Colloids and Surfaces A: Physicochemical and Engineering Aspects 151 (1999) 283291

Application of ultra-occulation and turbulent micro-otation to the removal of ne contaminants from water
Nickolaj N. Rulyov *
Institute of Biocolloid Chemistry of the Ukrainian National Academy of Sciences, Kiev, Ukraine Received 22 September 1997; accepted 10 July 1998

Abstract Considering that the capture eciency of micro-particles of contaminants by bubbles in the process of otation can be described by the formula E3d1.45 /D1.83, where d and D are average sizes of initial particles and bubbles p p accordingly, then the process can be facilitated either by way of using possibly smaller bubbles (for example bubbles generated by the electrolysis of water), or by way of implementing a stage of enlargement of particles, for example on the basis of occulation aggregation. To ensure the generation of large and dense aggregates in a short time, the occulation is performed in a highly non-uniform hydrodynamic eld, which is specied by an average velocity gradient G=300010 000 s1 (ultra-occulation). After hydraulically largest occules have been separated in a continuous thin-layer settler, water is saturated with micro-bubbles and then water is passed through a static mixer, where a turbulent ow dened by Reynolds number Re=800012 000 and average velocity gradient G=300600 s1 is created. As a result of this treatment, small ocs of contaminants and micro-bubbles remain in the water after passing through a thin-layer settler and will form foam akes comprising thousands of initial microbubbles and millions of occulated particles. These akes can easily be separated from water in a continuous foam separator due to their high buoyancy (turbulent micro-otation). This method has been developed further as a technology, and a pilot plant has been designed for separation of wateroil emulsions, water purication from soluble organic compounds, radionuclides and heavy metal ions with application of ultra-disperse sorbents. 1999 Elsevier Science B.V. All rights reserved. Keywords: Contaminants; Flocculation; Flotation; Purication

1. Introduction The issue of water purication from soluble and ne contaminants presents one of the most important applications for todays academic science. Conventional approaches to this challenge involve the methods of binding (by chemical or physical means) molecules or particles of contaminants with relatively coarse grains of active or passive lter bed (FB). One of these methods is schematically
* E-mail: rulyov@nick.relc.com

shown in Fig. 1 (alternative I ). Even though such methods are comparatively uncomplicated, they are not fully suitable for a number of applications, mostly due to the necessity of frequent ushing or regeneration of FB or the need for replacing and dumping it (as, for example, required in handling radioactive contaminants). Since, for obvious reasons, the grain size of FB cannot be less than #0.2 mm, amounts of such wastes are usually quite high, and this in turn involves high operational costs, particularly when expensive sorbents are used. In this connection, wide acceptance has

0927-7757/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved. PII S0 9 2 7- 7 7 5 7 ( 9 8 ) 0 06 4 1 - 4

284

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

that alternative IV presents the most promising option. Compared to three conventional methods in this case, a ne sorbent is removed from water by way of ultra-occulation and turbulent microotation as described below.

2. Micro-otation Numerous experimental and academic research works show that the factors inuencing the capture eciency of particles by a rising bubble in otation signicantly depend upon their sizes [1]. This is illustrated in Fig. 2, which shows liquid streamlines and trajectories of particles of various dimensions in rising bubble center coordinates. Table 2 contains formulae for the capture eciency (CE ) E and factors inuencing its value for four major dimensional classes of particles: submicronic, ne, medium-size and coarse [1]. According to conventional denition: E=j/pR2 u n (1) b b p where n is particle concentration, R and u are p b b accordingly bubble radius and rising velocity, and j is the entire particle ow on the surface of a separate bubble. Reference CE values have been calculated for a bubble of 1 mm diameter and spherical particles having specic weight of 7.5 g/cm3 [1]. Computational results diagrammatically presented in Fig. 3 show that, specically in the range of submicron and ne size particles (which are the most common particle classes in various water purication applications), there is an extremely deep minimum of the dependence of E vs. d (particle diameter) [24]. Besides, as p follows from the formula shown in Table 2, for ne particles CE rapidly decreases with increase in dimensions of a bubble compared to particle diameter [5,6 ]. Hence, ecient application of otation in water purication is feasible provided two principle conditions are met, particularly: (1) the maximum possible coarsening of particles of contaminants (and/or those of sorbent) through their aggregation by way of coagulation and/or occulation; (2) decreasing diameter of bubbles to values as close as possible to the dimensions of aggregates.

Fig. 1. Principle ow charts (IIV ) and major stages for water purication from ne contaminants: (a) sorption; (b) settling (discharging); (c) coagulation (occulation); (d) ltration, (e) ushing; (f/h) micro-otation; (f/g/h) turbulent micro-otation.

been given to water purication technology utilizing a ne sorbent (with particle size below 10 mm) with high sorption capacity, which does not require granulation and can be introduced into the water or generated directly in it as a suspension. When the sorption is complete, particles of the sorbent can be removed from water through settling (alternative II, Fig. 1) and/or by ltration (alternative III, Fig. 1) through passive FB (for example, sand). These stages are normally also preceded by the coagulation and/or occulation stages. These methods are quite common for such applications as drinking water treatment and municipal waste waters cleaning. For the former applications, aluminum hydroxide and/or clay minerals (for example, bentonite) are used as sorbents. For the latter, micro-organisms are introduced into the active sludge. Despite signicant advantages oered by the above methods, their performance eciency for water purication is rather low due to the slow rates of occulation and settling and/or ltration of ne sorbents as their concentrations are normally low. Besides, these methods involve signicant investment and require much space to build settlers. In addition to that, the operation and maintenance of lters usually require high power consumption. The advantages and disadvantages of the above described and proposed methods are compared in greater detail in Table 1, which shows

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

285

Table 1 Advantages and imperfections of conventional (IIII ) and proposed (IV ) methods of water purication (explanatory notes to Fig. 1) No. Principal stages of the process Imperfections I Filtration (sorption, ion exchange)ushing (regeneration, discharge) Large amount of waste, frequent replacement (regeneration, ushing) of ltering bed, high costs for sorbents Sorptioncoagulation (occulation)settling High investment costs, high space requirements, low purication standards Sorptioncoagulation (occulation)ltrationushing Discontinuity of the process, signicant power requirements, laboratory support Sorptionultra-occulationturbulent micro-otation Relatively sophisticated equipment, laboratory support Advantages

Uncomplicated equipment, easy in-service and maintenance

II

Uncomplicated equipment, continuous process, small amount of waste

III

Low amounts of waste, high purication standards

IV

High eciency, low investment requirements, exibility in adjustment and combination with existing equipment, high purication standards, low amounts of waste

Fig. 2. Trajectories of particles of various dimensional classes in the vicinity of a rising bubble: (1) ne; (2) submicron; (3) medium-size; (4) coarse; (5) (dashed line) liquid streamlines in the rising bubble center coordinate system.

So far this method, named micro-otation, has not yet found wide application due to two major reasons: (1) the majority of series otation plants (utilized primarily for minerals conditioning) usually have bubbles with dimensions over 200 mm, which is around one order of magnitude higher than the actual dimensions of aggregates; (2) conventional otation plants where ne bubbles are generated (electro-otation and dissolved air otation) cannot ensure conditions for both ecient aggregation of particles and removal of bubbles loaded with contaminants from water, as the rising velocity of bubbles is very low. As described in ref. [10], the latter presents one of the principle limitations in terms of micro-otation eciency. However, these diculties can be overcome by way of a special hydrodynamic treatment of puried water performed both at sorption stage and aggregation of sorbents and/or suspension particles and heterocoagulation stage of micro-bubbles and solid phase aggregates and their removal from water. The former of the above stages has been named ultra-occulation ( UF ) and the latter turbulent micro-otation ( TMF ).

286

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

Table 2 Capture eciency E of particles by a bubble in otation (explanatory notes to Figs. 2 and 3) NN I Dimension class, size (mm) Submicron 00.5 Fine 0.530 Medium size 3070 Coarse 70200 Predominant capture factors Convective diusion in the surface forces eld Relationship E3d2/3a p E3d1.45 /D1.83b p E3const Reference [2]

II

Long- and short-range hydrodynamic interaction, surface forces

[36 ]

III

Inertia, short-range hydrodynamic interaction, surface forces

[7]

IV

Inertia, collision energy dissipation, dynamics and stability of wetting lm

E3d3/2 p

[8,9]

a d =particle diameter. p b D=bubble diameter.

Fig. 3. Capture eciency E of particles of various dimensional classes (density 7.5 g/cm3) by rising bubble (diameter 1 mm) vs. d (particle diameter): (I ) submicron; (II ) ne; (III ) mediump size; (IV ) coarse.

3. Ultra-occulation According to von Smoluchowski [11,12], the process of the aggregation of particles in the eld of the shear ow can be described by the formula: 4Q Gat d (t)=d exp A p 3p

(2)

evident from Eq. (2), increasing G allows us to achieve as a high rate of growth of the diameter, d , of aggregates as desired, and hence to ensure A eective coagulation (occulation) even for very low values of suspension concentration Q and particle aggregation eciency a [14]. The only physical limitation (apart from power consumption requirements) is the strength of aggregates in a highly non-uniform hydrodynamic eld [15] (the exception is the case of the coalescent regime of the aggregation). However, experimental researches have shown [16 ] that the application of modern occulants can ensure the occulation (for example, in a cylinder or disk-type Couette occulator) at energy dissipation values e over 104 J/kg s, to which G values of over 105 s1 correspond. The occulation performed in highly non-uniform hydrodynamic elds (e>1 J/kg s, G>103 s1) has been called ultra-occulation. This can be optimized with regard to niteness of aggregate strength by way of gradual decrease of G value with the growth of aggregates in the process of hydrodynamic treatment [17]. As has been shown in ref. [18], the maximum permissible dimension of aggregates is: d =A/G (3) A where A is a specic constant dependent on properties of particles, occulants and medium. In this case, according to ref. [19], maximum dimensions of aggregates can be achieved in minimum time of

where d is the diameter of the supposedly spheriA cally shaped aggregates, t is the treatment time, d is the initial diameter of particles, Q is the p volume concentration of particles, G is the gradient of the average velocity of a liquid, a is the aggregation eciency of particles at collision [13]. As is

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

287

hydrodynamic treatment, through maintaining a non-uniform hydrodynamic eld, provided the value of G decreases with time following the principle: G(t)=A

NC

4aQ d + At p 3p(1p)

(4)

where p is the porosity of aggregates. In this case their diameter in initial time instants will vary according to the principle: 4aQ At d (t)=d + A p 3p(1p) (5)

However, it should be noted that in highly nonuniform hydrodynamic elds eects are observed which can be attributed to a turbulent ow structure, which is not yet fully understood. In this respect the product Ga in Eq. (2) should rather be considered as a specic unied phenomenological parameter G (the factor of the coarsening of a aggregates), the dependence of which in terms of energy dissipation, properties of the occulant, particles and medium is still dicult to interpret. Fig. 4 illustrates the dependence of characteristics of G vs. e measured for particles of various nature a (oil droplets [20], micro-bubbles [21], and quartz crystals [22]). It should be emphasized that for both oil droplets (curve 1) and micro-bubbles

(curve 2) (in both cases spherical objects and coalescent aggregation regime), characteristic G a (e) display nearly identical extremum behavior, the dierence being that for oil maximum and minimum are observed at e values of 0.1 and 0.46 J/kg s accordingly (after which rapid growth commences in the range e>1 J/kg s), and for micro-bubbles e values are 0.3 and 4.6 J/kg s accordingly and rapid growth is observed in the range of values e>10 J/kg s. ( This phenomenon is used in the technology for water purication which will be described below.) In the case of quartz particles (having an irregular tapered shape), similar extrema are observed only in the range of very small e [22], not shown in the gure. In the range of high e, G increases monotonously. These variaa tions in G (e) characteristics for oil, quartz and a gas can result from dierences in the shape and dimensions of particles (oil droplets B 0.53.5 mm, bubbles B 1050 mm and quartz B 1.54.5 mm).

4. Turbulent micro-otation As has already been mentioned, the microotation of the suspension of even occulated particles has very limited eciency when the process takes place in a bulk-space chamber [10]. This can be explained by the fact that micro-bubbles (which anyhow have a very low rising velocity which, according to Stocks law, increases with increase of their diameter following a square relationship) loaded with otated contaminants are very slowly removed from the water through sedimentation. This process can be signicantly facilitated if separate bubbles (with attached contaminants or in the process of contaminants attaching to bubbles) are aggregated into large foam aggregates containing thousands of initial micro-bubbles. As follows from results shown in Fig. 4, this can be achieved by subjecting the otation mixture to relatively gentle hydrodynamic treatment (for example by way of passing it through a static mixer), described by levels of the energy dissipation e of the order of 0.3 J/kg s (G=500 s1), which corresponds to the maximum capacity of micro-bubble aggregation (see Fig. 4, graph 2), providing minimal destruction of oto-

Fig. 4. Growth factor of particle aggregates G in the turbulent a ow: (1) oil droplets (diameter 0.53.5 mm) [20]; (2) microbubbles (diameter 1050 mm) [21]; (3) quartz crystals (diameter 1.54.5 mm) [22], e=energy dissipation level.

288

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

aggregates. As has been shown in researches, the most suitable static mixer for this application can be designed as a pipeline of an appropriate length and diameter [23]. The turbulent ow generated wherein, as the otation mixture passes through, on the one hand allows us to facilitate the adherence of aggregates of particles of contaminants (and/or of sorbent) to micro-bubbles, and on the other hand to have coarse foam aggregates, easily separated from water by sedimentation, in which thousands of micro-bubbles happen to build between particles of suspension. This method of micro-otation has been called turbulent microotation [24].

5. UF/TMF technology The above described theoretical ndings allowed us to develop a technology for water purication from soluble and ne contaminants where the ultra-occulation and turbulent micro-otation are combined ( UF/TMF technology). The vital characteristic of UF/TMF water purication technology lies in the fact (see Fig. 1, alternative IV ) that a sorbent which is initially nely dispersed is added into treated water and the sorption of soluble and/or colloid dispersed contaminants (stage a) takes place. Upon completion of a sorption stage or close to its completion, a occulant is introduced into water and after that the mixture is subjected to a vigorous hydrodynamic treatment (for example, in a disk-type Couette occulator) at levels of the energy dissipation e>3 J/kg s [G>1730 s1 (stage c)]. In this case the higher the volume concentration of a suspension of a sorbent and/or contaminants, the more vigorous the treatment is required to generate coarse ocs in a short time [see formula (2)]. When stage c is completed or close to its nishing, treated water is saturated with microbubbles and again subjected to hydrodynamic treatment, but in this case under relatively gentle conditions, in a static mixer at levels of the energy dissipation of e$0.11.0 J/kg s [G$3501000 s1 (stages f and g)]. As a result, aggregates formed of particles of suspension will adhere to bubbles during a short time (stage f ) and then merge into

large foam aggregates (stage g) which can easily be separated from water by the sedimentation (stage h). To improve the quality of purication stages f, g and h can be repeated. Normally, stages f and g do not require introduction of any additional reagents as the majority of occulants also facilitate the adherence of contaminants to micro-bubbles and the aggregation of the latter into foam aggregates. In case when contaminants are non-soluble species and their collection does not require a sorbent, stage a may be skipped. Besides, stages a and c can be combined, as a vigorous hydrodynamic treatment facilitates the sorption by several orders of magnitude. It should be noted that the introduction of occulants under conditions of vigorous hydrodynamic treatment allows us to overcome diculties related to dissolving of occulants and adsorption on a surface of particles due to intensive convection. [In the case of high concentrations of contaminants and/or of sorbent and correspondingly high dosages of the occulant, these diculties are usually overcome by a considerable (up to 50%) dilution of incoming treated water, which is not always suitable.] It has also to be mentioned that in treating water with a high content of suspension (over 0.5 g/l ), before stage f, it is possible to perform short settling (for example in a continuous thinlayer settler) so as to remove most dense and large ocs and decrease the load at turbulent microotation (stages f, g and h). It is obvious that the proposed method allows application of several dierent sorbents and occulants (for example, the combination of cation and anion polyelectrolytes, as used for separation of waste lubricating coolant emulsions). Besides, in cases when a multichamber continuous ultraocculator is utilized, in which the mean velocity gradient of a liquid decreases following the principle (4), all the stages a, c, f and g can be combined. In this case, according to results shown in Fig. 4 (graphs 1 and 2), in the rst chambers with more vigorous treatment (e>3 J/kg s) the adsorption and aggregation of particles of contaminants and sorbent will prevail (drastic rise in graph 1). The coalescence of micro-bubbles will

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

289

slow (minimum in graph 2). In the middle chambers (e#12 J/kg s) the process of aggregate adherence to micro-bubbles and aggregation of these takes place, and nally at the output side of a occulator (e#0.20.4 J/kg s) micro-bubbles with captured particles will predominately aggregate into foam aggregates (maximum in graph 2, minimum in graph 1). By way of selecting the appropriate number of chambers (for example, of disk-type occulator) and the energy dissipation level, it is possible to achieve high aggregation levels of multiphase suspension (sorbentcontaminantsbubbles) in a short time with low power consumption requirements. It is also obvious that the concentrations of sorbents and micro-bubbles can also be varied. For practical applications of the above described UF/TMF technology, a plant has been developed and tested. An operational ow chart is presented in Fig. 5. Feed pump 19 supplies treated water placed in series with ultra-occulator 18, continuous thin-layer settler 16, electrolytic microbubble generators 9a and b, gentle hydrodynamic treatment loops 10a and b, foam separators 8a and b, rotameter 11, sensor 12 installed for control of incidental contaminants passing, ow passage sensor 13 and ow interrupter 14. [ These components actually form a sorption/occulation (19, 18, 16) and two micro-otation stages (9a, 10a, 8a) and (9b, 10b, 8b) connected in series.] The plant also incorporates an automatic unit for preparation and dosage of occulant solution and ne sorbent suspension (2a and b, 3, 4, 5, 6, 7). Following introduction of a ne dispersed sorbent (particle size below 1 mm) and/or a cationic occulant by means of proportioning pump 2a, the suspension is then subjected to special vigorous treatment in ultra-occulator 18, in the middle part thereof anionic occulant is also fed by means of the proportioning pump 2b. As a result, on the outlet side of the ultra-occulator, a bulk amount of suspended particles (around 99%) are collected into large aggregates which can easily be separated from water in a continuous settler 16. Following this stage, water is saturated with gas microbubbles (diameter 525 mm) generated in an electrolyzer 9a. Passing the thus generated threephase mixture through gentle hydrodynamic treat-

Fig. 5. UF/TMF ow chart (example): 1, inlet for treated waste waters; 2a,b, proportioning pumps; 3, occulant and sorbent containers; 4, clean water feed for preparation of occulants (sorbents) solutions (suspensions); 5, screw feeders; 6, feeding funnel for dry anionic occulants; 7, feeding funnel for dry sorbent or cationic occulants; 8a,b, foam separators; 9a,b, electrolytic micro-bubble generators; 10a,b, gentle hydrodynamic treatment loops; 11, rotameter; 12, sensor to prevent contaminants passing; 13, ow passage sensor; 14, ow interrupter; 15A, light wastes outlet; 16, continuous thin-layer settler; 17B, heavy wastes outlet; 18, ultra-occulator; 19, feed pump.

ment loop 10a ( long pipe-type static mixer) results in intensive heterocoagulation of remaining suspension with micro-bubbles and aggregation of the latter into large foam ocs. The latter are then easily separated from water as oat slime in a ow-type foam separator 8a (manufactured as Hallimond tube). After that, water is subject to one more stage of micro-otation treatment (9b, 10b, 8b) and goes to the output unit for quality

290

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291

control. The principal element of the latter comprises the optical sensor 12 which will shut down the plant when the turbidity of outgoing water exceeds a certain reference level. (The reference quality standard can be dened on the basis of other parameters, for example on the level of the water radioactivity). The above described pilot plant, having a capacity of 0.25 m3/h, has been tested for water purication from various types of contaminants including ne dispersed oils, radionuclides, heavy metals, and micro-organisms. For these applications the following sorbents have been used: natural materials (bentonite, clinoptylolite, kaolinite), nonorganic compounds [hydroxides of polyvalent metals ( Fe, Al ), ferrocyanides, oxides and others], micro-organisms (fungi, active slime, etc.). Flocculants applied have been selected from Allied Colloids product range, namely Magnaoc and Zetag. Appropriate matching and proportioning of various sorbents and occulants allows us to achieve a high standard of purication (up to 99.5%) in combination with minimum possible wastes and minimum treatment time.

of waste treatment plants without signicant investment. Besides, depending on variations of load on treatment plants, the G and hence e values can be accordingly increased or decreased, minimizing total energy consumption. Therefore, the proposed UF/TMF technology allows us not only to develop a new space-saving (or even mobile) water purication system which can be placed, for example, at sea-going ships or oil platforms, but also to signicantly improve the eciency of existing facilities for waste treatment (for example, facilities for municipal waste waters treatment), without the necessity for signicant investment.

Acknowledgments The author is deeply grateful to INTAS-Fund, which has provided nancial support under Projects Ukraine 95-0165 and 96-1922 which ensured the possibility of carrying out the above research, as well as to Allied Colloids Co. who have kindly supplied samples of occulants for laboratory and eld tests of the pilot UF/TME plant. The author also expresses his appreciation and gratitude to the teams of Kiev Aircraft factory and Antonov Design bureau for their contribution and support in the process of manufacturing and testing the plant.

6. Conclusions The major advantage of the above mentioned UF/TMF technology consists in the fact that this technology allows us to clean signicant amounts of water with relatively low concentration Q of contaminants (for example, below 50 mg/l ). According to Eq. (2), the rate of aggregation of particles of contaminants varies exponentially with volume concentration Q of contaminants and/or sorbent. In conventional technologies (see Fig. 1, IIII ) similar results can be achieved during long treatment time (several hours) of relatively gentle hydrodynamic treatment (e<0.01 J/kg s, G<100 s1); these technologies also require much space for building operational tanks (as, for example, is the case in drinking water treatment applications), which involves signicant investment. In case of UF/TMF technology, the negative eect of low content Q of suspended particles is balanced through vigorous hydrodynamic treatment ( large G values) which allows us to increase the eciency

References
[1] N.N. Rulev (Rulyov), Khim. Tekhnol. Vody 11 (1989) 195. [2] D. Reay, G.A. Ratcliff, Can. J. Chem. Eng. 53 (1975) 481. [3] D. Reay, G.A. Ratcliff, Can. J. Chem. Eng. 51 (1973) 178. [4] G.L. Collins, G.J. Jameson, Chem. Eng. Sci. 31 (1976) 985. [5] J.F. Anfruns, J.A. Kitchener, Trans. Inst. Min. Metall. 86 (1977) 9. [6 ] N. Ahmed, G.J. Jameson, Int. J. Min. Proc. 14 (1985) 195. [7] N.N. Rulev (Rulyov), S.S. Dukhin, A.G. Chaplygin, Kolloidn. Zh. 49 (1987) 939. [8] H.J. Schulze, Min. Process Extract. Metall. Rev. 5 (1989) 43. [9] N.N. Rulev (Rulyov), A.G. Chaplygin, Kolloidn. Zh. 50 (1988) 1144. [10] N.N. Rulev (Rulyov), S.S. Dukhin, Khim. Tekhnol. Vody 2 (1980) 217. [11] M. von Smoluchowski, Phys. Z. 17 (1916) 583.

N.N. Rulyov / Colloids Surfaces A: Physicochem. Eng. Aspects 151 (1999) 283291 [12] M. von Smoluchowski, Z. Phys. Chem. 92 (1917) 129. [13] T.G.M. Van de Ven, S.G. Mason, J. Colloid Interface Sci. 57 (1976) 505. [14] N.N. Rulev (Rulyov), B.P. Rjaschenko, Khim. Technol. Vody 11 (1989) 697. [15] D.S. Parker, W.J. Kaufman, D. Jenkins, J. Water Pollut. Control Fed. 43 (1971) 1817. [16 ] K. Muhle, K. Domasch, T. Neee, Chem. Technol. 34 (1983) 14. [17] N.N. Rulev (Rulyov), Kolloidn. Zh. 47 (1985) 982. [18] K. Muhle, A. Ivanauskas, T. Neee, Chem. Ing. Tech. 55 (1983) 788.

291

[19] N.N. Rulev (Rulyov), Kolloidn. Zh. 47 (1985) 721. [20] N.N. Rulev (Rulyov), S.V. Karas, Khim. Technol. Vody 12 (1990) 887. [21] N.N. Rulev (Rulyov), S.V. Karas, Khim. Technol. Vody 12 (1990) 603. [22] A.J.G. Van Diemen, H.N. Stein, J. Colloid Interface Sci. 96 (1983) 150. [23] N.N. Rulev (Rulyov), A.A. Baichenko, Kolloidn. Zh. 48 (1986) 302. [24] N.N. Rulev (Rulyov), Khim. Technol. Vody 1 (1979) 9.