 6
2and the flow velocity numerical value under meter 13, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate 1101 constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate 1102, making the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally making tin particles and plating solution reach Homogeneous phase mixing state.
The diameter of described tin particles is 2.5 ~ 3mm, and described Critical Stability percentage of open area is 4 ~ 15%, and the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.In described mixing section, tin particles add-on scope is 5 ~ 8 tons.The effect of described 3rd valve 703 is the flows regulating plating solution in electroplating process, and the effect of the second valve 702 is the flows regulating plating solution in molten tin process.
Wherein, along with the increase of flow velocity, the corresponding increase of flow pressure drop in mixing section 102, when flow velocity reaches a certain value, now, actionless tin granulosa starts vibrations, then has small expansion, pressure drop in mixing section 102 slightly declines, and tin particles layer becomes the loose state mixed with plating solution by the state-transition compressed; Along with flow velocity increases gradually, the tin grain in tin particles can move freely, until do irregular random motion; Along with the further increase of flow velocity, whole tin particles layer demonstrates the feature of some liquid character; Along with tin intergranular is apart from expanding, tin particles layer expands further.The flow velocity when state of tin particles layer is flow state by the condition conversion compressed is called critical Homogeneous phase mixing speed.Actual conversion process, due to the heterogeneity of tin grain granularity and the heterogeneity of filling operation, even if lower than the speed of stagnation point, the turbulence of local tin particles layer will occur, along with the increase of flow velocity, be further development of the uneven mixing in hole, local, even under tin particles layer can be made to be in mixed uniformly flow velocity, still can there is not mixed uniformly particular in tin particles layer.Therefore, in systems in practice, critical Homogeneous phase mixing point is then without the meaning of absolute clarity, and the process of just fuzzy gradual change, and different according to condition difference.
Effect and the principle of design of porous web plate 11 provided by the present invention are as follows:
A porous web plate 11 is set between distributing chamber 103, mixing section 102, its effect: one is be uniformly distributed along the section of tin particles layer by plating solution to enter, and with tin grain uniform contact, forms uniform admixture; Two is play supporting role to tin grain, eliminates the unstable of system; Three is resist extraneous interference, the malignant development that restriction is unstable.Porous web plate 11 is important guarantees of the uniform and stable flowing of tin particles in mixing section 102.Porous web plate 11 action principle makes plating solution along the reallocation of tin particles layer section by " throttling " exactly, plating solution along degree of uniformity and the web plate of tin particles layer Latitudinal section throttle degree and on the characteristic of tin particles layer relevant.Usually assess with the drooping characteristic of plating solution by web plate and tin particles layer, the real-time percentage of open area α of pressure drop Δ P and web plate, namely the web plate perforate total area accounts for the percentage ratio % of the cross-sectional area of tin particles layer, plating solution by the height H of the voidage ε of the apparent velocity U of tin particles layer, tin particles layer, tin particles layer, plating solution by resistance coefficient ξ, Teeth granule density ρ in web plate aperture
s, fluid density ρ
frelevant.
The stagnation pressure of system is reduced to:
A mistake! Do not find Reference source.ε
mf) (mistake! Do not find Reference source.) (
a mistake! Do not find Reference source.m
Wherein, porous web plate have high pressure drop web plate and low pressure drop web plate point, by the relation of the total pressure drop of different web plate tin particles layer and apparent velocity as shown in Figure 1, for high pressure drop web plate, namely real-time percentage of open area α is less than Critical Stability percentage of open area α to plating solution
csweb plate, its stagnation pressure reduces to the single-valued function of bath flow rate, and tin particles lamination falls only relevant with tin particles layer thickness, for given pressure drop, tin particles layer only correspond to a flow velocity determined, namely flow velocity is equal everywhere for tin particles layer, namely reaches the admixture of stable and uniform.But for low pressure drop web plate, namely percentage of open area α is greater than Critical Stability percentage of open area α in real time
csweb plate, have three states in tin particles layer, the A point crossing with fixed pressure drop line, local tin particles layer shows as the fixing tin particles of low gas velocity; Intersection points B, local tin particles layer shows as good Homogeneous phase mixing; Intersection point C, local tin particles layer is in lower jet flow, i.e. local fountain tin particles at a high speed.This flow state has unstable, and it can collapse into the fixing tin particles layer in local and local channel, and tin particles layer loses good Homogeneous phase mixing completely, and this is completely undesirable.
In the step (C) of method provided by the present invention, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, whether tin particles is in mixed uniformly state, and namely according to contrasting with the curve in Fig. 1, thus confirm by after porous web plate 11 percentage of open area of current setting, whether tin particles is in mixed uniformly state.
In the step (D) of method provided by the present invention, if tin particles is not in Homogeneous phase mixing state, then repeating step (A) ~ (C), by keeping the percentage of open area of the first porous web plate 1101 constant, adjust the percentage of open area of the second porous web plate 1102, and then the percentage of open area of adjustment porous web plate 11, make the percentage of open area of porous web plate 11 reach Critical Stability percentage of open area, the α namely shown in Fig. 1
cS(Critical Stability percentage of open area).Thus effectively reduce the growing amount of tin mud.
The advantage of high pressure drop web plate is to ensure good Homogeneous phase mixing state, but causes dynamic consumable increase, and uneconomical; Although the consumption of low pressure drop web plate kinetic energy is lower, it can cause tin particles layer normally not mix.Can know by inference, certainly exist one and can ensure that tin particles layer stable and uniform flows, the rational web plate of kinetic energy consumption simultaneously, the i.e. percentage of open area of the web plate that existence one is suitable.We are referred to as Critical Stability percentage of open area.Its condition is
A mistake! Do not find Reference source.=0
Under this condition, when the flow velocity of plating solution is increased gradually by little, plating solution increases gradually by the pressure drop of tin particles layer is corresponding, when reaching a certain flow velocity, tin particles layer starts to expand, tin particles starts flowing, now, the weight of tin particles by plating solution to the drag force of tin particles and buoyancy balance, when increasing flow velocity further, the corresponding increase of the drag force that tin particles is subject to, the movement of the tin grain in tin particles layer makes tin particles layer expand further, tin particles stressor layer gradient reduces, but the total pressure drop of tin particles layer remains unchanged.The curve that tin particles layer pressure drop bath flow rate increases will be level by rising transition, and the bath flow rate corresponding to its flex point is minimum good Homogeneous phase mixing speed, and this is also the economic velocity that we pursue.
The percentage of open area of theoretical accurate calculation web plate is more difficult, a lot of metallic tin dissolving vessels calculate incorrect and cause tin particles layer can not form good Homogeneous phase mixing state due to web plate percentage of open area, patent documentation 1, Unexamined Patent 3-No. 180493 publications propose to metallic tin particle carry out mechanical stirring be exactly web plate in metallic tin dissolving vessel a suitable good Homogeneous phase mixing state cannot be provided a solution.Its objective is by mechanical stirring, make that tin particles and plating solution are full and uniform to be mixed, to accelerate the dissolution rate of tin, solve the situation that local exists excess of oxygen, thus reduce the generating capacity of tin mud.This method increase facility investment, meanwhile, when tin particles dissolving vessel have very large pressure, agitator turning axle just seems very important through the dynamic seal at dissolving vessel position, and under continuous duty, the reliability of normal work is difficult to ensure.The agitator increased too increases the extra consumption of the energy.
Therefore, method of the present invention is when not increasing extras and energy consumption, there is provided the design of a porous web plate to ensure that the tin particles in tin dissolving vessel can be in desirable good Homogeneous phase mixing state, thus make tin particles in dissolving vessel, be in a kind of free-pouring state, fully mix with the plating solution containing dissolved oxygen, avoid the excess of oxygen of local, make tin mud generating capacity lower.
The percentage of open area of porous web plate 11 provided by the present invention, is Critical Stability percentage of open area.
The realization of Critical Stability percentage of open area ensures tin particles unrestricted flow in dissolving vessel, key well-mixed with the plating solution containing dissolved oxygen.Because the present invention is a set of assembly reticular lamina, " stable and uniform mixing web plate " (i.e. second web plate 1102) on it can be dismantled very easily, as long as change the percentage of open area of " stable and uniform mixing web plate ", just can obtain the percentage of open area of new assembly reticular lamina.We know, high pressure drop web plate can ensure good Homogeneous phase mixing state, and shortcoming is consumable increase.Therefore we can just install the combination porous web plate thinking oneself as high pressure drop first time, in actual moving process, by being arranged on the upper and lower pressure warning unit of mixing section (as the first pressure warning unit 5, second pressure warning unit 6), under meter 13 observed and recorded data, mapping obtains the curve of similar Fig. 1, thus accurately can determine whether the tin particles that this web plate causes is in mixed uniformly state.So that the percentage of open area constantly improving " stable and uniform mixing web plate " reaches the good Homogeneous phase mixing state of best Critical Stability.The present invention is through verification experimental verification, and when tin particles diameter is 2.5 ~ 3mm, its combined type porous web plate 11 Critical Stability percentage of open area is 4 ~ 15%.Be less than 4%, although good Homogeneous phase mixing state can be ensured, cause dynamic consumable increase, and uneconomical; Be greater than 15%, although kinetic energy consumption is lower, it can cause, and tin particles layer can not with oxygen and tin plating electrolyte be full and uniform mixes.
But, the porous web plate 11 with Critical Stability percentage of open area is only provided, the tin particles layer in tin dissolving vessel can only be made to be in the state of suspension, thus ensure tin particles and plating solution the contacting with each other cmpletely containing dissolved oxygen, the oxygen excess of local can not be formed.Make tin mud generating capacity lower, also must accomplish that oxygen is inexcessive in whole tin process processed.
Patent documentation 2: Unexamined Patent-No. 131399 publication proposes to supply to the metallic tin particle in mixing section the method that dissolved oxygen is the electroplate liquid of below 300ppm, its essence is exactly for certain tin particles amount, ensures that the aggregate level of oxygen is inexcessive with low oxygen-supply quantity.Its shortcoming is when high tin coating produced by needs, and the molten tin ability of the method is unable to catch up with the spending rate of tin ion in plating solution, and production cannot normally be carried out.And patent documentation 3:CN1993502A provides is controlled by tin ion concentration between target bound, thus make tin ion formation speed close to the average predetermined spending rate of tin ion, thus can reduce the method for the generation of tin mud.The method of patent documentation 3 can not change for certain tin particles amount, when the dissolved oxygen supplied is the electroplate liquid of more than 300ppm, may occur the phenomenon that tin mud amount increases.When high tin coating produced by needs, although the molten tin ability of the method can catch up with the spending rate of tin ion in plating solution, now will inevitably occur the phenomenon that tin mud amount increases, only the method can accomplish accurate control, thus reduces tin mud generating capacity.The starting point of above-mentioned two patent documentations is all to avoid the generation of excess of oxygen in molten tin process, and so-called excess of oxygen is exactly that the add-on of oxygen has exceeded tin particles total amount in dissolving vessel and may be dissolved as the amount of oxygen required for tin ion.Above-mentioned patent is all find one's way out from the oxygen amount how controlling to add.
The present invention is the method proposing solution from other angle.Method of the present invention is:
The add-on of tin particles in mixing section is increased, and with excessive tin particles, under ensureing maximum molten tin rate behavior, oxygen also can not be excessive.
For MSA plating solution, the principal reaction process that tin particles dissolves in dissolving vessel is as follows:
1.2Sn+O
2+4H
+→2Sn
2++2H
2O
2.Sn+O
2+4H
+→Sn
4++2H
2O
3.2Sn
2++O
2+4H
+→2Sn
4++2H
2O
4.Sn
2++2MSA→Sn(MSA)
2
5.Sn+Sn
4+→2Sn
2
As can be seen from 5 formulas, tin or a kind of well reductive agent, therefore excessive tin not only can ensure that oxygen is inexcessive, meanwhile, can reduce tetravalent tin ion.In the presence of excess amounts of tin, can accomplish that the tin mud produced is lower.
Thus, the amount that the present invention introduces one " oxygen blast intensity " instructs the control to tin particles weight.Its 1 ton of metallic tin grain correspondence is blown into how many amount of oxygen (unit is standard liter/min), and when tin particles weight is greater than the tin particles weight that use " oxygen blast intensity " value calculates, the generating capacity of tin mud is minimum.For MSA tin plating electrolyte, at molten tin pressure 0.6 ~ 0.8MPa, bath flow rate 100 ~ 150mm/s in mixing section, the tin particles weight added should control by being greater than the tin particles amount that 50 ~ 100Nl/min.t calculates.Namely
The tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in tin ion dissolving vessel
Actually operating in large production is as control benchmark by the oxygen amount of being blown into required for the tin ion spending rate corresponding to the maximum tin coating weight in covering 80% product, calculate tin particles weight, that is tin process processed has 80% to be in stable process, just need the tonnage increasing tin particles in tin ion dissolving vessel when only having the tin coating weight when product to be greater than above-mentioned value, thus keep the excessive of tin particles constantly.In described mixing section, tin particles add-on scope is 5 ~ 8 tons.
The present invention is the control method of the low tin mud loss based on insoluble anode MSA plating solution.Very large effect is played in the generation of proportioning to tin mud of the various components in tin process processed.The solution additive that the present invention adopts is commodity TP-G7, also has a kind of additive that can be used for insoluble anode MSA plating solution to be commodity TP-H in addition.Following component proportion condition must be met can obtain low tin mud loss in tin process processed.
| Item controlled | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
For tin plating electrolyte of the present invention, the target of tin process processed makes the divalent tin ion concentration in work tin plating electrolyte remain on 15 ± 3g/l.Divalent tin ion in MSA tin plating electrolyte exists with the form of tin methane sulfonate.In the process of tin processed, when metallic tin particle runs into oxygen, its surface will generate tin protoxide, and as can be seen from above-mentioned reaction formula, tin protoxide can react with MSA plating solution the tin methane sulfonate generating us and need.Also can generate stannic oxide with the reaction of excessive dissolved oxygen, therefore, the total acidity of tin process processed being remained on a higher level is reduce an important means of tin mud generation.Therefore, we control with total acid in tin process processed.
Organic additive TP-G7 is compared with the additive of other trades mark, and itself just has the feature of low tin mud loss, in system of the present invention, as long as just can obtain the actual result of low tin mud loss in above-mentioned span of control.
Antioxidant just can play oxidation resistant effect when only reaching the amount of above-mentioned span of control.Be greater than above-mentioned controlling valu, can not effect be increased.
Provide a kind of embodiment reducing the method for tin mud generation in tin plating electrolyte preparation process provided by the present invention below:
Embodiment 1
A plating solution capacity be 45l for reducing tin plating electrolyte preparation process in tin mud generation device on test.Observe the numerical value P in the first pressure warning unit
1, numerical value P in the second pressure warning unit
2and the flow velocity numerical value under meter, according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determine the percentage of open area of described porous web plate, keep the percentage of open area of the first web plate 1101 constant, by regulating the percentage of open area of the second web plate 1102, obtain the percentage of open area of required porous web plate 11, this device carries out the comparative example that different percentage of open area, different MS A bath system and additive select the test of the tin metal particle of the two kinds of different trade mark TP-G7 or TP-H and different add-on, each test period is 1 hour, the oxygen amount of being blown into is 0.6l/min, and oxygen pressure is 0.6MPa.The additive trade mark that sequence number 1,2 adopts is TP-H, and concentration is respectively 27ml/l and 33ml/l, and the additive trade mark that sequence number 3 ~ 5 adopts is TP-G7, and concentration is respectively 15ml/l, 29ml/l and 35ml/l.Sequence number 1,4 to be percentage of open area be 27.5% porous web plate above be covered with one deck Stainless Steel Cloth, the combined type porous web plate that sequence number 2,3,5 is respectively provided by the invention, percentage of open area is 4%, 6.2% and 14%.In sequence number 1 ~ 5, the concentration of total acid is followed successively by 65ml/l, 58ml/l, 71ml/l, 73ml/l and 75ml/l.In sequence number 1 ~ 5, the concentration adding antioxidant is followed successively by 15ml/l, 16ml/l, 18ml/l, 22ml/l and 25ml/l.Concrete outcome sees the following form:
As seen from the above table, when adopting the MSA electroplate liquid formulation of TP-G7 trade mark additive, add low combined type porous web packing free ratio, the percentage of open area namely in 4% ~ 15% scope, and high tin particles add-on just can obtain low tin wastage rate.Here the percentage of open area of porous web plate arranges effect is the most obvious.
Embodiment 2
On the big scale production equipment of annual output 200000 tons of tin plates, need 80m
3tin plating electrolyte carry out cycle operation.It has an internal diameter to be about the tin dissolving vessel of 1m, on one block of porous web plate, be covered with one deck Stainless Steel Cloth, stops that tin particles drops to the effect in distributing chamber to play.The method improved is that porous web plate is made combined type web plate, and retain original porous web plate constant, the percentage of open area of porous web plate is originally 27.5%.Reprocess one block of thin web plate (i.e. the second web plate 1102) in addition, the Critical Stability percentage of open area percentage of open area after compound being reached measure in laboratory.Percentage of open area after compound is 6.1%, has been significantly less than original value.In order to reach the effect of tight compound, bolted method can be used, establishing a holding bolt at the center of web plate, on average establish 6 holding bolts in the mid-way at web plate center to edge by 60 ° of angles, so namely ensure that compound is tight, convenient disassembly again.The installation of newly-increased web edge can utilize the mounting means of original Stainless Steel Cloth.Improvement is in addition the tin particles amount added, and can attempt being increased to 8 tons from original 4 tons always, if the height of mixing section does not increase, the tin particles of 8 tons may be gone in separate chamber in tin process processed, and tin grain can be made to discharge tin dissolving vessel.Need to determine whether newly do tin dissolving vessel by practical operation situation.
This equipment runs MSA bath system, and the trade mark using additive is TP-G7, needs the component proportion according to the form below operation controlled during molten tin
| Item controlled | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
Solution presasure controls at 6kg/cm
2, the tin particles amount in dissolving vessel regulates according to the tin ion meltage needed for producing and blowing oxygen quantity, and that the tin coating weight that the product of this unit 80% covers is maximum is 5.6g/m
2.The corresponding maximum oxygen amount of being blown into required for tin ion spending rate is 300Nl/min, oxygen blast intensity calculates with 65 liters/min of tons, tin particles add-on controls at about 5 tons, namely according to formula: the tin particles add-on > oxygen amount of being blown into ÷ oxygen blast intensity in tin ion dissolving vessel, tin particles add-on is determined.Namely unit is when producing lower tin coating weight coating, as long as turn down blowing oxygen quantity, the tin particles weight in molten tin can keep 6 tons constant.If desired 5.6g/m is produced
2during tin plate, need the oxygen passed into will be increased to 400Nl/min and just can catch up with tin ion spending rate, at this moment need in advance tin particles weight to be increased to more than 6 tons.Run in such a mode, the per-cent that in tin waste and tin mud, the content of tin accounts for the usage quantity of total tin metal remains on about 1% all the year round.
Embodiment 3
Device after above-mentioned improvement carries out out cylinder operation with MSA, make open cylinder liquid requirement be generate to meet the tin plating electrolyte of production requirement tin ion content within the shortest time, namely open tin ion in cylinder liquid from 0.The trade mark using additive is TP-G7, needs the component proportion according to the form below operation controlled during molten tin
| Item controlled | Aimed concn and span of control | Unit |
| Total acid (with MSA content meter) | 70±5 | ml/l |
| Additive TP-G7 | 30±5 | ml/l |
| Antioxidant | 20±5 | ml/l |
Solution presasure controls at 8kg/cm
2, the tin particles amount in dissolving vessel is 8 tons, and in order to meet the requirement of tin processed fast, the oxygen amount of being blown into is 1000Nl/min, and oxygen blast intensity reaches 120 liters/min of tons, has been in the degree of excess of oxygen, and tin mud generating capacity will inevitably increase to some extent.Run 2 hours in such a mode, just make 80m
3the tin ion opened in cylinder liquid reaches 12.5g/l from 0.Open cylinder complete after tin mud only 0.3582g/l in plating solution.The per-cent that the content being converted to tin in tin waste and tin mud accounts for the usage quantity of total tin metal is 1.72%.Still the waste of same type units is significantly less than.
Claims (9)
1., for reducing a device for tin mud generation in tin plating electrolyte preparation process, described device comprises eleetrotinplate unit and tin dissolves unit,
Described eleetrotinplate unit comprises plating tank (10), and described plating tank (10) one end is connected with the second recycle pump (9) and the 3rd valve (704) respectively by pipeline (12);
Described tin dissolves unit and comprises tin dissolving vessel (1), described tin dissolving vessel (1) forms closed connection by pipeline (12) and oxygen supply device (3), the first recycle pump (2), plating solution storage tanks (8) and the first valve (701), described tin dissolving vessel (1) comprise set gradually separate chamber (101), mixing section (102) and distributing chamber (103);
Described plating tank (10) is connected with plating solution storage tanks (8) by pipeline (12), be connected with plating solution storage tanks (8) by the 4th valve (704) after described second recycle pump (9) is in parallel with the 3rd valve (703), it is characterized in that:
Be provided with porous web plate (11) between described mixing section (102) and distributing chamber (103), described porous web plate (11) comprises the first web plate (1101) and the second web plate (1102),
Described second web plate (1102) is arranged at the first web plate (1101) top, described first web plate (1101) thickness is 20 ~ 30mm, aperture is 6 ~ 8mm, percentage of open area is 28 ~ 32%, described second web plate (1102) thickness is 2 ~ 5mm, and aperture is greater than 0 and is less than 2.5mm.
2. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, is characterized in that being provided with the 3rd pressure warning unit (4) between described distributing chamber (103) and oxygen supply device (3).
3. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, it is characterized in that described mixing section (102) is connected with the first pressure warning unit (5), be provided with the second pressure warning unit (6) between described separate chamber (101) and the first valve (701), between described separate chamber (101) and the first valve (701), be also provided with under meter (13).
4. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, it is characterized in that also being provided with the second valve (702) between described oxygen supply device (3) and plating solution storage tanks (8), described second valve (702) and the first recycle pump (2) are formed and are connected in parallel.
5. a kind of device for reducing tin mud generation in tin plating electrolyte preparation process according to claim 1, is characterized in that: be bolted between described first web plate (1101) and the second web plate (1102).
6. application rights requires that the device described in 1 reduces a method for tin mud generation in tin plating electrolyte preparation process, it is characterized in that: described method comprises the steps:
(A), in mixing section (102) add tin particles, the add-on of described tin particles is determined by the following method:
The add-on > oxygen amount of the being blown into ÷ oxygen blast intensity of tin particles in mixing section
In above formula, the oxygen amount of being blown into is
oxygen blast intensity is 65 ~ 120L/mint;
(B), plating solution is inputted tin dissolving vessel (1), oxygen is blown in distributing chamber (103) according to the oxygen amount of being blown in step (A) and oxygen blast intensity and mixes with plating solution, the plating solution being mixed with oxygen enters mixing section (102) through porous web plate (11), dissolve the tin particles in mixing section (102), form tin plating electrolyte, finally, the tin plating electrolyte of generation discharges tin dissolving vessel (1) from separate chamber (101) top exit;
(C) the numerical value P in the first pressure warning unit (5), is observed
1, numerical value P in the second pressure warning unit (6)
2and the flow velocity numerical value under meter (13), according to pressure reduction, i.e. P
1-P
2value, and flow velocity numerical value, determines whether tin particles is in mixed uniformly state;
(D), keep the percentage of open area of the first web plate (1101) constant, then repeating step (A) ~ (C), by adjusting the percentage of open area of the second web plate (1102), make the percentage of open area of porous half tone 11 reach Critical Stability percentage of open area, finally make tin particles and plating solution reach Homogeneous phase mixing state.
7. a kind of method reducing tin mud generation in tin plating electrolyte preparation process according to claim 6, it is characterized in that: the diameter of described tin particles is 2.5 ~ 3mm, described Critical Stability percentage of open area is 4 ~ 15%, the scope of described pressure reduction is 0.48 ~ 0.50MPa, and the scope of described flow velocity numerical value is 2.35 ~ 2.50m
3/ h.
8. a kind of method reducing tin mud generation in tin plating electrolyte preparation process according to claim 6, it is characterized in that: described plating solution is metilsulfate plating solution, described metilsulfate plating solution comprises following component: methylsulphonic acid salt concn 65 ~ 75ml/l, additive concentration 25 ~ 35ml/l, antioxidant concentration 15 ~ 25ml/l.
9. a kind of method reducing tin mud generation in tin plating electrolyte preparation process according to claim 6, is characterized in that: in described mixing section, tin particles add-on scope is 5 ~ 8 tons.
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| CN106149017B (en) * | 2016-08-29 | 2019-03-05 | 首钢京唐钢铁联合有限责任公司 | A kind of pre-galvanized system of methane sulfonic acid electrotinning |
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|---|---|---|---|---|
| CN1107524A (en) * | 1993-11-27 | 1995-08-30 | Sms舒路曼-斯玛公司 | Apparatus for solving zinc by using of electrolyte of acid containing liquid |
| KR20010063655A (en) * | 1999-12-23 | 2001-07-09 | 신현준 | Tin electroplating process using insoluble anode for the metal strip |
| CN1993502A (en) * | 2004-08-05 | 2007-07-04 | 新日本制铁株式会社 | Method of electric tinning |
| CN102586851A (en) * | 2011-01-06 | 2012-07-18 | 宝山钢铁股份有限公司 | Electrolytic method for relieving and reducing tin sludge generated in tin plating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931699A (en) * | 1995-07-21 | 1997-02-04 | Kawasaki Steel Corp | Electro tin plating method using insoluble anode |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107524A (en) * | 1993-11-27 | 1995-08-30 | Sms舒路曼-斯玛公司 | Apparatus for solving zinc by using of electrolyte of acid containing liquid |
| KR20010063655A (en) * | 1999-12-23 | 2001-07-09 | 신현준 | Tin electroplating process using insoluble anode for the metal strip |
| CN1993502A (en) * | 2004-08-05 | 2007-07-04 | 新日本制铁株式会社 | Method of electric tinning |
| CN102586851A (en) * | 2011-01-06 | 2012-07-18 | 宝山钢铁股份有限公司 | Electrolytic method for relieving and reducing tin sludge generated in tin plating solution |
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