Mass transfer processes with limited sensible heat exchange

Abstract

A process of mass transfer is described which utilises latent heat transfer with little or sensible heat transfer. In a preferred process microbubbles are used under certain conditions of contact with a liquid phase to ensure highly effective mass transfer between a gaseous and liquid phase with significantly less than expected or little or no sensible heat transfer. The present invention in part provides a means by which the known state of a cold liquid of varying depths can be changed using a hot gas injected via a micro bubble inducing internal mixing without allowing the resultant mixture to reach equilibrium thereby ensuring the transfer process becomes continuous. Thus a process is described wherein at least one gaseous phase is contacted with at least one liquid phase such that the heat ratio of the system (AA) is maintained at an a value of greater than 0.5, and the mass transfer is effected by passing a gaseous phase comprising microbubbles through a liquid phase of thickness no more than 10 cm.

Claims

1. A process for the mass transfer of at least one volatile component in a gaseous phase at temperature t.sub.2 into a liquid phase of thickness D at a temperature to which is higher than the temperature t.sub.2 of the gaseous phase and the heat ratio (α) of the system in which Q.sub.T, is total heat loss and Q.sub.S is sensible heat transferred $\alpha =\frac{Q_T-Q_S}{Q_T}$ is maintained at a value of greater than 0.5, which process comprises contact of the gaseous phase in the form of microbubbles with control of liquid thickness D such that the volatile component dissolves into the liquid phase and the gaseous phase has traversed distance D through the liquid phase.

2. A process according to claim 1, wherein the heat ratio is maintained at a value of greater than 0.6.

3. A process according to claim 1, wherein the heat ratio is maintained at a value of greater than 0.7.

4. A process according to claim 1, wherein the heat ratio is maintained at a value of greater than 0.9.

5. A process according to claim 1, wherein the liquid phase thickness is no more than 5 cm.

6. A process according to claim 1, wherein the liquid phase thickness is no more than 4 cm.

7. A process according to claim 1, wherein the liquid phase thickness is no more than 3.5 cm.

8. A process according to claim 1, wherein the liquid phase thickness is no more than 3.0 cm.

9. A process according to claim 1, wherein the liquid phase thickness is no more than 2.5 cm.

10. A process according to claim 1, wherein the liquid phase thickness is no more than 2.0 cm.

11. A process according to claim 1, wherein the liquid phase thickness is no more than 1.0 cm.

12. A process according to claim 1, wherein the liquid phase thickness is no more than 0.5 cm.

13. A process according to claim 1, wherein the liquid phase thickness is at least 100 microns.

14. A process according to claim 1, wherein the microbubbles have a mean diameter of 2 mm or less.

15. A process according to claim 1, wherein the microbubbles have a mean diameter of 1.5 mm or less.

16. A process according to claim 1, wherein the microbubbles have a mean diameter of preferably 1 mm or less.

17. A process according to claim 1, wherein the microbubbles have a mean diameter of 0.5 mm or less.

18. A process according to claim 1, wherein the microbubbles have a mean diameter within the range of 0.03 to 2 mm.

19. A process according to claim 1, wherein the microbubbles have a mean diameter within the range of 0.03 to 1.5 mm.

20. A process according to claim 1, wherein the microbubbles have a mean diameter within the range of 0.05 to 1.5 mm.

21. A process according to claim 1, wherein the microbubbles have a mean diameter within the range of 0.05 to 1 mm.

22. A process according to claim 1, wherein the microbubbles have a mean diameter within the range of 0.05 to 0.5 mm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A present invention is exemplified and will be better understood upon reference to the following non-limiting examples in conjunction with the accompanying drawings in which:

(2) FIG. 1 is a schematic of the apparatus of the present invention as used in the examples;

(3) FIG. 2 is a simple schematic of the bubble column;

(4) FIG. 3 is a plot of percentage evaporation versus water level for Example 1;

(5) FIG. 4 is a plot of outlet air humidity versus time for different liquid levels for Example 1;

(6) FIG. 5 is a plot of methanol concentration in remaining mixtures versus liquid level for Example 2;

(7) FIG. 6 is a plot of temperature of mixture against time for different liquid levels for Example 2;

(8) FIG. 7 is a plot of heat ratio (a) against liquid level for Example 2,

(9) FIG. 8 is a plot of percentage evaporation versus water level for Example 4 deionised water; and

(10) FIG. 9 is a plot of percentage evaporation versus liquid level for Example 4 deionised water/ethanol mixtures.

EXAMPLES

(11) The main apparatus and general conditions used for the experiments include: a cylindrical tank, a micro-porous ceramic diffuser, a fluidic oscillator, an air heater and a temperature controller (for air—heater). A description of these apparatus is provided as follows.

(12) A cylindrical tank with a 14 cm internal diameter and 34 cm height was used for the experiments. The tank is constructed from Perspex (PMMA); a transparent material which allows monitoring of bubble behavior within the tank. A funnel is present at the upper area of the tank to help direct rising vapour to the gas outlet tube of the cylinder and to help reduce vapour condensation. The tank is rested on an aluminium base with three vertical support stands. The top of the cylindrical tank was covered with a Perspex lid and sealed with silicon adhesive. A micro-porous ceramic diffuser is fitted at the bottom of the tank for use in bubble generation. The diffuser together with the tank constitutes a bubble column.

(13) The diffuser used in this study is manufactured by HP technical ceramics limited, Sheffield. The ceramic used in constructing the diffuser is composed mainly of Alumina and fused silica. The diffuser has two gas stream inlets with diameters 6 mm. It has an internal and external diameter of 10.2 cm and 11.2 cm respectively and pore diameters of 20 μm. The internal area of the diffuser is 78.5 cm.sup.2 and its pore number density is 10000 pores/cm.sup.2.

(14) An electric heater with a power rating of 1.5 kW was used to raise the temperature of inlet gas to the desired value for experiments. A 25 m heating coil is contained within the heater. The temperature of the heater is controlled by a temperature controller. When connected to an electricity supply, the controller displays a set point temperature for the heater which can be varied depending on the required air inlet temperature to the diffuser.

(15) A fluidic oscillator as generally described in international patent application no. WO2008/053174 was used in generating the microbubbles used in some experiments. The principles underlying the operation of a fluidic oscillator has already been described earlier in this specification. A fluidic oscillator constructed from aluminium was used instead since aluminium is a better thermal conductor and can withstand the high temperatures that would be used during the experiments. The fluidic oscillator has a feedback loop 1 m in length connecting the two control terminals. The output and supply terminal have diameters of 6 mm, while the control terminal has a diameter of 5 mm.

(16) A Precision gold N18FR temperature and humidity probe meter was used in measuring the relative humidity of air streams. The probe is introduced in the pathway of an air flow to measure its relative humidity.

(17) Air flow meters (i.e. rotameters) were used to measure the flow rate of air entering and leaving the system. A flowmeter having a flow range of 30-150 Lmin.sup.−1 was used to measure the inlet-air flow rate in all experiments. The flowmeter used to measure outlet air flow was either of two types depending on the magnitude of the outlet flow which varied from 1 Lmin.sup.−1 to 50 Lmin.sup.−1 between experiments. A flowmeter with a flow range of 100-1200 cm.sup.3min.sup.−1 was used for measuring low outlet flow rates. For higher outlet flow rates, a flowmeter with a range of 6-50 Lmin.sup.−1 was used instead.

(18) A total of five thermocouples have been used for the experiments. They were all K-type thermocouples (Ni Cr.sup.+/Ni Al.sup.−). The thermocouples were connected to a Comark Model 6400 Microprocessor Thermometer which displays the temperature reading from the thermocouples. The microprocessor thermometer serves as a temperature monitor and it has a knob for switching between temperature readings from different thermocouples.

(19) A digital stopwatch timer was used to record time during experiments.

(20) The chemical concentration of methanol-water solutions were estimated using gas chromatography (GC) equipped with a thermal conductivity detector (TCD). Gas chromatography was chosen as the analysis method because it has a good sensitivity to volatile organics. A Varian 3900 reverse phase gas chromatography system equipped with a 2 m Hayesep P column was used. The column was pressurised using compressed nitrogen gas at 10 psi and the column oven temperature was held at 140° C. The TCD detector and injector were at 180° C. and 150° C., respectively. After each run, the GC equipment estimates the percentage peak area of methanol and water in a sample.

(21) Equipment Set-Up

(22) The equipments were set up in two different configurations depending on whether or not a fluidic oscillator is present.

(23) Set Up with Fluidic Oscillator

(24) A schematic of the set up is shown in FIG. 1. The system is fed with pressurised air from a main air supply. The air passes through a flowmeter to measure its flow rate before being sent to the air heater to raise its temperature. After passing through the heater, the air flows into the supply terminal of the fluidic oscillator after which the air flow is divided between the bleed valves and the inlet pipes to the diffuser. The bleed valves are present to remove excess air that is not required at the diffuser inlet. The inlet air that is not bled off passes through to the inlet ports of the diffuser into the cylindrical tank where bubbles are formed in a presence of a liquid.

(25) The inlet air temperature is measured at the pipe connection between the fluidic oscillator and the bubble column by two thermocouples having their sensor inserted into the middle section of the two inlet pipes. A thermocouple with its sensor located near the bottom of the bubble column was used in measuring the liquid temperature in the tank. A further thermocouple was located in the outlet air pipe for measuring the outlet air temperature.

(26) Valves (V.sub.1 and V.sub.2) were used to prevent the flow back of liquid into fluidic oscillator when the system is not in operation. V.sub.1 and V.sub.2 were also useful for controlling the gas flow into the cylindrical tank. The pipes connecting the heater, fluidic oscillator and bubble column are 6 mm in diameter and made from copper. Copper was used so that the pipes can withstand high temperatures used in the experiments. The drain valve (V.sub.5) is used to remove liquid from the cylindrical tank by employing a siphon effect.

(27) Set Up without Fluidic Oscillator

(28) The apparatus set up without fluidic oscillator is very similar to that with the fluidic oscillator. The main difference is that the fluidic oscillator was replaced with a Y-Junction as illustrated in FIG. 1.

(29) Materials

(30) The pressurised air used in the experiments was obtained from a main air supply pipe present in the laboratory. The pressure of the air supply could be read from a pressure gauge located on the supply pipe line. The flow rate of the air supply is controlled by an isolation valve (V.sub.6) before entry into the equipment. The relative humidity of the air supply was measured using the humidity probe and observed to be zero percent.

(31) Methanol and water were selected to make up a binary mixture for investigating microbubble mediated distillation. Methanol-water mixtures can be readily separated by normal batch distillation since the relative volatility between methanol and water is greater than one and the mixture does not suffer from complexities such as azeotrope formation. The methanol (Chromasolv®, for HPLC, ≥99.9%) used in this work was purchased from Sigma-Aldrich, UK.

(32) Tap water was used in all experiments except those involving methanol-water mixtures. High purity deionised water of resistivity 18.2 MΩ.Math.cm was used in making up mixtures of methanol-water because a relatively high purity level of the mixtures was considered important for chromatographic measurements. The deionised water has been filtered through a Millipak express 20 filter unit −0.22 μm (Cat no. MPGP02001)

(33) Experimental Methods

(34) The liquid height or level being considered in the experiments is that which is above the diffuser. The following approach was used to calculate the approximate volume of water required for different liquid levels. Consider a simple schematic of the bubble column as shown in FIG. 2.

(35) The following relations can be deduced from FIG. 2:

(36) $V_B=\frac{\pi D^{2}h}{4}=\frac{\pi \times {0.14}^2\times 0.022\times 1000}{4}=0.339\mathrm{Li}\mathrm{tres}$$V_D=\frac{\pi d^{2}h}{4}=\frac{\pi \times {0.112}^2\times 0.022\times 1000}{4}=0.217\mathrm{Litres}$$V_{\mathrm{RS}}=V_B-V_D=0.339-0.217=0.122\mathrm{Litres}$$V_A=\frac{\pi \times {0.14}^2\times H\times 1000}{4}=15.39H\left(\mathrm{in}\mathrm{litres}\right)$$\mathrm{Volume}\mathrm{required}\mathrm{for}\mathrm{any}\mathrm{given}\mathrm{liquid}$$\mathrm{height}H=V_A+V_{\mathrm{RS}}=15.39H+0.122$
For example, the volume for a liquid height of 8 cm is: Volume of liquid required for 8 cm height=(15.39×0.08)+0.122=1.351 litres

(37) In the above calculations, it has been assumed that the diffuser is non porous hence it does not store water in its pores. This assumption is considered reasonable for such minute pore sizes. In addition only the outer diameter of the diffuser has been used in calculating the volume of diffuser. Knowing that the diffuser has an inner diameter of 10 cm, it can be inferred that the volumes of liquid estimated for a given height is slightly lower than the true volume required.

EXAMPLE 1

(38) Preliminary experiments were performed to study the effect of operating variables (air flow rate, liquid level and evaporation time) on evaporation rate from a single component liquid i.e. water. The results from preliminary experiments show that decreasing liquid level provides higher evaporation rates and lower sensible heat transfer compared to changing other operating variables.

Procedure for Example 1

(39) Equipment set-up with the fluidic oscillator was used for experiments in this Example. The procedure for each experimental run is as follows:

(40) Pressurised air supply valve (V.sub.6) was open to allow the desired air inlet flow rate into the system. The bleed valves were completely closed (i.e. no fluidic oscillation) while valves V.sub.1 and V.sub.2 were completely open. Due to fluctuations in the flow rate of the main air supply, the air flow through the system (indicated by the outlet flow meter) was continually monitored and adjusted when necessary to maintain it at the desired value throughout the experiment. Power supply to the temperature controller and microprocessor thermometer was turned on. The column was filled with a small amount of water for heating purposes i.e. to minimise temperature rise within the tank. The temperature controller was given a set point of 250° C. to allow rapid heating of the inlet air stream. Thereafter, the temperature of the inlet air to diffuser was monitored until it reached approximately 135° C. After the desired inlet air temperature was attained, the set point of the temperature controller was frequently adjusted between 210° C. and 235° C. (depending on the air flow rate) to maintain the inlet air temperature within 135° C.±5 (i.e. average value between two inlets) for the duration of the experiment. High controller set point temperatures were used to allow for heat losses in the pipe connection to the diffuser. When the desired air temperature was attained, the bubble column was emptied by siphon action. This was achieved by closing the end of the air outlet pipe with finger tip, so that the water in the tank is forced out through the drain valve (V.sub.5) into a pipe whose other end is inserted in a beaker below the level of liquid in tank. Some tap water was collected in a beaker and the water temperature adjusted to 20° C.±0.2. The water temperature was measured using a fifth thermocouple also connected to the microprocessor thermometer. The required volume of water (e.g. 1.35 L for 8 cm height) was transferred from the beaker into a measuring cylinder. The measured volume of water was then poured into the tank through a funnel. Immediately after filling the tank, the stop watch timer was started and readings of inlet air temperatures, outlet air temperature and water temperature were recorded. These readings were again recorded every 5 minutes for the duration of the experiment.

(41) At the end of each experimental run, the remaining water in the cylindrical tank was emptied into a measuring cylinder. The volume of the remaining water in the tank was then measured and subtracted from the initial volume in the tank to get the amount of liquid evaporated. The above procedure was repeated for all experimental runs.

Results from Example 1

(42) The amount evaporated during each experimental run was used to estimate the percentage evaporation by applying the following equation.

(43) $\mathrm{Percentage}\mathrm{Evaporation}\left(\%\right)=\frac{\mathrm{Amount}\mathrm{evaporated}}{\mathrm{Intial}\mathrm{volume}}=\frac{V_0-V}{V_0}\times 100\%$
Where:
V.sub.0=Initial volume of liquid in tank (ml).
V=Final volume of liquid after evaporation (ml)

(44) TABLE-US-00001 TABLE 1 Inlet air Level of Time for Amount Run flow rate water evaporation Evaporated % no (L/min) (cm) (min) (ml) Evaporation 1 35 ± 2 4 70  95 ± 5 12.8 2 45 ± 2 4 70 125 ± 5 16.9 3 35 ± 2 10 70  80 ± 5 4.8 4 45 ± 2 10 70 105 ± 5 6.3 5 35 ± 2 4 130 172 ± 5 23.2 6 45 ± 2 4 130 240 ± 5 32.4 7 35 ± 2 10 130 165 ± 5 9.9 8 45 ± 2 10 130 225 ± 5 13.6 9 30 ± 2 8 100 110 ± 5 8.1 10 50 ± 2 8 100 210 ± 5 15.6 11 40 ± 2 2 100 170 ± 5 39.5 12 40 ± 2 12 100 151 ± 5 7.7 13 40 ± 2 8 40  52 ± 5 3.9 14 40 ± 2 8 160 263 ± 5 19.5 15 40 ± 2 8 100 152 ± 5 11.3 16 40 ± 2 8 100 150 ± 5 11.1 17 40 ± 2 8 100 152 ± 5 11.3 18 40 ± 2 8 100 152 ± 5 11.3 19 40 ± 2 8 100 160 ± 5 11.9 20 40 ± 2 8 100 155 ± 5 11.5 21 40 ± 2 4 100 160 ± 5 21.6 Table 1 summarises the main results from Example 1. It is worth noting that the relative humidity of the outlet air from all experimental runs was 100%.

(45) The mean and standard deviation of percentage evaporation from replicated experimental runs (i.e. Run 15 to 20) has been calculated using Microsoft Excel and found to be 11.4% and 0.276, respectively. This standard deviation may be assumed for experimental runs which have not been replicated.

(46) Effect of Water Level on Evaporation Rate

(47) Table 2 presents the results for percentage evaporation at different water levels. In these experiments, the air flow rate and evaporation time were kept the same. This data is also represented in FIG. 3. From FIG. 3 it is observed that percentage evaporation increases with decrease in water level.

(48) TABLE-US-00002 TABLE 2 Inlet air flow Level of Time for % Run no rate (L/min) water (cm) evaporation (min) Evaporation 11 40 2 100 39.5 21 40 4 100 21.6 15-20 40 8 100 11.4 (Mean) 12 40 12 100 7.7

(49) As noted earlier, observing the trend of outlet air humidity at different liquid levels should also provide an indication of variation of evaporation rate with liquid level. FIG. 4 plots outlet air humidity against time for different liquid levels. The air flow rate and evaporation time was kept at 40 L/min and 100 minutes, respectively, for all conditions plotted. FIG. 4 shows that the humidity of outlet air increases with time for all liquid levels until an approximate steady value is attained. The magnitude of outlet humidity is mostly higher at lower levels especially before the attainment of a near steady humidity value. This indicates that the evaporation rate is higher at lower liquid levels.

EXAMPLE 2

(50) The purpose of this example was to investigate microbubble mediated distillation using a binary mixture of methanol and water.

(51) Different experimental runs have been performed using methanol-water mixture. In each run, a 50 vol % methanol-water solution was poured into the cylindrical tank. After passing hot air bubbles through the solution over a period of time, the final volume of the solution in the tank was measured. Samples of the remaining solutions in the tank were collected and analysed using gas chromatography to determine the liquid concentration.

(52) Liquid level was varied between experimental runs to observe any effects on final concentration of remaining mixture. For comparison purposes, some experiments were performed with fluidic oscillation and others without fluidic oscillation.

(53) Preparation of Methanol-Water Solutions

(54) Mixtures of methanol and water were prepared via a measured volume of methanol poured into a cylinder containing an equal volume of deionised water to obtain a 50 vol % solution. After mixing, the temperature of the mixture rose indicating an exothermic interaction between methanol and water. The volume of the mixture also contracted by about 4% upon mixing. To reduce the temperature of solution down to 20° C. which is the reference temperature used for the experiments, the cylinder was inserted into a large beaker containing water at a lower temperature. A reduction in the temperature of solution was achieved by the transfer of heat from the solution to the surrounding water in the beaker. After achieving a temperature of 20° C.±0.2, the beaker containing the mixture was then placed on a magnetic stirrer for better mixing of the solution.

Operating Conditions for Example 2

(55) The operating conditions for the Example 2 are presented in Table 3 and 4. A low flow-rate of 1 Lmin.sup.−1 was chosen to allow the formation of smaller bubbles compared to previous experiments. For all experimental runs, the initial mixture temperature was kept within 20° C.±0.2. The inlet air temperature to the diffuser in all tests was controlled to be within 90° C.±2. This value for air temperature was chosen because it is above the boiling point of methanol (65° C.) and below that of water (100° C.), hence it is expected that the bubbles generates at 90° C. will preferentially evaporate more of methanol than water.

(56) TABLE-US-00003 TABLE 3 Table 3 operating conditions for binary liquid experiments without fluidic oscillation. Height of 50 vol % Flow rate of methanol inlet air to Flow rate of Temp of inlet Test mixture Vol of Y-Junction inlet air to air to diffuser Evaporation no (cm) water (ml) (L/min) diffuser (L/min) (° C.) time (mins) 1 0.5 200 ± 5 100 ± 2 1 ± 0.1 90 ± 2 200 2 2 430 ± 5 100 ± 2 1 ± 0.1 90 ± 2 200 3 4 738 ± 5 100 ± 2 1 ± 0.1 90 ± 2 200

(57) TABLE-US-00004 TABLE 4 Table 4: Operating conditions for binary liquid experiments with fluidic oscillation. Height of 50 vol % Flow rate of methanol inlet air to Flow rate of Temperature of Test mixture Volume of oscillator inlet air to inlet air to Evaporation no (cm) water (ml) (L/min) diffuser (L/min) diffuser (° C.) time (mins) 4 0.5 200 ± 5 80 ± 2 1 ± 0.1 90 ± 2 200 5 2 430 ± 5 80 ± 2 1 ± 0.1 90 ± 2 200 6 4 738 ± 5 80 ± 2 1 ± 0.1 90 ± 2 200

Procedure for Example 2

(58) At the start of each experiment, the air inlet flow to heater was set to the desired value after which the bleed valve or valves were open just enough to remove excess air not required at diffuser inlet. When fluidic oscillation is required, the bleed valves must be adjusted until the oscillation frequency of the air in the fluidic oscillator is within its resonance range (indicated by a continuous vibrating sound) whilst ensuring the outlet flow rate is 1 L/min. The temperature controller was given a set point of about 150° C. before the tank was filled with a small amount of water for heating purposes. The temperature of the inlet air to diffuser was monitored until it reached around 90° C. After achieving the required air inlet temperature, the set point of the temperature controller was frequently adjusted to maintain the inlet air within the required temperature range of 90° C.±2 throughout the experiment. The tank was then emptied and the required volume of methanol-water mixture at 20° C.±0.2 was measured and poured into the cylindrical tank through a funnel. Immediately after filling the tank, the stopwatch was started and readings of inlet air temperatures, air outlet temperature and mixture temperature were recorded. These readings were recorded every 10 minutes for the duration of the experiment. At the end of each experimental run, the remaining solution in the tank was emptied into the measuring cylinder. The tank was emptied by using a syringe to create additional suction because a low air flow rate was used in these experiments. The volume of the remaining water in the tank was then measured and subtracted from the initial volume in the tank to get the amount of liquid evaporated. A small amount of the remaining solution was stored in tightly sealed and labeled 15 ml centrifuge tubes as sample for gas chromatography measurements. The samples were stored in a fridge to minimise evaporation. After each test the tank was then rinsed with a small amount of water before the start of the next run.

Results from Example 2

(59) Effect of Liquid Level and Fluidic Oscillation on Final Methanol Concentrations.

(60) Table 5 presents results from Experiment 2. An inlet air flow rate of 1 L/min, evaporation time of 100 minutes and an average inlet air temperature of 90° C. has been used for all Tests.

(61) TABLE-US-00005 TABLE 5 Concentration Level of Amount Peak area of of methanol in Test mixture Fluidic evaporated methanol remaining no (cm) Oscillation (ml) (%) mixture (vol %) 1 0.5 No 30 ± 5 20.96 37.42 2 2 No 30 ± 5 22.15 39.52 3 4 No 26 ± 5 23.64 42.15 4 0.5 Yes 36 ± 5 20.72 37.00 5 2 Yes 28 ± 5 23.13 41.25 6 4 Yes 36 ± 5 24.32 43.34

(62) FIG. 5 is a plot of the final methanol concentration in mixtures versus liquid level. It is observed that the final concentration of methanol is lower at low liquid levels compared to higher liquid levels. This indicates that separation is improved as liquid level decreases. The final concentration of methanol from tests performed with fluidic oscillation is slightly higher than those performed without fluidic oscillation for liquid levels of 2 and 4 cm, suggesting that less of methanol has been evaporated with fluidic oscillation at these levels. However at a liquid level of 0.5 cm, the methanol concentration obtained with fluidic oscillation is slightly lower than that obtained without fluidic oscillation suggesting that more of methanol has been evaporated with fluidic oscillation.

(63) Data for mixture temperature against time for Tests 1 to 6 is plotted in FIG. 6 showing the effect of liquid level and fluidic oscillation on temperature of binary mixtures. In FIG. 6, WF represents tests performed with fluidic oscillation while WOF represents tests performed without fluidic oscillation. A decrease in mixture temperature with time was observed in all tests performed without fluidic oscillation. In contrary, an increase in mixture temperature was observe in all test performed with fluidic oscillation, although the temperature increase was less significant at the lowest liquid level used i.e. 0.5 cm.

(64) Determining the Ratio between Latent Heat and Sensible Heat Lost in Inlet Air

(65) The data from this example was used to estimate the heat ratio (∝) between the heat which is transferred as latent heat of vaporisation, to the total sensible heat lost in the inlet air. It is assumed that all the heat lost in inlet air is either loss as sensible heat to mixture or as latent heat of vaporization. The following equations and approximations have been used:

(66) Sensible heat loss in inlet air (Q.sub.T)=Heat loss as latent heat (Q.sub.L)+Sensible heat transferred to mixture (Q.sub.S)

(67) 0$\alpha =\frac{\mathrm{Heat}\mathrm{loss}\mathrm{as}\mathrm{latent}\mathrm{heat}\left(Q_L\right)}{\mathrm{Sensible}\mathrm{heat}\mathrm{lost}\mathrm{in}\mathrm{inlet}\mathrm{air}\left(Q_T\right)}=\frac{Q_T-Q_S}{Q_T}$

(68) Specific heat at constant pressure of methanol mixtures is taken as 0.917 cal/g° C. (3851.4 J/kg.Math.K). This specific heat was obtained from Perry, R. H. and Green, D. W. (2008). Perry's Chemical Engineers' Handbook. 8.sup.th ed. New York: McGraw-Hill. p 14-88, 2-183, 2-176, 14-16, 2-116, for a 27.3 mol % aqueous methanol at 20° C. Specific heat at constant pressure of air is taken as 1010 J/kg.Math.K.

(69) The pressure of the air stream is taken as 1.513 bar for an air flow rate of 3 L/min. Furthermore, it is assumed that density and volume of methanol-water mixture remains constant during each experimental run.
Q.sub.T={dot over (m)}.sub.airC.sub.p,air(T.sub.i,air−T.sub.o,air)t={dot over (n)}MW.sub.airC.sub.p,air(T.sub.i,air−T.sub.o,air)t
Q.sub.S=m.sub.mixC.sub.p,mix(T.sub.o,mix−T.sub.i,mix)=ρV.sub.mixC.sub.p,mix(T.sub.o,mix−T.sub.i,mix)
Where:
Subscript ‘air’ and ‘mix’ represents air and mixture, respectively.
m=mass (kg)
{dot over (m)}=mass flow rate (kg/min)
C.sub.p=Specific heat in J/kg.Math.K
T.sub.i=Initial/inlet temperature
T.sub.o=Final/outlet temperature
t=Time for evaporation (minutes)
{dot over (n)}=molar flow rate of air stream. Assuming ideal gas law holds,

(70) $\stackrel{.}{n}=\frac{P\stackrel{.}{V}}{\mathrm{RT}}$
R=Ideal gas constant=8314 J/kmol.Math.K
ρ=Density is 50 vol % (44 wt %) methanol-water mixture=0.9272 g/ml (Perry & Green, 2008, p 2-116).
For better clarity, the parameters that have been used for calculations in this section are given in the table below.

(71) TABLE-US-00006 Parameter Value Pressure of inlet air 1.513 bar (151,300 Pa) Specific heat of methanol mixture 3851.4 J/kg .Math. K Specific heat of air 1010 J/kg .Math. K Density of 50 vol % methanol- 0.9272 g/ml water mixture Air flow rate 1 L/min = 0.001 m.sup.3/min Time for evaporation 200 minutes Air inlet temperature 363 K (90° C.) Molecular weight of air 28.96 kg/kmol (Perry & Green, 2008, p2-176)

(72) The heat lost by air stream and sensible heat transferred to mixture was calculated for Test 4, 5 and 6 only as these were the only tests during which the mixture temperature increases with time. An example calculation is given below for Test 4. Liquid volume used in Test 4 is 200 ml. Average outlet air temperature (T.sub.o,air) and final liquid temperature (T.sub.o,mix) from Test 4 was 25.26° C. and 21° C. The initial mixture temperature was taken as 20° C., which is the temperature of the mixture before it was poured into the bubble column.

(73) Heat Lost in Inlet Air

(74) $\begin{array}{c}\left(Q_T\right)=\frac{\stackrel{.}{P\stackrel{.}{V}}}{\mathrm{RT}}M{W}_{\mathrm{air}}{C}_{p,\mathrm{air}}\left(T_{i,\mathrm{air}}-T_{o,\mathrm{air}}\right)t\\ =\frac{151,300\mathrm{Pa}\times 0.001m^3/\min }{8314J/\mathrm{kmol}.Math.K\times 363}\times 28.96\mathrm{kg}/\mathrm{kmol}\times \\ 1010J/\mathrm{kg}.Math.K\times \left(363-298.26\right)K\times 200\min \\ =18.99\mathrm{kJ}\end{array}$
Sensible Heat Transferred to Mixture

(75) $\begin{array}{c}\left(Q_s\right)=\rho V_{\mathrm{mix}}{C}_{p,\mathrm{mix}}\left(T_{o,\mathrm{mix}}-T_{i,\mathrm{mix}}\right)\\ =0.9272g/\mathrm{ml}\times 200\mathrm{ml}\times 3851.4J/\mathrm{kg}.K\times \left(21-20\right)\times {10}^{-3}\\ =0.714\end{array}\begin{array}{c}\alpha =\frac{Q_T-Q_S}{Q_T}\\ =\frac{18.99\mathrm{kJ}-0.714}{18.99\mathrm{kJ}}\\ =0.962\\ =96.2\%\end{array}$

(76) Therefore an estimated 96.2% of the sensible heat lost in inlet air is transferred as latent heat while the remaining 3.8% is transferred as sensible heat.

(77) The above calculations were repeated for Test 5 and 6, and the result are given in Table 6.

(78) TABLE-US-00007 TABLE 6 Test Liquid level no (cm) Q.sub.T (kJ) Q.sub.S (kJ) α (kJ) 4 0.5 18.99 0.714 0.962 5 2.0 19.60 4.914 0.749 6 4.0 19.19 7.643 0.602

(79) The results from binary distillation experiments of Example 2 show that microbubbles can indeed achieve appreciable liquid separation with minimal sensible heat transfer. Separation efficiency was improved with decreasing liquid level. Highest separation efficiency was observed in experiments performed using the lowest liquid level (i.e. 0.5 cm) combined with fluidic oscillation, where the methanol concentration reduced from an initial value of 50 vol % to a final value of 37 vol %. This was achieved with a low liquid temperature rise of 0.2° C. Fluidic oscillation was observed to reduce separation efficiency and increase liquid temperature rise at high liquid levels (2 cm and 4 cm) but at a lower liquid level (0.5 cm) fluidic oscillation slightly improved separation efficiency with negligible liquid temperature rise. Therefore, if a fluidic oscillator is to be employed, it should be limited to low liquid levels to allow higher separation efficiencies and to limit temperature rise.

(80) Assessment of the Data.

(81) Not wishing to be bound by any theory it is believed that the following observations provide further insight into the data obtained in the Examples.

Assessment Example 1

(82) FIGS. 3 and 4 effectively demonstrate that upon decreasing water level, evaporation rate is increased. The conditions plotted are for an air flow rate of 40 L/min. At such a high air flow rate, the bubbles formed (considering the absence of fluidic oscillation) should be relatively large, perhaps a few mm in size. Nevertheless, the size distribution of the bubbles formed in each experiment should be similar since the same air flow rate has been used. It is believed that after the bubbles are formed, they rise through the liquid and transfer latent heat to the surrounding fluid hence initiating the evaporation of liquid around the ‘skin’ of the bubbles. As the bubbles rise, maximum evaporation will occur at very low liquid levels after which the vapour will begin to lose heat and condense back into the liquid until it equilibrates. It is believed that there exists a critical height or residence time at which maximum re-condensation will occur. Before that critical height is achieved, the amount of condensation will increase as liquid level increases. Therefore, the amount of vapour that is not condensed hence vaporised increases as the liquid level is decreased. It is believed that for this reason, evaporation rate is observed to increase with decreasing level, which is counterintuitive.

(83) Enhancing evaporation rate by decreasing liquid layer is a favourable option when considering the objective of the present invention since the augmentation in liquid temperature upon decreasing the water layer is not as significant at that observed from increasing air flow rate. Moreover, decreasing liquid layer from 12 cm to 2 cm increases percentage evaporation by 413% (see FIG. 3) which is huge amount when compared to a mere increase of 92.6% achieved when air flow rate was increased from 30 L/min to 50 L/min.

(84) Increasing the gas flow rate can result in increased cost associated with evaporation, especially if an expensive gas is to be employed. Moreover, the energy required to heat the gas phase to the desired temperature will increase as the flow rate increases which will also incur additional cost. Whereas, decreasing liquid level may add little if any additional cost to the operation of the system. Furthermore, if a high gas flow rate is to be employed, it may necessitate the use of larger equipment which will increase capital cost. The safety of the procedure will also be affected when using high gas flow rates especially because the gas flow would be at a very high temperature and pressure. Therefore, it is highly favourable to improve evaporation rate by decreasing liquid level rather than increasing gas flow rate. This counterintuitive outcome from these experiments is highly significant.

Assessment Example 2

(85) As indicated above, if the residence time of microbubbles is too high in a liquid, the evaporated vapour will lose heat to its surroundings and re-condense until it equilibrates with the liquid phase. Microbubbles will normally rise slowly in liquid compared to large bubbles as a consequence of Stokes law as discussed above. Although this behavior is seen as an advantage in many applications (especially in mass transfer), it constitutes a problem in the present invention since the goal is to achieve short residence time in the liquid layer to prevent sensible heat transfer and vapour re-condensation. As observed from FIG. 6, the increase in methanol concentration of remaining mixtures on moving from low to high liquid levels (for conditions with and without fluidic oscillation) indicates that methanol separation is reduced as liquid level increases, which is counterintuitive. It is believed that this behavior is most likely due to an increase in re-condensation of methanol vapour caused by an increase in residence time of bubbles in the liquid phase.

(86) The diameter of microbubbles generated by fluidic oscillation is expected to be smaller than those generated without fluidic oscillation using the same gas inlet flow rate. It is believed that as they are smaller in size, microbubbles generated by fluidic oscillation are expected to give higher separation of methanol from a ‘thin’ liquid layer when compared to those generated without fluidic oscillation. It is believed that this is because small microbubbles will exhibit higher internal mixing rates compared to larger microbubbles. The results demonstrate that fluidic oscillation helps improve separation efficiency at low liquid levels (e.g. 0.5 cm) but the opposite effect occurs at higher liquid levels. It is believed that the tendency for fluidic oscillation to reduce separation at high liquid levels may be attributed to the idea that the microbubbles generated by fluidic oscillation are smaller in comparison to those generated without fluidic oscillation; hence their residence time in liquid will be higher. Even though fluidic oscillator generated microbubbles may provide maximum evaporation from a thin layer, for a thick liquid layer they would have greater chance of sensible heat transfer and vapour re-condensation than microbubbles generated without fluidic oscillation. At lower liquid levels (i.e. 0.5 cm), the liquid layer is gradually approaching conditions of being ‘thin’, hence a slight increase in separation efficiency by fluidic oscillation is observed. The highest separation of methanol was also observed in Test 4, which was performed using a low liquid level of 0.5 cm combined with fluidic oscillation. In Test 4 methanol concentration was decreased from 50 vol % to 37 vol %. These observations show the surprising results obtained with microbubbles obtained via fluidic oscillation passing through thin liquid layers.

(87) In FIG. 6, the increase in mixture temperatures observed in experiments performed with fluidic oscillation can be explained by considering that smaller microbubbles have a higher residence time in the liquid layer. Therefore, more time is available for the transfer of sensible heat to the mixture.

(88) It FIG. 6 it is believed that the decrease in mixture temperature observed in tests performed without fluidic oscillation can be attributed to concept of microbubble evaporative cooling. Evaporative cooling is a phenomenon that occurs when a liquid evaporates into a moving air stream with the latent heat for vaporisation taken from the surrounding liquid. Consequently, the surrounding liquid remains in its liquid state but at a lower temperature. As the microbubbles generated without fluidic oscillation are larger than those generated with fluidic oscillator, their residence time in the liquid is less. It is believed that this lower residence time could mean that the bubbles can transfer a higher fraction of the mixture into the vapour phase, with the latent heat taken from the liquid phase.

(89) From FIG. 6 it is observed that the temperature of mixtures in all Tests does not change substantial from their initial value, with a maximum temperature rise of 2.7° C. observed in Test 5 which was performed without fluidic oscillation and with a liquid level of 2 cm. The mixture temperature in Test 4 was increased by 0.2° C. only. This indicates that good separation can be achieved with minimal sensible heat transfer since the highest separation of methanol was also observed in Test 4.

(90) The heat ratios (α) between latent heat and sensible heat lost in inlet air for Test 4, 5 and 6 have been calculated. The results plotted in FIG. 7 show that the fraction of heat lost in inlet air which is transferred as latent heat goes up as liquid level decreases. Therefore maximum latent heat and minimum sensible heat transfer is expected to occur at very low liquid levels approximating to a ‘thin’ liquid layer'. Consequently, separation efficiency would increase as liquid level decreases especially when microbubbles are introduced at a temperature higher than the boiling point of the most volatile component (e.g. methanol) and less than that of the least volatile component (e.g. water). This is the behavior observed in FIG. 7, which shows an increase in methanol separation with decreasing liquid level.

(91) Thus the Examples show that in microbubble mediated batch distillation experiments microbubbles can offer appreciable liquid separation with little or no liquid temperature rise. Decreasing the liquid level used in distillation enhances separation which is counterintuitive. Maximum separation of methanol was observed in experiments performed using the lowest liquid level (i.e. 0.5 cm) combined with fluidic oscillation, where the methanol concentration decreased from an initial value of 50 vol % to a final value of 37 vol %. This was achieved with a low liquid temperature rise of 0.2° C., which at this scale is an insignificant amount of sensible heat transfer to the liquid phase. In microbubble batch distillation experiments, fluidic oscillation was observed to reduce separation efficiency and increase liquid temperature rise at high liquid levels (i.e. 2 cm and 4 cm). At lower liquid levels (i.e. 0.5 cm) fluidic oscillation slightly improved separation efficiency with minimal liquid temperature rise. Therefore if fluidic oscillation is involved, it is best used at low liquid levels to allow better separation and limit temperature rise. Furthermore, microbubble induced evaporative cooling of the liquid phase with time was observed in experiments performed without fluidic oscillation and gas at elevated temperature, which is considered advantageous for separation of thermal sensitive liquids.

EXAMPLE 3

(92) In a further experiment, hot bone-dry air at a temperature around 145° C. was made to flow upwards through a micro porous diffuser into a cylindrical tank (i.e. bubble column) containing some water at room temperature, over a period of 250 minutes. The water temperature rose from 21.5° C. to 27.6° C. over 250 minutes of evaporation, while about 34 ml of liquid had evaporated. Surprisingly, the relative humidity of the outlet air was 100% for the duration of the experiment. As an attempt to achieve less than saturation relative humidity of the outlet air, they performed further experiments using lower liquid levels in the bubble column. Upon decreasing the liquid height, the outlet air remained at saturation relative humidity throughout the experiments. However, an increase in the absolute humidity of the outlet air was observed, while the water temperature did not increase as much.

(93) This behavior signified that there exists a competition between the sensible heat transferred to liquid and the latent heat used in vaporisation. Bearing in mind that an increase in absolute humidity of outlet air indicates more evaporation, their results suggest that upon decreasing the liquid layer height (i.e. reducing residence time of microbubbles in liquid), evaporation starts to dominate over sensible heat transfer.

EXAMPLE 4

(94) A further series of experiments were undertaken as follows with liquid heights of 0.5 cm or less and utilising water/ethanol mixtures. The experimental apparatus was as previously described. Pure ethanol was used (99.7%) and was mixed with deionised water in a 50:50 volume ratio for the water/ethanol experiments.

(95) Deionised Water Experiments at 0.5 cm or Less

(96) All of the experiments were carried out under the same operating conditions of inlet airflow rate and temperature (1±0.1 L/min & 135±2° C.). Table 7 presents the overall experiments that were performed on deionised water including the operating conditions and the rate of evaporation.

(97) TABLE-US-00008 TABLE 7 Table 7: Summary of the experimental results of evaporating deionised water with and without using fluidic oscillation. Inlet air Average Water Average Time of Exp. Fluidic flow inlet air Level water evaporation % no. oscillation rate (L/min) Temp. (C.) (cm) Temp. (° C.) (min) Evaporation 1 No 1 ± 0.1 135.8 0.1 19.6 100 3.93 2 No 1 ± 0.1 136.5 0.2 21.3 100 3.025 3 No 1 ± 0.1 136.9 0.3 20.5 100 2.62 4 No 1 ± 0.1 136 0.4 20.1 100 2.4 5 No 1 ± 0.1 136.4 0.5 21.5 100 1.6 6 Yes 1 ± 0.1 136.4 0.1 23 100 28.7 7 Yes 1 ± 0.1 136 0.2 23.1 100 17.94 8 Yes 1 ± 0.1 136.5 0.3 21.9 100 11.8 9 Yes 1 ± 0.1 136.9 0.4 21 100 4.5 10 Yes 1 ± 0.1 136.5 0.5 20.5 100 4.7

(98) As mentioned in the previous experiments, the level of water has a considerable effect on the evaporation percentage over the other parameters (e.g. inlet air temperature and flow rate). FIG. 8 presents the results highlighted in Table 7 as percentage of evaporation vs. water level.

(99) Ethanol/Deionised Water Experiments at 0.5 cm or Less.

(100) These experiments were carried out on standard mixtures of ethanol-water at a volume ratio of (50:50) and at the same operating conditions of inlet airflow rate and temperature of (1±0.1 L/min & 135±2° C.) respectively. Table 8 presents the overall experimental results with and without using fluidic oscillation.

(101) TABLE-US-00009 TABLE 8 Summary of the experimental results of evaporating ethanol/ deionised water with and without using fluidic oscillation. Mix- Average Time of Inlet air ture mixture evapor- % flow rate Level Temperature ation Evapor- Experiment no. (L/min) (cm) (° C.) (min) ation  1-Without oscillator 1 ± 0.1 0.1 22.27 100 36.3  2-Without oscillator 1 ± 0.1 0.2 19.75 100 14.83  3-Without oscillator 1 ± 0.1 0.3 20.4 100 7.5  4-Without oscillator 1 ± 0.1 0.4 19.98 100 6.37  5-Without oscillator 1 ± 0.1 0.5 19.19 100 3.4  6-With oscillator 1 ± 0.1 0.1 22.43 100 43.15  7-With oscillator 1 ± 0.1 0.2 20.86 100 19.24  8-With oscillator 1 ± 0.1 0.3 20.08 100 13.2  9-With oscillator 1 ± 0.1 0.4 19.91 100 9.5 10-With oscillator 1 ± 0.1 0.5 19.85 100 7.5

(102) These experiments show that decreasing the level of the mixture caused a significant increase in the percentage of evaporation. The same phenomenon as has been observed in the single liquid evaporation system of deionised water. FIG. (9) illustrates the effect of mixture level on the percentage of evaporation of binary mixture of ethanol and water.

(103) Observations on Water and Ethanol/Water at 0.5 cm Liquid Height.

(104) According to Table 7 and FIG. 8 decreasing the level from (0.5 cm to 0.1 cm) has resulted in an increase in the percentage of evaporation from 1.6% to 3.93% without use of the fluidic oscillator. However, when the fluidic oscillator is used the percentage evaporation increases from 4.7% to 28.7% under the same liquid levels and conditions. This means that the percentage of evaporation achieved at 0.1 cm with the fluidic oscillator is 7.3 times greater than that without use of the fluidic oscillator. For a liquid height of 0.5 cm, the ratio is only 2.94 times greater than that without the fluidic oscillator. These ratios demonstrate the high efficiency of the microbubbles produced by the fluidic oscillator over that of microbubbles produced without the fluidic oscillator. They also demonstrate a remarkable increase in efficiency with decrease of liquid level when used in combination with microbubbles.

(105) According to Table 8 and FIG. 9 the same general trend and hypothesis was obtained in the evaporating ethanol/water binary mixtures. The liquid level has significant effects on the evaporation percentage of the mixture, for example decreasing the level from 0.5 cm to 0.1 cm resulted an increase in the percentage of evaporation from 7.5% to 43.15% for ethanol water mixture by using the fluidic oscillator.

(106) The ratio between the results obtained with oscillator to that without the oscillator are not as great as those seen with the deionised water experiments. There may be technical reasons for this difference associated with the design of the apparatus and the relative efficiency of the ceramic diffuser used in the experiments. This diffuser produced microbubbles having an approximate diameter in the range of 800-900 μm without using the fluidic oscillator. The estimated bubble size produced by the same diffuser with the aid of the fluidic oscillator is about 300-500 μm or less according to the operating conditions. Furthermore as illustrated in FIG. 9 ethanol is evaporating very fast because of its high volatility and thus it would be expected to have a high percentage of evaporation with and without the fluidic oscillator.

(107) Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, means “including but not limited to”, and is not intended to (and does not) exclude other components, integers or steps.

(108) Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise. Features, integers, characteristics, compounds described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

(109) All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

(110) The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.