DESALINATION

ELSEVIER Desalination 152 (2002) 237-244 www.elsevier.com/locate/desal

Fluidised bed crystalliser and air gap membrane distillation as a solution to geothermal water desalination
Salah Bouguecha, Mahmoud Dhahbi*
INRST, BP 2050 Hammam-Lif, Tunisia Fax +216 (71) 430 934; emails." mahmoud dhahbi@inrst.rnrt, in, salah,bouguecha@innotech, rnrt.tn Received 30 March 2002; accepted 10 April 2002

Abstract

Tunisia has five major geothermal districts. Recorded hot spring temperatures range from 294 to 340 K with flow rates 0.1-102 L/s. In southern parts available groundwater resources are mostly hard and brackish (3 g/L). Recently, Tunisia has resorted to this resource for agriculture and potable water uses. Cooling towers have been built to lower down the temperature and hardness. Cooled brackish water irrigates greenhouses and feeds desalination plants. The cooling operation of groundwater rejects an important quantity of thermal energy in the atmosphere. However, energy requirements of thermal desalination plants are too excessive to be supplied by a geothermal resource. Membrane distillation (MD) is an emerged desalination technology, which can be driven by a thermal energy at low enthalpy (less than 363 K) as geothermal energy, and a fluidised bed crystalliser can ensure reduction of an important portion of hardness without significant loss of temperature. MD is realised by means ofa microporous hydrophobic membrane separating a warm solution from the cooling chamber, which contains either liquid or gas. A fluidised bed crystalliser permits production of from it of a granular crystal calcium carbonate from the consumption rates of calcium ions, using aragonite or sand as seeding materials. The purpose of this paper is to realise experimental assembly constituted of fluidised bed crystalliser (FBC) and a cell of air gap membrane distillation (AGMD). It presents preliminary results related to characterisation of fluidised bed, growth of seeded particles size of CaCO 3 and operating parameters of AGMD. In laboratory scale, the technical feasibility has been shown. More investigation is needed to prove the efficiency and availability of coupled AGMD with FBC. Keywords: Fluidised bed crystalliser; Air gap membrane distillation; Geothermal groundwater

*Corresponding author. Presented at the EuroMed 2002 conference on Desalination Strategies in South Mediterranean Countries: Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European Desalination Society and Alexandria University Desalination Studies and Technology Center, Sharm El Sheikh, Egypt, May 4-6, 2002. 0011-9164/02/$-- See front matter 2002 Elsevier Science B.V. All rights reserved PII: S0011-9164(02)01069-X

238 1. Introduction

S. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244

A number of places with geothermal springs have been known for a long time in Tunisia, some of which have been used for bathing therapeutic treatments (e.g. Korbous, EI-Hamma, and Hammam-Zriba). Ben Dhia subdivided Tunisia into five major geothermal districts [ 1]. In the southern part of the country, where the fresh water problem is most acute, available groundwater resources are mostly hard and brackish. Since the 1980's, Tunisia has resorted to these resources, so cooling towers have been built to lower hardness and temperature. Softened and cooled waters obtained are used for agricultural greenhouses [2] and for feeding RO plants [3]. The cooling operation dissipates an important quantity of energy, and 4 5% of water in the form of steam is lost in the atmosphere. Moreover, cooling towers operate at a discontinuous regime due to adhesion of sludge on the walls and an important deposition ofCaCO 3 in the pipeline transporting cooled waters. Hanafi [4] concludes that geothermal groundwater resources, at low enthalpy, are not expected to play a role in conventional desalination technologies (MSF or MED). However, thermal MD using a sensitive heat can be driven by a solar heater such as plane captors. Hogan et al. [5] have studied the feasibility of solar powered domestic drinking water in arid rural regions of Australia. For the domestic sized plant of 50 kg/d the optimum configuration appears to be a solar collector area of around 3 m 2, a membrane area of 1.8 m 2 and a total heat exchange are of 0.7 m 2. This configuration presents a competitive cost with RO. The integration of different membrane operations is becoming quite attractive as a way for increasing the performance of the processes. For a desalination operation the integrated RO+MD operates on the RO reject brine and further increases the overall performance but the system requires higher energy consumption due to the thermal demand (MD requirement). The energetic balance has shown that the integrated MD systems have better performance with respect to thermal processes

such as MSF or MED and might represent an interesting option for desalination operations [6,7]. M.C. de AndrOs et al. [8] have coupled a MD module to a multiple effect distiller for pure water production. The study has shown that the best operating parameters are 85C for a feed brine temperature at the evaporator inlet and a circulation flow of about 170 kg/h. Under these conditions, a GOR value of 3.7 and a water production of 16 kg/h may be reached. The integration of one membrane module distiller as a second step at the MED outlet permits an increase of distilled water production by about 7.5% and improvement of the energetic efficiency by practically 10%. Energetic analysis shows that MD can be driven by low enthalpy sources such as geothermal groundwater. Nevertheless, hardness must be shut down without a sensitive loss in temperature. Fluidised bed crystalliser presents a possible solution for sensitive hardness reduction with a non-significant temperature loss. FBC using a suspended seed is applied to produce granular CaCO 3 from hardness mother solution. The seed growth is ensured by only a loss of CO 2 in the atmosphere and at a low supersaturation value of a mother solution. A conical FBC with a tangential orifice is developed and characterised in the first part of this study. The second part is devoted to realisation of an AGMD cell using a frigorific cycle as a cooling chamber. The results obtained for FBC and AGMD are presented and discussed in the present paper.

2. Fluidised bed crystalliser Calcium carbonate is the predominant component of hard and tenacious scale deposited from natural waters. The inverse solubility of calcium carbonate is often responsible for scaling occurring in heat transfer processes. Among the methods dealing with the problem of CaCO3 deposited is the a FBC or pellet reactor. FBC operates with lime or sodium hydroxide in

S. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244

239

contact with a hardness solution in granular media (seed of carbonate or sand). Van Dijk et al. [9] have presented the fundamentals and state of the art of pellet softening water as an example of clear technology, instead of gelatinous sludge by pure solid grains. Several models of pellet are performed concluding that the performances are dependant on particles of the size of milk lime. Moreover, a short-circuit may occur as a result of improper distribution o f the water by the inlet nozzle, and the high flow velocity leads to erosion of pellets. Most works concerning hardness removal use FBC as a liquid-liquid system, such as milk lime or sodium hydroxide. The growth of crystalline car-bonates in supersaturated solutions, the effect of pH, ionic strength, size, nature of seed, and effect of certain ions such as magnesium and iron have been extensively studied [9-11]. The problems in the geothermal systems arise mainly from the loss of carbon dioxide as the pressure is reduced when the water in a well moves close to the earth surface respect to calcium carbonate takes place with the loss CO 2.The composition of Chott EL-Fejjij depth well (southern Tunisia) is summarised in Table 1. Table 1 Water composition of Chott EL-Fejjij well depth
Cationic Ca 2+, mg/L

Few studies have been made on crystallisation by gas-liquid reaction in which solid particles are formed by the dumped gas (carbon dioxide). The influence of the mass transfer coefficient on crystal-lisation size distribution during the batch precipi-tation of calcium carbonate was studied and compared with the prediction theory [12]. Several reactor models have been developed [ 13]. In the present work, a conical fluidised bed granulator with vortex orifice is realised and characterised.
2.1. Experimental setup

440

Mg2,mg/L Na, mg/L K, mg/L

NH4+

51.03 601.0 48.2

0.2

Anionic HCO3-, mg/L SO42-, mg/L CI-, mg/L F-, mg/L SiO2, mg/L Free CO2 TDS TAC, of Temperature, K pH

Fig. 1 shows a schematic diagram of the experimental setup. Feed solution was mixed and pumped from a tank (5 L) to the crystalliser at different temperatures. The FBC is composed of three parts. The conical column with a large apex angle o f 30 is 0.02 m in inlet diameter (ID) and 0.195 m in height. The cylindrical column has 0.195 m ID and 0.190 m in height. The third part is a cylindrical column to avoid dumping fine particle of seed. All columns are made of Plexiglas. The vortex orifices realised in an independent cylindrical room are mounted at the bottom o f the cone part. There are four tangential injection nozzles with 4.10 -3 m ID and convex orifice for creating a partial vacuum in the bottom o f the FBC when we open the valve; the granular ofCaCO 3 is ejected out the FBC without a liquid entrainment. The height of the bed is calculated from the introduced seed mass, particle density and occupied volume. The flow meter gives the feed flow. pH sensor measures the value of pH in the mother solution and in FBC.
2.2. Results and discussion 2.2.1. Pressure drop

122.0 1047.8 1000.0 0.3 35 19.5 3230 132 338 6.6

Fig. 2 shows the pressure drop (AP) as a function of feed flow. AP increases linearly from 0 to APm~ with feed flow. After that AP decreases as a curvilinear curve and then reaches a constant value dependant on particle sizes. Increasing and

240

S. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244

1 Resistance 2 Feed tard 3 3 Motor 4 l.txapl e r 5 Pressure Value

6 Pump 7 Vortex Orifice

8 Conical Colutnn 9 Cyiindrica Column

10 G r a n u l a t o r exit N2
Co2 11 Value 12 I~H meter 13 Liquid ]Flow meter 14 M a n o m e t e r 15 Differential manometer

13

10

)._14

.~

~:~
Fig. 1. Experimental setup of FBC.

0.9 d p = 0 . 6 ~
dp=lmm

0.8 06 y = 0.8958x .2=, ~_O

-~0.6

"~ 0.4
"~0.3 .o 0 0 70 1O0
Feed flow (Q L/h)

-5/
i 0 ~ 0.2 Kmr=0'90% 0.4 APmf,Cal 103 (Pa) 0.6 0.8

0.2

160

250

Fig. 2. Pressuredrop as a function of feed flow. decreasing feed flow do not give the same curves between the fixed bed and fluidised bed. Experimental minimum feed flow is taken at an intersection point of the two straight lines in a decreasing mode. Minimum velocity is estimated by the relation
U = Q/21-I R 2 (with R = H.sincz)

Fig. 3. Comparisonbetween AP:co~ and APml:,~p.

AP,,~r<,a, Kr(l - e,,~) = (9.,-pr)g'HB,.f.

(2)

~Omfi, a/VS. L~kPmfex presented in Fig. 3 gives Kmj p equal to 0.905%. The value proposed by Kurita et al. is K r = 0.8510% in the case of air taken as fluid. For cylindrical fluidised bed, K / = 1 [13].

(1)

To predict pressure drop A P t at minimum particle fluidisation in a conical fluidised bed, an empirical correlation equation was used:

2.2.2. Minimum fluidisation velocity

The correlation of log Remr with log (HBm/ D)L25Ar~ is shown in Fig. 4. The fitted value of 0~

S. Bouguecha, M. Dhahbi / Desalination 152 (2002)237-244

f .....................................................................................................................................................................................

241

1.90 1"75 l

log Rc,,~/.,,,~, = 1.0046 log (HBmf/Di).Ar osl + 2 . 2 4 2 ~

160,
~ 1.45 1.30 1.15 -I .2 " -1 -0.8 ' . . . . . . . . . . . ~' " -0.6 -0.4

-0.2

log (Hl~,,,t/Dt).Ar 'sl

entrainment for a wide range size. Experimental pressure drop complies with the theoretical calculation. The value obtained for the Archimedes number power agrees with those proposed in literature. The conical granulator fluidised bed with vortex orifice has several advantages such as stability of incipient fluidisation and 30 apex angle suppress slugging and reduce bed extension and its fluctuation effectively over a much wider range of fluidisation feed flow.
3. Membrane distillation

Fig. 4. Relationship between (HH,JD).Ar-~I and Re t:~p.

is equal to 0.51 .Then: Re,,/:~x~,=17 10-:.(H~,,/D,)' 2'.Ar ~' (3)

The Archimedes number powers (c~) in cylindrical column proposed by Kumar et al. [14] and Markowski et al. [15] are respectively 0.61 and 0.57.
2. 2. 3. Seed growth

The aragonite powder (11 for 5.5.103 mg) was dissolved in 5 L of distillate water. The obtained solution was stirred for 4 h in an agitated vessel and the solution circulated in the loop under CO 2 atmosphere. The FBC valve was opened at feed flow of 150 l/h and the FBC was bubbling with nitrogen during a few minutes. The aragonite seed was introduced by the FBC's top and maintained in a cylindrical column by high feed flow. Experimental runs were made with seed of 0.3 mm at two temperatures - - 333 and 353 K. The preliminary qualitative results show that seeds have occupied two levels. The first one is constituted by fine and dispersed particles, and in the second level particles have more density. After 5 rain, we observed that some particles occupied the conical column and fold down at the FBC's bottom. The visual observation showed an increase of the particle size. The X-ray diffractogram shows that tile precipitate nature is the same as that of the initial seed. The results show a constant pressure drop for high feed flow and consequently no particles

The desalination of brackish or seawater can be accomplished by two procedures - - thermal distillation processes and membranes processes. The thermally driven membrane desalination considered here is a sort of a hybrid process, in which a microporous hydrophobic membrane separates a warm solution from a cooling chamber, which contains either liquid or gas. Vapour molecules migrate through the membrane pores from the high to the low vapour pressure side that is from the warmer to the cooler compartment. The separation mechanism of membrane distillation is based on vapour-liquid equilibrium (VLE). The membrane distillation process exists in four configurations [16]. Direct contact membrane distillation (DCMD), the oldest and most widely configuration used, has liquid phases on direct contact with both sides of the membrane. It is best suitable for applications in which the major fluxing component is water, such as desalination or concentration of aqueous solutions. AGMD has an additional air cavity interposed between the membrane and condensation surface. It is applied when water is volatile and can also be used to remove trace volatile components from aqueous solutions. Vapour membrane distillation (VMD) and gas membrane distillation (SGMD) are respectively applied to remove volatile components and to recover organic compounds from aqueous solution. An AGMD cell is realised and tested in the laboratory as described below.

242 3.1. Experimental tool

s. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244 Fig. 6. At constant temperature, the permeate fluxes increase rapidly with feed velocity, and they seem to reach maximum values asymptotically for higher feed flow. This is due to the reduction of the boundary layer thickness when the Reynolds number increases, approaching a limiting value [ 17]. At constant feed flow rate, we observed that increasing temperature was accompanied with increasing permeate flow. Fig. 7 represents the variation of permeate flux vs. temperature difference between the feed temperature solution and condensate plate ( T - ~). The permeate flux increases sensitively with AT. At 45 K, the flux varies sensitively with Re number or the feed velocity. We noted that the transmembrane temperature increases as a function of feed flow and the conductivity of the permeate remains invariable around 6 gs/cm. 3.2.2. Effect of concentration Fig. 8 shows the relationship between the permeate flux and the concentration of sodium chloride feed solution. The permeate flux insensitively decreases when the feed NaCi concentration was raised from 3 to 35 g/L, the permeate quality was 6 gs/cm. The flux reduction can be attributed

The AGMD experiments were performed with the apparatus schematically shown in Fig. 5. The feed was contained in a thermostatic reservoir and it was circulated through the membrane cell using a variable peristaltic pump in a cross-flow mode. The membrane cell was made of Plexiglas. Two membranes in parallel have been used and separated by a 12 mm thick cell of Plexiglas. The last one includes a cooper serpentine where the frigorific fluid is circulated. A polypropylene grid supported the membrane, and immediately after a gasket (2 mm thick) was placed. The effective membrane area was 64+0.04 cm 2 for each one. The cooling plates on which the permeate vapour condensed were placed. A calibrate graduated cylinder was used to collect directly the permeate that fell through a channel and two outlet tubes located at the lower part of the cooling plates. 3.2. Results and discussion 3.2.1. Effect o f feed flow rate The variation of the permeate flux as a function feed flow at different temperatures is plotted in

worm chamber membrane support grid

I thermostatic reservoir

2 peristatie pump 3 manometer

4 compressor 5 heat exchanger 6 graduate cylinder

membrane
condensing plate gap gasket cooling chamber

Fig. 5. Experimentalsetup of AGMD.

S. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244

243

7
6

.....................................................................................................................................................................

E=2mm'C=3000ppm'Tr=274K/'-'~.
~

T =333 K

ff 4 ~ 3 o 2 ~, I 0

~ / / = . ... 2 2.5 T=313K 303 K ~ T 4~4~-"'0.5

3.6 ..................................................................................................... * Tf= 294 K, E=2mm 3.4 ~-~ 3.2 Q = 0.0011C2 - 0.0655C + 3.5509 3 2.8 7 t

426

~ 2.4 a. 2.2 5 10 15 20 25 30 NaCI concentration of feed solution, C (g/L) 35

1 1.5 Feed flow rate, D (L/rain)

Fig. 6. Permeateflux vs. feed flow rate.

Fig. 8. Permeateflux vs. salt concentrationin feed solution. of single fluxes in each of the membranes. In this case, three stages can be connected successively allowing a permeate flux mostly larger than those given by only one stage. However, the global permeability ofhydrophobie membrane remains very low to produce a high flux. Then the MD has a low recovery fraction compared to other membrane processes as RO (75 kg.m-:h-~) [16].
4. Conclusions

~'1018............................................................................................................................................................................... E ffi2 rra'a, Tf = 294, C = 3000 ppm

~-6
~4]
t~

10

20 30 Temperature difference, AT (K)

40

Fig. 7. Permeateflux vs. temperaturedifference.

to several causes - - vapour reduction due to the salt effect, increased temperature polarization, and concentration polarisation at membrane surface. Schneider et al. [18] found similar results of marginal feed concentration effect on permeate flux and quality. The effect on AGMD processes on relevant operating parameters such as temperature, feed flow rate and feed concentration has been analysed. The permeate flow is strongly dependant on the temperature. An increase of the permeate flow with feed velocity seems to reach maximum value asymptotically to 7.5 kg.m-2h-~. Flux is practically insensitive to the feed concentration. Moreover, it is possible to connect more than one membrane by using conventionally high values of the circulation velocities. The permeate flux is the addition

Tunisian geothermal springs are characterised by high hardness and low-grade temperature. The FBC vortex orifice granulator tool was realised and tested for the precipitation of calcium carbonate under aragonite variety. MD using a low-grade temperature is the suitable desalination process for this case. An experimental setup AGMD has been proposed, and relevant operating parameters are studied. Preliminary results seem to be in favour of coupling the two processes with the aim of geothermal desalting. More investigation is needed to optimise FBC design and operating parameters and to prove the efficiency and the availability of coupled AGMD or other MD configuration, such as SGMD with FBC. However, it seems that MD recovery fraction is not able to reach a high value using only a sensible heat from a geothermal well. In this case, two possibilities can be envisaged. The first one, taking advantage of solar energy potential, the coupled solar plan

244

S. Bouguecha, M. Dhahbi / Desalination 152 (2002) 237-244

- - Water density, kg.m -3 - - Particle density, kg.m -3

collectors and geothermal energy can increase considerably MD efficiency. The second way consists o f integrating several membrane processes, such as M D + R O where RO uses softening and warm brine o f MD. This configuration can give a very high recovery factor widely superior to 80%.

o,,

References
[ 1] H. Ben Dhia, Les provinces g6othermiques en Tunisie, Th~se d'Etat, Universit6 de Bordeaux I, 1983. [2] F. Ben Jemaa, I. Houcine and M.H. Chahbani, Renewable Energy, 18 (1999) 331-347. [3] F. Kamel and H. Cheheibi, Desalination, 136 (2001) 263-272. [4] A. Hanafi, Desalination, 97 (1994) 339-352. [5] P.A. Hogan, Sudjito, A.G. Fane and G.L. Morrison, Desalination, 81 (1991) 81-90. [6] E. Drioli, F.L. Lagana, A. Criscuoli and G. Barbieri, Desalination, 122 (1999) 141-145. [7] A. Criscuoli and A. Drioli, Desalination, 124 (1999) 243-249. [8] M.C. de Andr6s, J. Dria, M. Khayet, L. Pena and J.l. Mengual, Desalination, 115(l 998) 71-81. [9] J.C. van Dijk and D.A. Wilms, J. Water Sci. Tech., 40(5) (1991) 263-280. [10] M. Clifford, C.Y. Tai, W.C. Chien and C.Y. Chert, AIChE J., 45(8) (1999) 1605-1614. [11] R. Vacassy, J. Lemaitre, H. Hofmann and J.H. Gerlings, AIChE. J., 46(6) (2000) 1241-1252. [12] S. Wachi and A.G. Jones, Chem. Eng. Sci., 46(12) (1991) 3289-3293. [13] Y. Kurita, H. Iida and I. Sekiguchi, J. Chem. Eng. Japan, 30(1) (1997) 166-169. [14] A. Kumar, Y. Chandra and N.G. Krishana, Canadian J. Chem. Eng., 61 (1983) 377-381. [15] A. Markowski and W. Kaminski, Canadian J. Chem. Eng., 61 (1983) 377-381. [16] K.W. Lawson and D.R. Lloyd, J. Membr. Sci., 124 (1997) 1-25. [17] M.C. Garci-Payo, M.A. lzquierdo-Gill and C. Fernandez-Pineda, J. Membr. Sci., 169 (2000) 6180. [18] K. Schneider, W. Holz and R. Wollbek, J. Membr. Sci., 39 (1988) 25-41.

Symbols
Ar
D
0 i --

- - A r c h i m e d e s n u m b e r (= gd3(p/, - 9 )

p/F/

DP E g
HBn!f

----

J
K~/
Q

---

Re,,!t - R i

T Tc'
v,

---

Feed flow rate, L.min -~ Diameter o f vortex orifice, m Diameter o f seed, m Thickness o f air gap, mm Gravitational acceleration, ms -2 Total depth at minimum fluidisation, m Permeate flux, kg.m-Zh -1 Correction coefficient defined equation Water feed flow, Lh -I Reynolds number at minimum fluidization (= dppp U , ] g ) Radius o f vortex orifice (= D/2), m Temperature, K Hot (or warm) temperature, K Cold temperature, K

Greek
AP - - Pressure drop at minimum fluidisation, Pa APe, / - - C a l c u l a t e d pressure drop at minimum fluidisation, Pa A P / . - - Experimental pressure drop at minimum fluidisation, Pa AT - - Temperature difference, K ~1 - - Void fraction at minimum fluidisation ktI - - Water velocity, kg.m-~s -L