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Minerals Engineering 18 (2005) 567–573 This article is also available online at: www.elsevier.com/locate/mineng
Minerals Engineering 18 (2005) 567–573 This article is also available online at: www.elsevier.com/locate/mineng

Minerals Engineering 18 (2005) 567–573

Minerals Engineering 18 (2005) 567–573 This article is also available online at: www.elsevier.com/locate/mineng

This article is also available online at:

www.elsevier.com/locate/mineng

Quantitative assessment of hydrophobic agglomeration performance

X.Q. Wu a, * , A.J. Monhemius b, * , R.J. Gochin b

a School of Resource Processing and Bio-engineering, Central South University, Changsha 410083, Hunan, China b Department of Earth Science and Engineering, Royal School of Mines, Imperial College, SW7 2BP London, UK

Received 15 July 2004; accepted 9 September 2004

Abstract

The process of agglomeration is quantitatively described by the use of two factors: (i) the hydrophobic compatibility between the solid and the liquid, and (ii) an agglomeration coefficient. If in an agglomeration system, the gap between the hydrophobicities of the agglomerants (i.e. the solid and the liquid) exceeds certain tolerances, it is difficult for the agglomeration process to proceed prop- erly, especially to produce appropriately sized, dense, agglomerates. By the use of certain organic surfactants, it is possible to adjust agglomerant compatibilities and make the agglomeration system work well. This promotion action of surfactants is explained in terms of the interfacial interactions and the immersion energy of the system. In addition, the agglomeration efficiency of different agglomerants can be evaluated by the agglomeration coefficient , which is measured by the capillary rise method and reflects the physical properties of the liquid and the mutual interactions between the solids and the liquid. 2004 Elsevier Ltd. All rights reserved.

Keywords: Agglomeration; Coal; Fine particle processing

1. Introduction

Oil agglomeration is a process in which oil-solid agglomerates are formed by mixing oil with hydropho- bic solid materials. The main purpose of oil agglomera- tion is to selectively separate fine coal from coal shale slimes (Szymocha, 2003). In recent years, however, the oil agglomeration process has been used directly to re- cover gold particles, and the dense oil-carbon agglomer- ates formed by oil agglomeration have been used as a carrier or absorbent to recover gold from gold-bearing ores (House et al., 1988; Calvez et al., 1998). It is this lat- ter application of oil agglomeration that is the main focus of this paper. Specifically, the paper is primarily concerned with the quantitative assessment of the oil

* Corresponding authors. Tel.: +44 207 594 7329; fax: +44 207 594

7444.

E-mail addresses: xiqingwu@hotmail.com (X.Q. Wu),

0892-6875/$ - see front matter 2004 Elsevier Ltd. All rights reserved.

doi:10.1016/j.mineng.2004.09.005

agglomeration process on the basis of the surface prop- erties of the liquid and solid agglomerants. The solid materials most commonly used for agglom- eration are various types of coal. Generally speaking, anthracite and bituminous coals respond better than lig- nite (Mehrotra et al., 1983). Furthermore, the moisture content, the porosity and the compositional parameters (carbon content, hydrogen content, oxygen content, atomic ratio of hydrogen/carbon, atomic ratio of oxygen/carbon) of coal are among the factors that affect the agglomeration response (Hatten, 1982; Moxon et al., 1987; Labuschagne et al., 1988). Labuschagne et al. (1988) proved that the moisture content of coal corre- lated more closely with its agglomeration response than the compositional parameters. Oil is preferentially ab- sorbed into the coal pores instead of spreading over the surface to form a film, and this results in the loss of collecting or bridging power. Being more porous, the coal surface is thus less easily covered by the oil (Moxon et al., 1987).

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X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

In general, the properties of oil are expressed in terms of several parameters, namely: density, viscosity, surface or interfacial tension, composition, etc. Certain of these properties have been recognised as important for agglomeration. Sun and Mcmorries (1959) concluded that the oils with specific gravities in the range of 0.70 and 0.85 are the most effective, while ones with specific gravities below 0.64 or above 0.97 are not effective. Sar- ket et al. (Mehrotra et al., 1983) claimed that oils with medium surface tension (30mN/m) and medium viscos- ity are the most effective, and that oils with lower or higher surface tensions (and viscosities) are not as effec- tive. Labuschagne et al. (1989) investigated the effect of bridging liquid composition on the selective agglomera- tion of various coals in terms of four aspects of molecu- lar structure: double bonds, structure of polar groups, alkyl groups and quantity of polar groups. After analy- sing the mechanism of hydrophobic oil film formation on coal particles, Marcello et al. (1989) proposed the fol- lowing requirements for the oil: low repulsive energy in the interaction with coal, limited interfacial tension at the coal–oil boundary, relatively low viscosity and a weak tendency to adsorb into the coal pores; they de- signed a binary mixture of diesel oil and fuel oil to meet these requirements. Hence, regarding the effects of the agglomerants (solid and oil) on agglomeration, it appears difficult to draw a firm and general conclusion, let alone in a quan- titative manner. This paper will pay particular attention to calculating and adjusting the hydrophobic compati- bility between liquid and solid agglomerants, and will also attempt to use a combination of physical properties of the agglomerants to reflect and compare quantita- tively the differences of different agglomeration systems. From a thermodynamic standpoint, the driving force for the wetting of a solid by oil and the subsequent agglo- meration of oil-wetted particles is the reduction in the total surface energy of the system, thus the success in making oil–coal agglomerates depends on the surface properties of the coal and those of the oil. To avoid the above-mentioned complexity of coal surfaces, the solid agglomerant used here is graphite, which is a much simpler carbon material. Furthermore, while much work has been published on the agglomera- tion of coal, there are few papers dealing with graphite agglomeration.

2. Theory of hydrophobic compatibility

The process of immersion of a fine solid particle into a larger oil drop can be visualised as shown in Fig. 1. Taking the sizes of solid and liquid agglomerants into account, the immersion process can be thermodynami- cally analysed by estimating the resultant free energy changes. The free energy change of the whole system under isothermal conditions can be expressed as follows:

D G imm

¼ c hw ðsurface area of the oilsolid aggregate in waterÞ

þ c sh ðsurface area of the solid inside the oil dropletÞ

c sw ðsurface area of the solid in waterÞ c hw ðsurface area of the oil droplet in waterÞ

¼

¼ 4 p R 2 ðð1 þ n 3 Þ 2=3 c hw þ c sh c sw n 2 c hw Þ ð1Þ

4 p ðR 2

s

sh c hw þR 2

s

c sh R 2 c sw R

s

2

h c hw Þ

where D G imm is the free energy change of oil engulfing the fine solid particle, and R s , R h and R sh are the radii of the solid, the oil and the solid covered completely with oil (oil-solid aggregate) respectively, and n = R h / R s represents the ratio of the size of the oil drop to that of the solid particle. c hw , c sh and c sw are the interfacial tensions of hydrocarbon oil/water, solid/hydrocarbon oil, and solid/water, respectively. It should be noted that in the above derivation, the irregularity of the solid particle and oil entering pores in the solid are ignored. In order for the immersion pro- cess to occur spontaneously, DG imm <0, namely,

ð2Þ

D G imm ¼ ðð1 þ n 3 Þ 2=3 c hw þ c sh

For the special case where n 1, i.e. a system with a fine powder and comparatively large oil droplets, the approximation n 3 1 + n 3 holds and accordingly, Eq. (2) can be simplified to:

ð3Þ

D G imm ¼ c sh c sw < 0

Obviously, this is the free energy change of immer- sion for unit solid surface transferring from water into an oil drop. Fowkes (1964) defined liquids that have only the capability of Van der Waals interactions as dispersive because their entire surface tension is due to the loss of Van der Waals interactions from the molecules on

0

c sw n 2 c hw Þ < 0

0

+ = solid oil drop solid immersion into oil (oil-solid aggregate)
+
=
solid
oil drop
solid immersion into oil (oil-solid aggregate)

Fig. 1. Schematic model of oil engulfing a fine hydrophobic solid particle immersed in water.

X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

569

their surfaces. All other interactions were described as polar , including dipole/dipole interactions, hydrogen

bonding, p -electron interactions, and so on. For the case where one of the related two phases (liquid or solid) has only a dispersive component at its interface, Fowkes de- rived the following Eq. (4); otherwise there is an extra

polar interaction (polar

ð4Þ

For cases where both dispersion and polar forces operate, Owens and Wendt (1969) assume that Eq. (4) has a more general form, shown below,

c 1;2 ¼ c 1 þ c 2 2½ð c D c D Þ 1=2 þ ð c P c P Þ 1=2 ð5Þ

where c 1,2 is the interfacial tension between two liquids or liquid and solid; c 1 is the overall surface tension of li- quid 1; c 2 is the overall surface tension of liquid 2 or solid 2; c D and c D are the dispersive components of the

are

surface tensions c 1 and c 2 respectively; c P

attraction) I P

12 .

c 1;2 ¼ c 1 þ c 2 2ð c D c D Þ 1=2

1

2

1

2

1

2

1

2

1

and c P

2

the polar components of the surface tensions c 1 and c 2 , respectively.

2 . Thus, the polar attraction at the interface can be as-

sumed to be,

Here, c 1 ¼ c D þ c P , and

1

1

c 2 ¼ c D þ c P

2

I 12 P ¼ 2

It should be noted that, for the estimation of interfa- cial tensions, Van Oss et al. (1988) proposed a more complicated equation involving three components of the surface tension, i.e. a dispersion component, an acid component and a base component. The last two compo- nents represent polar interactions. So, putting Eq. (5) into Eq. (2), one can calculate DG imm 0 and thus know the thermodynamic probability for immersion of the solid into the oil drop. More spec- ifically, by substituting Eq. (5) into Eq. (3), another expression of free energy change can be obtained for the immersion of a fine solid particle into a large oil droplet,

q

ffiffiffiffiffiffiffiffiffi

c P c P

1

2

ð6Þ

0

DG imm ¼ c sh c sw

ð3Þ

¼ c h c w þ 2½ð c D c D

s

w Þ 1=2 þ ð c P

s

c

w P Þ 1=2

ð7Þ

If the liquid is a pure hydrocarbon, i.e. complete non- polarity c P ¼ 0 and c D ¼ c h , then,

ð c D c D Þ 1=2 ðc P c P Þ 1=2

s

h

s

h

h

h

DG imm ¼ c h c w þ 2½ð c D c D

ð8Þ

Now, assuming that solid surfaces inevitably have some surface polarity, it is necessary to estimate the maximum polarity of the solid for a given hydrocarbon to be able to agglomerate it, i.e. for the requirement that DG imm 0 < 0, what is the maximum compatible solid polarity c s;max P ? The maximum will occur when

0

s

w Þ 1=2 þ ð c P

s

c

P

w Þ 1=2 ð c D c h Þ 1=2

s

0

D G imm ¼ 0 and thus, rearrangement of Eq. (8) shows that a pure hydrocarbon can tolerate a maximum polar- ity of solid in order for immersion to happen, when

c

P

s;max ¼

"

p

s

ffiffiffiffiffiffiffiffiffiffi # 2

c

c w c h þ 2

p ffiffiffiffiffiffiffiffiffi c

D

s

c

h

D c D

w

2

p

ffiffiffiffiffi

c

P

w

ð9Þ

On the other hand, according to Eq. (7) the incom- patibility or compatibility between a polar solid and a liquid can be modified or adjusted by introducing a polar component into the liquid. For a given polar solid, to make DG imm < 0, the corresponding polarity of the liquid oil phase (or the minimum polarity of the oil)

should be,

0

c P

h;min ¼

ffiffiffiffiffiffiffiffiffi c P c P # 2

"

c w c h þ 2

p ffiffiffiffiffiffiffiffiffiffi c D c D

s

h

p

ffiffiffiffiffiffiffiffiffiffi

c D c D

s

w

p

s

w

 

ffiffiffiffiffi

 
   

2

p

c

P

s

ð10Þ

Thus, theoretically, there exists an issue of compati- bility between a solid and an oil for agglomeration to

occur. More importantly, this compatibility can be im- proved in the direction of favouring agglomeration by introducing polarity into the oil phase (for example, by means of surfactants) and consequently changing the interfacial interactions.

3. Experimental details

3.1.

Materials

(a)

Graphite powder, nominally –50 l m, mostly plate- shaped particles, with an estimated mean size of about 15 l m.

(b)

Hydrocarbon oils, octane (purity 99+%), decane (99+%), dodecane (99+%), tetradecane (99+%), and pentadecane (99+%).

(c)

Di-n-butylphthalate (DBP) C 6 H 4 -1, 2-[CO 2 (CH 2 ) 3 - CH 3 ] 2 , 99% purity.

3.2.

Methods

3.2.1. Agglomeration Agglomeration experiments were carried out in a

600ml beaker with two baffles 180 apart. Graphite

powder (25 g) was slurried with 400ml de-ionised water and then 10 g hydrocarbon oil plus DBP was added and mixed at 1100 rpm for 10–15min to form agglomerates. After agglomeration, the slurry containing the agglom- erates was poured on to a pair of sieves with openings of 0.6mm and 2.35mm, and the agglomerates were screened in water. The resultant size fractions were dewatered over a filter, dried overnight at 80 C, and

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X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

weighed separately. The yield of each agglomerate size was calculated by the oversize fraction(s) of this size sieve divided by the sum of all fractions, and its percent- age value was used for evaluating the agglomeration process. In other words, the so-called agglomeration yield in this study is actually the percentage of agglom- erates larger than a given sieve opening.

3.2.2. Surface and interfacial tension measurement

Surface and interfacial measurements were made at room temperature (around 20 C) on a Kru¨ ss K10 auto- matic tensiometer, which has an accuracy of 0.1mN/m.

3.2.3. Capillary rise measurement

The apparatus used for capillary rise measurements consisted of a beaker containing 50 to 100ml of liquid hydrocarbon as the reservoir and a calibrated vertical cylindrical tube supported by a clamp. The latter was made from a 10ml graduated volumetric pipette by cut- ting off the tip of the pipette. Before measurement, the tube was filled with a known mass of powder and pressed to a given bed density. At time zero, the vertical tube was lowered into the reservoir until the liquid sur- face touched the bottom of the powder bed. The height attained by the wetting front was recorded after different times.

3.2.4. Viscosity measurement

The viscosities were measured at room temperature (around 20 C) by an Ostwald viscometer.

4. Results and discussion

4.1. Compatibility

It was found in the initial experiments that it was dif- ficult to produce strong and appropriately sized agglom- erates by agglomerating graphite powder with pure hydrocarbon oils, and that adding some organic surfac- tants, such as octanol, DBP, or even edible olive oil, considerably changed the agglomeration performance. The influence of DBP on agglomeration is shown in Fig. 2. For a given oil dosage, the agglomeration im- proved rapidly with a small increase of DBP addition in terms of both the extent of agglomeration and the size of agglomerates produced. The interfacial tension of tetradecane–water ( c hw ) is decreased with the addition of DBP, as shown by the measured values listed in column 2 of Table 1, below, whereas the surface tension of oil-air (c h ) and the viscos- ity are virtually unchanged over the addition range. Using the interfacial tension measurements (oil + DBP)–water ( c hw ) shown in Table 1, in conjunc- tion with some known data for water (c w = 72.8mN/ m, c D w ¼ 21:8mN/m and c w P ¼ 51mN/m), values of c D

h

100 80 60 40 +0.6mm +2.36mm 20 0 Agglomeration yield (%)
100
80
60
40
+0.6mm
+2.36mm
20
0
Agglomeration yield (%)

0123456

Amount of DBP in tetradecane oil (% wt)

Fig. 2. Influence of additive DBP on agglomeration.

Table 1 Influence of DBP on interfacial interactions

DBP (%)

c hw

c h

c D

h

c

P

h

c sh

I P

sh

DG

0

imm

0

50.2

26.2

26.2

0

 

54.94

0

4.27

1.1

40.3

26.1

25.4

0.65

49.61

6.88

1.07

2.2

34

26.2

24.47

1.73

47.57

11.22

3.11

3.75

31.5

26.2

24.2

2.0

47.33

12.07

3.34

5.5

30

26.1

23.33

2.77

47.06

14.20

3.61

Note: c sw = 50.67 mN/m.

can be calculated by using Eq. (5). The polar

interaction ð c P Þ of the mixture (tetradecane + DBP) in- creases with DBP addition, indicating that in the mix- tures, unlike the pure hydrocarbon, there exists a polar component, which can interact with corresponding polar sites on the solid. According to the Washburn equation (Washburn, 1921), using a simple capillary model, the relationship between the liquid rise height through the powder bed and time is simplified below for the present purpose:

l 2 ¼ r c h cos h h

ð11Þ

and c P

h

h

2

g h

t

where l is the liquid rise height, r is the imaginary capil- lary radius of the powder bed; c h is the liquid surface tension, h h the contact angle (through the liquid), g h vis- cosity of the hydrocarbon liquid, t the time taken for the liquid to reach height l. So, for a given liquid and a pow- der with a uniform bed density throughout its height, a plot of the square of liquid rise height (l 2 ) versus time (t) should be linear. If the liquid properties, such as surface tension ( c h ) and viscosity ( g h ), are known, the wettability ðcos h h Þ can be obtained from the slope (a ) of the line, as shown in the following equation.

a ¼ r c h cos h h

ð12Þ

2

g h

The rates capillary rise of oil with different DBP addi- tions through the graphite bed were measured, and the

results are shown in Fig. 3. It can be seen that the square

X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

571

4 3 C14 2 C14+1.1%DBP 1 C14+2.2%DBP C14+5.5%DBP 0 0 5 10 15 20 25
4
3
C14
2
C14+1.1%DBP
1
C14+2.2%DBP
C14+5.5%DBP
0
0
5 10
15
20
25
30
35
40
2 ,cm 2
l

Time,(min.)

Fig. 3. Capillary rise of tetradecane with the change of DBP addition.

of rise height (l 2 , cm 2 ) versus time (t, minutes) is a per- fectly straight line for each concentration of DBP, and their correlation coefficients (R 2 ) are all better than 0.99. With increasing DBP, the lines become steeper, i.e. the oil rises faster in the capillary bed with DBP addition. All of these lines were obtained by measuring the same graphite powder with almost the same powder bed density. Therefore, considering that the surface ten- sion and viscosity did not change significantly with addi- tion of DBP (see Table 1), the following equation can be obtained to avoid the complexity of calculating the cap- illary radius (r),

cos h h;2

ð13Þ

cos h h;1

or,

a 2

a 1

c s c sh;2

c s c sh;1

a 2

a

1

ð14Þ

So, the fact that, with the addition of DBP, the slope of the line l 2 versus t increases means that the interfacial free energy of the solid/oil interface ( c sh ) is reduced with increasing DBP, i.e. adding DBP improves the affinity of the oil with the graphite surface. On the other hand, if there was no polar component in the graphite surface interaction, it would be found, by incorporating Eq. (4) into Eq. (14), that adding DBP would not result in increases in the slope, a . Hence, it is concluded that a polar interaction or some polar sites must exist on the so-called, non-polar surface of graphite. Kitchener (1992) suggested that the broken carbon– carbon bonds on the faces or the edges of graphite sheets must presumably be reactive. The fact that the zeta- potential of graphite particles changes with pH (Lasc- kowski, 1992) indicates that their surfaces have some active sites . Fowkes (1964) also found that some extra interfacial interactions arose at the interface of graphite– benzene beyond dispersive force, and he suggested that the graphite had some polarity that gave rise to an inter- action component with the polar liquid benzene. In more general situations, coal, commonly used in oil agglomeration and a quasi-graphitic solid, is inevitably

subject to progressive oxidation in air or water with the formation of various chemical groups at its surface. The polarity of various solid agglomerants is inevitable regardless of the type of material, and the interfacial interaction of solid and liquid agglomerants has to be analysed in terms of two components (dispersive and polar) in order to get a deeper understanding of the agglomeration process. In the literature, there are values for the dispersive surface energy of graphite c D , for example, c D ¼ 115

s

s

132 (Fowkes, 1964), and 127.6 or 121.7 (Janczuk and Chibowski, 1983). In this paper, an intermediate value of c D ¼ 125 will be assumed in the following calcula- tions. However, so far there are no data available for the polar part of the surface energy of graphite. In the following section, the polar surface free energy of the graphite powder used in this paper c P is estimated. This then allows the calculation of the maximum tolerance of

s

s

the polarity of the solid for immersion c s;max

minimum polarity of the corresponding oil for compat- ibility with the polar solid c P

and the

P

h;min .

If Eq. (5) is incorporated into Eq. (14), and the two slopes of the pure oil and oil + 1.1%DBP (0.1021 and 0.1067, respectively), are put into the resultant equation, the polar interaction of the graphite is estimated to be

18.2mN/m.

The graphite particles used in this study vary consid- erably in size, as described previously; the maximum size of the graphite particles was about 35 l m, while the mean size was about 15 l m. The maximum size of the oil droplets was about 90 l m with the mixing conditions used in the agglomeration experiments. The possible size ratio of the oil droplets to the solid particles is in the re- gion of n 3 (Wu, 2002). So, applying Eq. (9), the pos- sible tolerance of the pure hydrocarbon oil towards the polarity of the solid can be estimated for the immersion of the fine solid particles into the completely non-polar hydrocarbon, i.e.

P

c s;max

¼ 15:7 mN=m

So, pure tetradecane oil can permit graphite with a polarity of less than 15.7mN/m to immerse. On the other hand, according to Eq. (10), for the graphite pow- der with a polarity of 18.2mN/m, the minimum polarity of the corresponding oil for compatibility should be, c h;min P ¼ 0:26mN/m. So, the estimated graphite polarity c P ¼ 18:2 is larger

for

than the maximum allowable solid polarity c P

s

s;max

immersion (=15.7mN/m), and thus the energy change D G imm for immersion of the graphite into pure tetrade- cane will be positive, i.e. thermodynamically impossible. In order to meet the requirement D G imm < 0, the oil

should have a minimum polar interaction c P

0

0

h;min ¼

0:26mN/m. In addition, introducing a polar component into the liquid by adding the DBP surfactant not only

2 l 2

η

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X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

makes DG imm become negative, but also increases the polar attraction between the solid and the liquid I P shown in Table 1. The notion that the pure hydrocarbon has a toler- ance to the polarity of the solid implies that a non-polar hydrocarbon can agglomerate not only completely non- polar solid materials, but also other solids, provided the polarity of these lie within a certain limited range. In other words, the compatibility between the liquid and the solid can fluctuate within a certain range without fatally influencing the agglomeration process. In addi- tion, this compatibility is adjustable by introducing a certain amount of corresponding polar interactions.

sh ,

0

4.2. Agglomeration coefficient

As mentioned in the introduction, there have been many attempts to establish a relationship between agglomeration and the properties of the agglomerants; however, only some rules of thumb have been obtained. From the above discussion, it can be perceived that the product ( c h cos h ) in Eq. (12) reflects the affinity of the solid with the oil. The viscosity term in that equation is a measure of the ability of the liquid to either convey momentum or resist deformation. Even at the point at which micro-agglomerates coalesce to form larger agglomerates, the viscosity of the micro-agglomerates affects the dynamic bridging force between the two par- ties. Mazzone et al. (1987) studied the behaviour of li- quid bridges between two moving particles relative to each other, and found that the dynamic bridges were sometimes orders of magnitude stronger than corre- sponding static bridges, especially if the liquids were very viscous and the particles moved at large enough velocities. Thus, agglomeration models that take into ac- count only interparticle forces due to surface tension, will grossly under-predict agglomerate sizes when the particle surfaces are covered by a liquid film. In these circumstances, other factors, in addition to the viscosity, should be taken into consideration, such as surface ten- sion and contact angle. In fact, rearrangement of Eq. (11) gives,

1

g h l 2 ¼ 2

2

r g h c h cos h h

t

ð15Þ

Here, g h l 2 versus t should be linear. Five hydrocarbons (octane, decane, dodecane, tetradecane and pentadecane) were used for agglomera- tion to investigate the relationship between agglomera- tion and the physical properties of the agglomerating liquid. The plots of g h l 2 versus t for these five oils are shown in Fig. 4. It is evident that the plots are good straight lines, showing that the results obey Eq. (15). The slopes of these lines are called the agglomeration coefficient of the hydrocarbon ( x 0 ).

2

2

C12 C14 20 C15 C8 C10 10 0 0 5 10 15 20 25 30
C12
C14
20
C15
C8
C10
10
0
0
5 10
15
20
25
30
35
40

Time, (min.)

2 Fig. 4. g h l 2 versus t. 100 y = 176.2x - 15.06
2
Fig. 4. g h l 2 versus t.
100
y = 176.2x - 15.06
R 2 = 0.9175
80
y = 155.14x - 8.8488
R 2 = 0.9668
60
40
20
0
0
0.2
0.4
0.6
0.8
1
Agglomeration yield (%)

Agglomeration coefficient

Fig. 5. Relationship of agglomeration to agglomeration coefficient

Illustrators: (m) x = g h c h /100, ðdÞ

1

x 0 ¼ 2

r g h c h cos h h .

The relationship between the agglomeration yield and the agglomeration coefficients is shown in Fig. 5, where it is seen that a reasonable linear relationship can be established. It was also found that the product of liquid viscosity and surface tension ( x = g h c h /100) is also a good indicator of agglomeration performance. Basi- cally, in both cases, the linear correlations of agglomer- ation yield to agglomerant properties ( x 0 or x) show acceptable R 2 coefficients. So, in essence, both agglomeration coefficients are good indicators for comparing or predicting the agglom- eration of graphite with different hydrocarbon oils. More importantly, with the aid of the capillary rise method, values x 0 of are directly measurable.

5. Conclusions

1. It has been shown that the addition of organic sur- factants, such as DBP, to hydrocarbon oils improves the oils abilities to agglomerate graphite powder. By mea- suring the surface and interfacial tensions, and the vis- cosities of the oils and their wetting characteristics on graphite powders by the capilliary rise method, it was

X.Q. Wu et al. / Minerals Engineering 18 (2005) 567–573

573

found that the improvements in their agglomeration performance can be attributed to two factors. These are either (i) decreases in the interfacial tension between the hydrocarbons and water, which results in better dis- persity of the hydrocarbons in water or (ii) increases in the wettability of hydrocarbons on graphite powders, which results in easier adhesion of oil to graphite particles. 2. So-called non-polar graphite surface actually exhibits some amount of polarity. The addition of polar DBP into pure non-polar hydrocarbon oils gives the mixture some some polarity. Thus, adding DBP in- creases the compatibility of the oil with the solid in an oil-water-solid agglomeration system, thus making solid particles more easily immerse into oil droplets by increasing polar attractions at the solid/oil interface. Numerically, the compatibility can be represented by two concepts: the maximum tolerance of solid polarity for immersion, c s;max P , and the minimum polarity of the corresponding oil for compatibility with the poplar solid, c P

h;min .

3. By modeling the agglomeration process empiri- cally, the agglomeration performance has been related to the so-called agglomeration coefficient . This coeffi- cient is quite easily obtained, and it quantitatively com- pares the agglomeration behavior of different liquids and solids, and should have practical meaning in the prediction of agglomeration performance and the selec- tion of suitable agglomerants.

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