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Glue Analysis and Behavior in Copper Electrolyte

V.K. BLECHTA, Z.Z. WANG, and D.W. KRUEGER Animal glue in combination with other chemicals is often used as a leveling agent in the copper electroplating industry. The control of the glue concentration in the electrolyte is critical to the quality of copper produced. A quantitative galvanostatic technique for glue analysis in copper electrolyte containing lignin sulfonate and C1- was developed. The kinetics of glue hydrolysis in industrial electrolytes was studied and found to follow first-order reaction kinetics, with sulfuric acid acting as a catalyst. The dependence of the glue hydrolysis rate constant on temperature follows the Arrhenius equation. By adding fresh glue to the electrolyte, the glue activity first rises and then falls. This effect can be explained by the presence of long-chain molecules in the glue which are less active but hydrolyze into the more active medium-sized molecules. A mathematical model of this process shows good agreement with experimental data. The bulk of the electrolyte flow in the INCO commercial electrolytic plating cell bypasses the electrodes, probably across the bottom of the cell. The electrolyte circulation between electrodes is not very intense. A simple equation for the glue concentration calculation in the cell inlet and outlet, depending on the glue addition rate, was derived.

I.

INTRODUCTION

G L U E has been used as an addition agent in electrorefining electrolytes for a long time. Usually, glue is used in combination with other addition agents, such as chloride, thiourea, alkyl sulfonate, and or lignin sulfonate. At the INCO Copper Refinery, a combination of three addition agents is used: chloride, glue, and Tembind (lignin sulphonate produced by Tern fibre Inc. of Temiskaming, PQ, Canada). It is common knowledge that there is an optimum glue concentration which has to be maintained and controlled in the electrolyte. There are several electrochemical techniques described in the literature which are used for glue analysis. The Kennecott procedure uses cyclic voltammetry, tjl This technique was later extended for analysis of both thiourea and glue. I2j Norddeutsche Affinerie (Hamburg, Germany) developed a procedure for continuous glue analysis in electrolyte using a moving copper cathode.13] Noranda Inc. (Montreal) developed a method for glue analysis consisting of two steps: the glue is first separated by a molecular filtration from electrolyte and then determined by overpotential measurement at constant current, tS] Just recently, after the first manuscript of this article was written, Saban e t al. t6j published an article where the kinetics of glue degradation in water and in electrolyte was measured by size-exclusion chromatography. The authors found that the kinetics of glue degradation can be correlated by an equation: 1/(Mn), = 1/(Mn)0 + k ' t "where (Mn), and (Mn)0 are number-average molar mass at time t and at time zero, respectively; k' = k [ A ] / ( M n ) o
V.K. BLECHTA, formerly Section Leader of Process Technology, INCO Limited, is retired. Z.Z. WANG, formerly Research Scientist, INCO Limited, is Researcher, Laurentian University, Sudbury, ON, Canada. D.W. KRUEGER, Superintendent of Process Technology, is with INCO Limited, Copper Refinery, Copper Cliff, ON, Canada POM 1N0. Manuscript submitted August 26, 1992. METALLURGICAL TRANSACTIONS B

is the observed degradation rate constant [rnin -1] in which [A] is the concentration of the catalyst (sulphuric acid) and k is the intrinsic degradation constant." Beginning in 1986, cyclic voltammetry was used for glue analysis at the INCO Copper Refinery. [4] This technique was not sensitive enough and was only able to distinguish between low and high glue concentration in electrolyte. In 1990, cyclic voltammetry was abandoned and a new, quantitative, galvanostatic technique was developed and has been used since for routine glue analysis and control. II, G A L V A N O S T A T I C T E C H N I Q U E F O R G L U E ANALYSIS Figure 1 shows the principle of the technique. A constant current is applied between a copper anode and a platinum cathode in the electrolyte to be measured. The potential between the cathode and copper reference electrode is then recorded. Figure 2 shows such a potentialtime profile at different glue concentrations. The difference in potential at 2.5 minutes and at 0.1 minute of plating, the so-called potential shift (PS), is then recorded and is proportional to the glue content. The highest sensitivity was obtained at a current density of 300 A / m 2 and at a temperature of 65 ~ The PS is then plotted vs glue content, and a typical "S" curve is obtained (Figure 3). Constants for a third-order polynomial best-fit equation are then calculated, recorded, and used for the glue analysis calculation. After each overpotential measurement, the platinum cathode is cleaned by current reversal. The constants and the position of the calibration curve are dependent on the electrolyte copper content and on the electrolyte background, e . g . , organic degradation products, acid concentration, CI' content, e t c . , which affect the cathode potential (Figure 3). Usually several calibration curves, using electrolytes with different copper content, are generated. To eliminate the effect of background, plant electrolyte is used for calibration curves. It is heated at 95 ~ for 1.5 hours to decompose all of
VOLUME 24B, APRIL 1993--277

4,

Constant current
generator

O"
Voltage recorder

f
I I I

Pt cathode

Cuanoe t
Fig. 1--Cell for galvanostatic measurements.
Cathode potential, mV
- 120

the glue present and then doped with increasing amounts of glue. The effect of nickel and sulfuric acid concentration on the calibration curve is negligible and is usually included in the background (Figures 4 and 5). The Tembind (lignin sulfonate) is itself a cathode polarizing agent. However, in combination with glue, Tembind significantly decreases the glue polarization effect (Figure 6). The Tembind concentration in our electrolyte fluctuates in the range 168 + 14 mg Tembind/L. In this range, the effect on glue polarization is small and is included in the background. Reproducibility of the galvanostatic technique which was developed, including three different glue preparations and three different plant electrolytes in a span of 14 days, is 25 -+ 1.3 mV or, expressed in glue concentration, 5.0 - 0.2 mg/L.

./Cu

reference electrode

III.

KINETICS OF GLUE DECOMPOSITION

Once a technique for glue analysis became available, the kinetics of glue decomposition in electrolyte was investigated. Glue is known to be a long-chain protein which is split by hydrolysis into shorter molecules and finally to amino acids. The hydrolysis is carried out in aqueous
Glue, mg/L
10
8 Potential Shift, mV

-100

7
6

70 6050 40 30 20 ~ P"

-80

5 4

-60

-40

-20

2 Time, rain

10 0 I
0

I
2

I
4

I
6

I
8

Fig. 2--Potential-time profile at different glue concentrations.

i/L v 27 g Ni/L I 10

Glue concentration, mg/L

Fig. 4--Effect of nickel concentration on calibration curve.


Glue, mg/L
9 8 Potential Shift, mV

70 7
6 5 4

60
50
-

~~
~ ' ~
I 0 I 2 I I 4 6 Glue concentration, mg/L O 100 g H2SO4/L V 200 g HzSO4/L I I 8 10

40 i

2
1 10 ~

~
~'

/ /

9 95g c~/L o~gC~L


G l u e = a + b . (PS) + c . (ps)2+ d ' ( P S ) 3
I I I I I I

30 20 ~
10 -

20

30

40 50 Potential Shift (PS)

60

70

80

Fig. 3--Standard calibration curve for electrolyte from electrorefinery. 278--VOLUME24B, APRIL1993

Fig. 5--Effect of sulfuric acid concentration on calibration curve. METALLURGICAL TRANSACTIONSB

Potential

Shift, mV

7O

'I
95% of plant electrolyte
samples are

Ln of glue concentration 2.0

Plant electrolyte

.~.5 I

60 1.0 50

0.5

,,=in this range=. 0 40 0 50 100 150 Tembind, mg/L 200 250 -0.5
I I ...... I I

Fig. 6 - - E f f e c t of Tembind on glue polarization.

3 Time, h

Fig. 7 - - K i n e t i c s of glue decomposition.

medium and should, therefore, follow first-order reaction kinetics with respect to the glue concentration.
dC /dt = -kC

[1]

Ln of kinetic constant 0 -1 -2! -3

Arrhenius plot

where c = concentration of active component; k = kinetic constant; and t = time. By integration, we arrive at In C = In Co - kt [2]

where Co is the concentration of active component at t=0. By plotting the logarithm of the glue concentration vs elapsed time, a linear relationship should be obtained. The results of glue hydrolysis in a plant electrolyte at 65 ~ are shown in Figure 7. It can be seen that, indeed, glue hydrolysis follows first-order reaction kinetics. The slope o f the line is the kinetic constant k. Similar kinetic measurements were repeated at 25 ~ 55 ~ and 75 ~ and the rate constants were calculated. By plotting the logarithm of rate constant vs the reciprocal value of the absolute temperature, a straight-line relationship was obtained (Figure 8). This shows that the change of the rate constant with temperature follows the Arrhenius equation. The kinetics o f glue decomposition was also measured at different sulfuric acid contents in the electrolyte. Figure 9 shows that a straight-line relationship between sulfuric acid concentration and the rate constant was obtained. This indicates that sulfuric acid acts as a catalyst for the glue hydrolysis.

o Experimental points Best fit line ,, I t I I I -6 0.0030 0.0032 0.0028 Reciprocal of absolute temperature, K -1 -5
--

0.0034

Fig. 8 - - G l u e hydrolysis rate constant vs temperature.

Rate constant, 1/h 0.6 Temperature, 65"C 0.5

0.4

0.3

0.2 140

150

IV. MECHANISM OF GLUE HYDROLYSIS IN ELECTROLYTE


All the above-mentioned information was obtained by measuring the kinetics of glue decomposition in plant electrolyte where the glue had been present for at least 1 hour. Different behavior was observed when a fresh solution of glue in water was added to a plant electrolyte in which the original glue had been decomposed by heating. The relationship between potential shift and time is different (Figure 10).
METALLURGICAL TRANSACTIONS B

160 170 H2SO4, g/L

....

I 180

190

Fig, 9 - - G l u e hydrolysis rate constant vs sulfuric acid concentration.

By definition, glue activity is the ability of glue to form a resistance layer on the cathode. It is measured by the overpotential or PS (at a constant current). Figure 10 shows that the glue activity first increases and then decreases exponentially with time. This behavior can be explained as follows.
VOLUME 24B, APRIL 1993--279

Potential

70

Shift,mV 65"C;170g HzSO~/L o Experimental data m Correlateddata ~, ~ r o l y Freshgluewas t e


added

Gmo = concentration of glue in the form of

oo?e
50 ~40 3020 100 1
I

medium-sized molecules present in electrolyte before hydrolysis takes place, mg/L. The medium-sized glue molecules are more active. (2) The long-chain molecules of glue are hydrolyzed to medium-sized molecules after the glue is added to electrolyte:
Glo --~ G m

[4]

Time,h

where G m is the concentration of glue in the form of medium-sized molecules produced from Glo in time t, mg/L. (3) Assuming that the kinetics of the hydrolysis of longchain molecules to medium-sized molecules is fh-st order,
Gl = Glo exp ( - k i t )

Fig. 1 0 - - K i n e t i c s of glue hydrolysis.

(1) Glue is a positively charged long-chain protein molecule. The length of all of the molecules is not the same. Some molecules are longer and some are shorter. (2) The glue molecules are polarized, and they attach to the cathode by one end only. A very long and heavy molecule will cover only a small area of the cathode. If the long glue molecule is split (let us say in 10 parts), the same amount of glue will have I0 times as many molecules which are able to cover 10 times as much of the surface of the cathode. Higher resistance on the cathode surface will develop, and a higher glue activity will be experienced. (3) As glue hydrolysis continues, the glue is finally hydrolyzed to short molecules which are not able to form a resistance barrier on the cathode surface, and the glue loses its activity. (4) This hydrolysis is a statistical process. To split a long glue molecule to 10 shorter molecules requires only nine hydrolyses to take place. That means that this process of producing "active glue" from long glue molecules is a relatively rapid process (i.e., hydrolysis rate constant will be large). If 10 short glue molecules are to be hydrolyzed to nonactive molecules (short ones), many (about 100 to 200) hydrolysis "cuts" have to be made and the hydrolysis rate constant will be small. (5) It was shown in Figure 7 that the hydrolysis of medium-sized molecules follows first-order reaction kinetics. Because the hydrolysis of long glue molecules is virtually the same process, first-order kinetics was anticipated. The above assumptions about the mechanisms of glue hydrolysis were expressed in chemical and mathematical equations. The final mathematical model is then compared with experimental data. (1) Glue, when dissolved in water, is a mixture of longand medium-sized molecules:
G = Glo + Gmo

[5]

where Gl = Concentration of long molecules left in electrolyte after time t, mg/L; kl = rate constant for Reaction [4]; and t = tme elapsed after adding glue to electrolyte, hours. (4) Concentration of glue with medium-sized molecules formed from glue with long molecules in time t:
G m = Glo - Gl

[6]

By substituting Eq. [5] into [6], we obtain


Gm = Glo (1 - Glo exp ( - k l t ) ) [7] (5) Glue with medium-sized molecules either initially present in the glue Gmo or formed from long-chain molecules G m is hydrolyzed in electrolyte to glue with very short molecules Gi which are electrochemically inactive: Gmo --~ Gi G m --~ Gi

[8] [9]

where Gi is the Concentration of hydrolyzed, inactive glue, m g / L . (6) The concentration of active glue in time t is
G m r = [Gmo + Gm] exp ( - k , , t )

[10]

where Gmr = total amount of active glue at time t, mg/L; and k,, = hydrolysis rate constant for Reactions [8] and [9], h -l. By substituting Eq. [7] into [10], we obtain
G m r = [Gmo + Glo - Glo exp (-k/t)] exp (-kmt) [ 11 ]

[3]

where

G = total concentration of glue in electrolyte before hydrolysis takes place, mg/L; Glo = concentration of glue in the form of long molecules present in electrolyte before hydrolysis takes place, mg/L; and

(7) The PS, which is the difference in potential at 2.5 minutes and at 0.1 minutes of plating at a constant current, is the measure of glue activity in the electrolyte. PS consists of the activity of long glue molecules, the activity of medium-sized molecules, and the PS caused by the electrolyte background: PS = G l F + GrnT + PS8 where PS = potential shift, mV;
METALLURGICAL TRANSACTIONS B

[12]

280--VOLUME 24B, APRIL 1993

F = a factor denoting the relative activity of long chain glue molecules with respect to the activity of medium-sized molecules. F < 1. (PS)B = potential shift caused by electrolyte background. By substituting Eqs. [5] and [11] into [12] and rearranging; we obtain PS = GloF exp (-kit)

Gc' = a numerical constant, mg/L. In Eq. [16], both sides have the same dimensions (mg/L) and the constants have a physical meaning. Table V summarizes the results. V. FLOW PROFILE IN INCO C O M M E R C I A L E L E C T R O L Y T I C CELL Analysis of the glue concentrations at the inlet and outlet of the INCO commercial electrolytic cell shows that 30 to 37 pet of the glue is hydrolyzed in the cell, with the average being 33 pet. The average residence time of electrolyte in the cell is 3.4 hours. Since the kinetics of glue decomposition in electrolyte is known, the degree of glue decomposition in the electrolytic cell can be calculated assuming either (a) plug flow or (b) perfectly mixed flow. The calculation was done and is listed in the Appendix. The results are presented in Table VI. Table VI shows that at 160 g H2SO4, 57 and 74 pet of the glue would be decomposed in the electrolytic cell if the flow was perfectly mixed or plug, respectively. Actually, only 33 pet of the glue was decomposed. Therefore, the residence time of the electrolyte in the cell must be much shorter. This can only be explained by a "bypass flow," probably across the bottom of the electrolytic cell. This information is useful in developing a model of electrolyte mixing in the cell during electrolysis. The fresh electrolyte is released by the downpipe close to the bottom of the cell. The main stream of electrolyte follows the path of least resistance across the cell bottom. When the flow reaches the cell end, it turns up and overflows the dam (Figure 11). Besides the main flow, some local flow patterns develop. A circulation flow develops between each anode and cathode. At the cathode surface, the electrolyte is depleted of copper and has a lower than average density. At the anode surface, the electrolyte has a higher copper concentration and a higher density. This difference in electrolyte densities causes the circulation flow. At the cathode surface, the electrolyte flows up, and at the anode surface, it flows down, taking some slimes with it. It is probable that some intermixing between these two flows also develops. The down stream at the anode surface partially mixes with the main electrolyte flow across the cell bottom. If the circulation flow between each pair of electrodes in the cell is intense, the mixing between electrolyte located between electrodes and electrolyte in the main stream will also be more intense. This will result in a longer average residence time of electrolyte in the cell and a lower glue concentration in the cell outlet. The maximum glue decomposition should be between 57 and 74 pet (a mixture of piston and perfectly mixed flow). Since only 33 pet glue decomposition was observed, it can be concluded that the circular mixing between electrodes is not very intense. Also, the actual residence time of electrolyte between electrodes must be longer than the calculated average. Therefore, the actual glue concentration
VOLUME 24B, APRIL 1993--281

+ [Gmo + Glo - Glo exp (-ktt)]


9exp (-k~O + PSB Equation [13] can be rewritten as PS = Glo[F exp ( - k t t ) - exp (-(kl + k,,)t)l + G, exp (-kmt) + (PS)~ [141 [13}

where G, = Gmo + Glo The semiempirical Eq. [14] was used to correlate the change of experimentally determined PS with time for plant electrolytes containing 170 and 180 g H 2 S O 4 / L . The LOTUS* 1-2-3 regression package was used. The
*LOTUS is a trademark of Lotus Development Corporation, Cambridge, MA.

results are presented in Tables I and II. In both cases the correlation was excellent (Figure 10). As was shown earlier (Figure 3), the relationship between PS and the active glue concentration can be expressed by a polynomial equation. In the case of experiments listed in Tables I and II, the equation is Glue (mg/L) = - 6.02 + 0.67224-PS - 0 . 0 1 5 2 2 , ( P S ) 2 + 0.000141*(PS) 3 [151 For every calculated PS listed in Tables I and II, the corresponding glue concentration was calculated using Eq. [15] and is listed in Tables III and IV. Finally, the calculated glue concentrations were correlated with expressions similar to the ones used in Tables I and II. An equation similar in shape to Eq. [14] but with different constants was obtained. It describes the glue concentration as a function of time: Glue (mg/L) = Glo' [ F e x p ( - k / t ) - exp ( - ( k / + km')t] + G,' exp ( - k / t ) + G,.' [16] where Glo' = concentration of glue in the form of long molecules present in electrolyte before the hydrolysis takes place, mg/L; Gs' = Glo' + Gmo' Gmo ' = concentration of glue in the form of medium-sized molecules present in electrolyte before hydrolysis takes place, mg/L; k/ = hydrolysis rate constant for long molecules used in Eq. [ 16], hk,,,' = hydrolysis rate constant for medium-sized molecules used in Eq. [16], h-~; and
METALLURGICAL TRANSACTIONS B

Table I.
kl = 4.3

Kinetics PS

vs

Time (65 *C; 170 g H2SO4/L)


F=0.1

km = 0.6
Time (Hour) 0.058 0.208 0.375 0.541 0.708 0.875 1.040 2.041 3.041 4.041 5.041 6.041 30.000 Exp. PS (mV) 46.9 59.4 62.3 59.9 59.7 54.8 49.5 30.9 23.2 17.6 15.3 13.3

H*
-0.67468 -0.31999 -0.13927 -0.06082 -0.02637 -0.01141 -0.00497 -0.00002 -0.00000 0.000000 2.0E-11 3.8E-13 9.5E-58

e^(-kmt)
0.965798 0.882673 0.798516 0.722816 0.653900 0.591555 0.535796 0.293875 0.161282 0.088513 0.048577 0.026659 0.000000 11.12284 1.053821 0.997615 12 9 73.45793 1.270664

Calc. PS (mV) 46.89 59.28 62.52 61.05 57.78 53.98 50.22 32.71 22.97 17.62 14.69

13.08
11.12

Regression Output Constant Standard error of Y estimate R squared Number of observations Degrees of freedom X coefficient(s) Standard error of coefficients 52.13669 2.138331

H* = F exp ( - k t t ) - exp [-(kt + kin)t] Calc. PS = 52.14 [F exp (-ktt) - exp [-(kt + k,,)t]] + 73.46 exp (-kmt) + 11.12

Table II.
kl = 3.50 k,, = 0.66 Time (Hour) 0.058 0.208 0.375 0.541 0.708 0.875 1.040 2.041 3.041 4.041 5.041 6.041 30.000 PS (mV) 45.8 55.8 61.2 57.0 57.4 53.3 47.7 29.7 20.1 17.0 14.0 13.2

Kinetics PS

vs

Time (65 ~

180 g HzSO4/L)
F = 0.05

H*
--0.74480 -0.39678 -0.19667 -0.09781 -0.04839 -0.02391 -0.01190 -0.00016 -0.00000 -0.00000 0 . ~ 2.1E-I 1 1.3E-47

e^(-kmt)
0.962443 0.871726 0.780750 0.699730 0.626704 0.561299 0.503384 0.260003 0.134383 0.069456 0.035898 0.018554 0.000000 11.10692 1.203029 0.996728 12 9 75.43105 1.565994

Calc. PS (mV) 45.60 56.56 59.94 58.88 55.90 52.22 48.47 30.71 21.24 16.35 13.81 t2.51 11.11

Regression Output Constant Standard error of Y estimate R squared Number of observations Degrees of freedom X coefficient(s) Standard error of coefficients 51.16163 2.359174

H* = F exp ( - k t t ) - exp [-(k~ + km)t] Calc. PS = 51.16 [F exp ( - k t t ) - exp [-(k~ + k,,)t]] + 75.43 exp (-k,,t) + 11.11
282--VOLUME 24B, APRIL 1993 METALLURGICAL TRANSACTIONS B

Table III.
k~=7 k,, = 0.5 Time (Hour) 0.058 0.208 0.375 0.54l 0.708 0.875 1.040 2.04l 3.041 4.041 5.041 6.041 30.000

Kinetics Glue Concentration

vs

Time (65 *C; 170 g H2SO4/L)


F=O.1

PS (mV) 46.9 59.4 62.3 59.9 59.7 54.8 49.5 30.9 23.2 17.6 15.3 13.3

H* -0.58063 - 0 . 18681 -0.05281 -0.01502 -0.00423 -0.00119 -0.00034 -0.00000 - 6 , 7 E - 11 -1,7E-14 1.3E-18 2.2E-20 6.3E-93

e"(-km t)
0.971416 0.901225 0.829029 0.762997 0.701874 0.645648 0.594520 0.360414 0.218602 0.132589 0.080419 0.048776 0.000000 0.07954 0.374133 0.991955 12 9 13.33714 0.407253

Calc. Glue (mg/L) 6.57 9.72 10.97 t0.37 9.21 8.10 7.21 4.62 3.10 1.87 1.02 0.48 - 0.23

Regression Output Constant Standard error of Y estimate R squared Number of observations Degrees of freedom X coefficient(s) Standard error of coefficients H* = F exp ( - k t t ) exp [-(kt + km)t] 10.85947 0.806498

Calc. Glue = - 6.02 + 0.67224.PS - 0.01522.(PS)^2 + 0.000141.(PS)^3

Table IV.
kl =7.00

Kinetics Glue Concentration

vs

Time (65 ~

180 g H2SO4/L)
F = 0.05

km -- 0,51
Time (Hour) 0.058 0.208 0.375 0.541 0.708 0.875 1.040 2.041 3.041 4.041 5.041 6.041 30.000 PS (mV) 45.8 55.8 61.2 57.0 57.4 53.3 47.7 29.7 20.1 17.0 14.0 13.2 H* -0.61357 -0.19804 -0.05620 -0.01606 -0.00455 -0.00129 -0.00037 -0.00000 -9.2E-11 -4.0E-14 -1.3E-17 1.8E-21 3.1E-93

e^(-km t)
0.970853 0.899352 0.825926 0.758881 0.696923 0.640023 0.588369 0.353133 0.212054 0.127338 0.076465 0.045917 0.000000 0.15440 0.275885 0.995075 12 9 12.54766 0.300361

Calc. Glue (rag/L) 6.36 8.83 9.96 9.58 8.63 7.66 6.86 4.35 2.74

1.52
0.73 0.28

Regression Output Constant Standard error of Y estimate R squared Number of observations Degrees of freedom X coefficient(s) Standard error of coefficients H* = F exp (-ktt) - exp [-(k/ + km)t] Calc. Glue = - 6 . 0 2 + 0.67224,PS - 0.01522*(PSf12 + 0.000141*(PSfl3 9,418774 0.564306

METALLURGICAL TRANSACTIONS B

VOLUME 24B, APRIL 1 9 9 3 - - 2 8 3

Table V.

S u m m a r y of C o n s t a n t s in E q u a t i o n [16]

Constant Description Glue present in long chain molecules Total glue Hydrolysis rate constant for long molecules Hydrolysis rate constant for medium-sized molecules Activity factor for long glue molecules Regression Fit R squared Standard error of Y Estimate mg/L Symbol
Glo' Gs'

H2SO 4 (g/L) Dimension mg/L mg/L h -l h -1 -170 10.86 13.34 7.0 0.5 0.1 0.992 0.374 180 9.42 12.55 7.0 0.51 0.05 0.995 0.276

k/ k,,' F

T a b l e V I . Fraction o f G l u e R e m a i n i n g in Solution after Electrolyte Has F l o w e d t h r o u g h the Cell

Glue, mg/L

Copper,

g/L
46

Electrolyte Acidity

(g H2SO4/L)
Cell Flow Profile Actual Calculated Plug flow Perfectly mixed flow 160 0.669 0.258 0.430 170 -0.235 0.411
~ ~O"" ~ ~ ~ ~ .O /
Anode 42 _44

jceth~e
--'e
I I I 1 2 3 Distance from electrolyte inlet, m

9 Copper o Glue
4 40

Fig. 12--Copper and glue concentration between plating electrodes. Samples taken 45 cm beneath the surface.

Glue mg/L

Copper, ~L

3.0-

Fig. 11 --Scheme of electrolyte flow through the electrolytic cell.

2.52.0 pper oGlue I 0.8

47

in the electrolyte b e t w e e n the electrodes must be lower than the average concentration. To verify the a b o v e statement about glu e concentration between working plant electrodes, samples o f electrolyte were taken at different areas and depths in the electrolytic tank and analyzed for c o p p e r and glue content. The s a m p l i n g was done three times, and the results are shown in Figures 12 and 13. As can be seen, the analytical results confirm the m i x i n g theory.

I 0.2

Distance from electrolyte surface, m

I 0.4

I 0.6

45

Fig. 13--Copper and glue concentrations between plating electrodes at different depths.

VI. MATHEMATICAL MODELING OF ELECTROLYTE RECIRCULATION PROCESS IN THE TANKHOUSE Electrolyte, which is being fed to each electrolytic tank in the I N C O tankhouse, has 1.6 m g / L o f fresh glue added to it. A portion of this amount is decomposed in the tank, and the rest is recirculated back. 284--VOLUME 24B, APRIL 1993

The concentration o f follows: in the first pass, C i = in the second pass, C i in the third pass, C i ~

glue in electrolyte then is as

A; = A + A * B; A + (A + A * B ) * B = A + A,B+A*B2; in the fourth pass, C i = A + [A + (A + A * B ) * B] 9 B =A +A*B +A*B 2

in the nth pass, C i = A *

+A'B3 (1 + B + B 2 + B 3 + . . . + B~,,- I))

METALLURGICALTRANSACTIONSB

where Ci = concentration of glue in electrolyte entering the cell, m g / L ; A = fresh glue addition rate to electrolyte in each pass, rag/L; B = fraction of glue remaining after each pass; and n = number of recirculations. The nth pass equation is a sum of a geometric row and has the following solution:
C i = A * (l - B~n-l))/(1 - B)

[17]

At steady-state conditions, n ---> ~ and limCi=A/(1


n ~ ~

-B),

becauseB< 1
[18]

The concentration of glue in the cell outlet (Co) then is as follows:


Co = Ci * B
or

cell bypasses the electrodes, probably across the bottom of the cell. (b) The circulation flow between electrodes is not very intense or that some intermixing between up and down streams takes place. (c) The actual residence time of electrolyte between electrodes is longer than average. Therefore, the resulting glue concentration in this area is lower than average. (d) Average copper concentration between electrodes is higher than in the cell inlet, probably due to chemical dissolution of copper. The higher copper concentration between electrodes again indicates a relatively small circulation between the main electrolyte flow and the electrolyte between electrodes. (e) Glue concentration in the electrolyte between the electrodes is independent of the distance from the electrolyte surface. Average copper content in the electrolyte increases with the distance from the electrolyte surface (Figure 13). 4. Electrolyte glue concentration in the cell inlet and outlet depends on the glue addition rate and can be calculated using the following formulas:
Ci = A / ( 1 - B) Co = Ci*B = A,B~(1 - B)

[ 19]

Co = A * B/(1-

B)

[20]

SUMMARY 1. A quantitative galvanostatic technique for glue analysis in INCO copper electrolyte was developed and is used for glue analysis and control in plant electrolyte. 2. A mathematical model based on the probable glue hydrolysis mechanism was developed and found to be in good agreement with experimental data. The model suggests the following.

where C i = concentration of glue in electrolyte entering the cell, mg/L; A = glue addition rate to electrolyte, mg/L; B = fraction of glue remaining after each pass through the cell; and C o = concentration of glue in electrolyte outlet from the cell, m g / L .

(a) The glue, when dissolved in water, contains a spectrum of molecular sizes. Some molecules are long, and some are medium-sized. (b) The long molecules appear to be 10 to 20 times less active (F = 0.1 to 0.05) than the medium-sized molecules and are probably 10 to 20 times longer. (c) The proportion of glue in the form of long chain molecules is G/~ --- 75 - 80 pet. (d) In electrolyte, both long- and medium-sized molecules are split by hydrolysis to shorter molecules. The long molecules are first split into medium-sized molecules, which are then hydrolyzed to short inactive glue molecules. (e) The hydrolysis rate of medium-sized and long glue molecules follows first-order reaction kinetics with respect to glue concentration. (f) Sulfuric acid acts as a catalyst for glue hydrolysis. (g) The dependence of the glue hydrolysis rate constant on temperature follows the Arrhenius equation. (h) The hydrolysis rate of long molecules is about 10 to 20 times faster than the hydrolysis of medium-sized molecules. Since the hydrolysis process is a statistical one, this suggests that medium-sized molecules are on average about 10 to 20 times longer than the hydrolyzed inactive molecules. 3. The glue and copper analyses of electrolyte in INCO working electrolytic cells show the following. (a) The bulk of electrolyte flow in a working electrolytic
METALLURGICAL TRANSACTIONS B

APPENDIX Calculation of glue concentration in the outlet from an electrolytic cell assuming the cell is perfectly mixed

The formula used for this purpose is 171 u = T where u (t) exp ( - t / r ) d t [211

u = concentration of component flowing out from a perfectly mixed system; u(t) = is the equation for the rate of component concentration change with time in a batch reactor; t = is the time, hours; T = average residence time in the mixer, hours; and exp ( - t / T ) = time distribution function for the perfectly mixed case. In our case, u(t) = PS(t) is the dependence of the PS measured in the electrolyte on time. As derived earlier, for fresh glue added to electrolyte, the dependence of PS on time is expressed by the following equation ( e . g . , in electrolyte starting with 11.0 m g / L glue and 170 g H 2 S O J L at 65 ~ PS(t) = 52.137.[0.1 exp ( - 4 . 3 . t ) - exp ( - 4 . 9 * 0 ] + 73.458 exp ( - 0 . 6 * 0 + 11.122 [22]

VOLUME 24B, APRIL 1993--285

By substituting Eq. [22] into [21], we obtain PS = - 3.4 {[5.2137 exp ( - 4 . 3 . t ) - 52.137 exp ( - 4 . 9 * 0 + 73.458 exp ( - 0 . 6 * 0 + 11.122] 9exp ( - t / 3 . 4 ) } d t [23]

B = 1.975/(1.6 + 3.2) = 0.411

[29]

Calculation of glue concentration in the outlet from an electrolytic cell assuming plug flow Value of PS was calculated using Eq. [22] (3.4 hours were substituted for t: PS = 20.67 [30]

The above integral has an analytical solution which is


1

PS = - - * [ 3.4

1.135 exp ( - 4 . 9 5 4 * 0 + 10.038 exp ( - 5 , 1 9 4 . t )


-

Glue concentration in the outlet from an electrolytic cell was then calculated using Eq. [26]: Glue = 2.62 m g / L [31] Ratio of glue left in cell outlet: B = 2.62/11.0 = 0.238 [24} [32] [31]

82. 167 exp ( - . 8 9 4 . t )

- 37.815 exp ( - t / 3 . 4 ) ] o
1

PS = - - * [ 1 . 1 3 5 - 10.038 + 82.167 + 37.815] 3.4 = 32.67 [25]

This is again correct for the portion of fresh glue which was added to the electrolyte. For the calculation of the portion of glue recirculated, Eq. [27] was used:
Co = 3.2 exp ( - 0 . 4 2 8 * 3 . 4 ) = 0.747 m g / L

[33]

The relationship between glue concentration and PS (calibration curve) is Glue ( m g / L ) --: - 6 . 0 2 + 0.67224,PS - 0.01522,(PS) 2 + 0.000141 *(PS) 3 [26]

The total glue content in cell outlet is 1.6.0.239 = 0.381 + 0.747 = 1.129 m g / L glue The ratio of glue left in electrolyte assuming piston flow is: B = 1.129/(1.6 + 3.2) = 0.235 [34]

By substituting Eq. [25] into [26], we found the following: (1) the glue concentration in the outlet (from an ideally mixed reactor) was 4.61 m g / L ; (2) the cell inlet glue concentration was 11.0 m g / L ; and (3) the proportion of glue left in electrolyte was B = 4.61/11.0 = 0.42. The preceding calculation will be correct only if fresh glue is added to the electrolyte. At plant conditions, 1.6 m g / L of fresh glue is added and 3.2 m g / L is recirculated. The equation for the kinetics of glue decomposition (glue was at least 1 hour in electrolyte) is much simpler:
Co =- Ci exp ( - 0 . 4 2 8 * 0 ,

Similarly, as shown earlier, the ratio of glue left in the outlet from an electrolytic cell was calculated for electrolyte containing 160 g HzSO4/L. The results are shown in Table VI.

NOMENCLATURE
a, b, c,

d A
B

[27]

where Co = glue concentration in electrolyte outlet, rag/L; and Ci = glue concentration in electrolyte inlet, 3.2 mg/L. By substituting Eq. [27] into [21], we obtain C = -3.4

C Ci Co Co F

lfo

3.2 exp ( - 0 . 4 2 8 . t ) [28]

constants for polynomial equation expressing glue content in electrolyte vs PS concentration of fresh glue addition to electrolyte in each pass (rag/L) fraction of glue remaining after each pass concentration of active component concentration of glue in electrolyte at the inlet to the electrolytic cell (rag/L) concentration of glue in electrolyte at the outlet of the electrolytic cell (rag/L) concentration of active component at time = 0 factor which defines how many times the activity of long glue molecules is less than the activity of medium-sized molecules

9exp ( - t / 3 . 4 ) d t = 1.303 m g / L

( F < 1)
G
Gc t

The total calculated glue concentration in cell outlet is 1.6 mg/'L * 0.42 = 0.672 + 1.303 = 1.975 m g / L glue The fraction of glue left in electrolyte is
2 8 6 - - V O L U M E 24B, APRIL 1993

Gi GI

total concentration of glue in electrolyte before hydrolysis took place ( m g / L ) numerical constant used in Eq. [16] ( m g / L ) concentration of hydrolyzed, inactive glue (from medium-sized molecules), m g / L . concentration of glue in long molecules left in electrolyte after time t ( m g / L )
METALLURGICAL TRANSACTIONS B

concentration of glue in medium long molecules produced from Glo in time t (mg/L) Gmr total concentration of active glue (medium long molecu!es) in time t (rag/L) Glo or concentration of glue in the form of long Glo' molecules present in electrolyte before hydrolysis took place (rag/L)* Gmo or concentration of glue in the form of mediumGmo' sized molecules present in electrolyte before hydrolysis took place (rag/L)* = Glo + Gmo as G~' = Glo' + Gmo' (Eq. [16]) k kinetic constant (h -z) kt or k/ hydrolysis rate constant for long glue molecules (h-Z) * km o r hydrolysis rate constant for medium-sized glue molecules (h-l) * PS potential shift (difference between potential reading at 2.5 minutes and 0.1 minute of potential measurement (mV)
*Constants with primes are used in Eq. [16].

Gm

PSB
t

potential shift caused by electrolyte background (mV) time elapsed after glue addition in electrolyte (hour)
ACKNOWLEDGMENT

The authors thank 1NCO Limited for the support of this program and for allowing us to publish the results.
REFERENCES
1. T.N. Andersen, R.D. Budd, and R.W. Strachan: Metall.
Trans. B, 1976, vol. 7B, pp. 333-38.

2. S. Krzewska, L. Pajdowski, H. Podsiadly, and J. Podsiadly: Metall. Trans. B, 1984, vol. 15B, pp. 451-59. 3. U.S. Patent No 4,834,842, May 30, 1989. 4. Canadian Application for Patent Serial No. 2,027,156, INCO Limited, Copper Refinery, Copper Cliff, ON, Canada, filed Oct. 9, 1990. 5. N.R. Bharucha, Z. Zavorsky, and R.L. Leroy: Metall. Trans. B, 1978, vol. 813, pp. 509-14. 6. M.D. Saban, J.D. Scott, and R.M. Cassidy: Metall. Trans. B, 1992, vol. 23B, pp. 125-33. 7. V. Vanecek: Collection Czech. Chem. Commun., 1960, vol. 25, p. 2395.

METALLURGICAL TRANSACTIONS B

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