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Desulination, 91 (1993) 279-292 279

Elsevier Science Publishers B .V., Amsterdam - Printed in The Netherlands

High recovery reverse osmosis using
a recycle loop

Cal C. Herrmann*

Bionetics,Inc., Mailstop239-l 1, NASAAmes Research Centel;
MoffeettField, CA 94035-1000 (USA)
(Received November 12,1992)

SUMMARY

A single-pump configuration with feedback has been found useful
in reaching high brine osmotic pressures in continuous-flow operation.
Enhanced brine concentration, and enhanced product/feed water recov-
ery fraction, can be obtained by recycle of a second-stage permeate of
intermediate quality.
For spaceflight recycling of hygiene water this permits lower pressure-
vessel ratings, or higher water recovery, or both. With feed of 1,000 ppM
concentration, recoveries of 95-97% are achieved at a pressure of 1.65 MPa.
With feed of seawater concentration, recoveries of 50% to 70% have been
achieved using a single pump at 5.5 MPa.
Membrane performance parameters have been obtained for high water
recovery operation in the pressure range up to 1.4 MPascals (200 psig) for
system modeling. Simple equations can be fitted to these measurements,
from which RO system performance can be predicted, or simulated as part
of a model of system performance.

*Current address: University of California, Berkeley, Richmond Field Station Bldg. 478,
1901 So. 46th St., Richmond, CA 94804. Tel: 510-231-9456,Fax: 510-231-9535

001 l-9164/93 /$06.00 @ 1993 Elsevier Science Publishers B.V. All rights reserved.

Swamikannu [7] measured conductivity rejections vs. permeate flux in the 0. RECYCLE APPROACH A modification of the conventional configuration can be proposed to recycle a partially desalted permeate with intermediate osmotic pressure.8 MPa and recoveries up to 90%. [S] tested RO membranes at 5 MPa. To evaluate this concept and gener- ate designs requires experimental measurements from actual membranes: salt re_jections at low pressures. Polyakov et al.7-2. including operation to pasteurization temperatures.5 MPa and water recoveries over 80%. [3] tested RO systems with bioreactor and similar waste. Hitt et al. at 2. in the presence of soap and urea. at 1.1 MPa range. and at elevated temperatures and recoveries of 70 to 99%. at pressures up to 5. over a range of salinities and concentration factors. [6] described RO systems operating from 4 to 7 MPa with 90% water recoveries. In this report RO parameters are examined toward optimization of efficiency and operational simplicity. Reysa et al. can be identified: high water recovery. such as a spacecraft on an extended or planetary mission. These measurements can be utilized by a simulation methodology to study performance over an extended range of operating conditions. and high efficiency. reaching 99% recovery from wash water. using a partial nonselective brine recycle. However the substantial increase of osmotic pressure with reject brine concentration necessitates examination of the low pressure performance of RO membranes for optimum conditions. using a single feed pump and pressure. Previous papers on spacecraft application of RO have addressed system performance and selectivity and membrane structures. McCray et al. Ray [5] reported on a new membrane design.2] tested a RO shower water recovery system.8 MPa and water recoveries to 95%. simplicity of operation. [4] tested several RO membranes with soap and urea solutions.280 INTRODUCTION The needs for a water recycling function in a remote environment with limited fresh water supply. at 2. Verostko [ 1. . The low salinity and osmotic pressure of typical wastewater permits consideration of low-pressure reverse osmosis in this task.4 MPa and 90% recovery.

and brine outlet flow.” There results a transient pattern on change of feed concentrations. small reverse-osmosis thin-film composite spiral wound cartridges similar to some previously tested [3. with many options. 91 for space applications. based on updated effective feed values. These functions of three variables are poorly known at very low pressures but are easily established by use of a test facility. brine flow and concentration: these characterize the input for the second membrane element. to obtain a “mapping” of membrane performance over the test range of pressures and salinities. Pulse-generating flowmeters were used. a permeate flow and concentration is to be calculated. From a second membrane element. SW30-2521). salinity. An analog-to-digital I/O card was obtained. These are func- tions of the applied pressure. Pressure and brine-outlet flow controls were provided. . There is an additional important condition of recycling RO: the water volume in the cartridge and associated plumbing is enough to cor- respond to several minutes or more of delay or “inertia. Digital display conductivity controllers provide setpoints and relay contacts as both upper and lower limits. plus analog voltage outputs to the A/D computer entry card. The card also contains three 16 bit counters. 4. and added to the first element feed. Calibration data for conductivity and osmotic pressure of sodium chlo- ride used LeskovSek [lo]. pressure or brine flow. valid to over 5 moles/liter concentrations. of importance in the design of a control system for the RO device. to plug into a computer. The initial measurements were made using single membranes. plus float-type visual flowme- ters for measurement of the lowest flow ranges. however more recent equations based on associ- ation theory are found in Stewart and Zener [ 111. used for data entry from the flow sensors. usually converge at reasonable speed. In-line conductivity cells with 6 mm tubular connections were con- venient for integration into the flow paths. This provides 12 bit A/D conversion of 8 differential channels. Such iterative calculations. in the above recycle configuration. EXPERIMENTAL Membrane elements chosen were Filmtec type BW30-2514 (and at higher pressure and salinity. 281 An optimization study by simulation requires the following data: For the first stage or membrane element.

128*MPa + 3. so the term in pressure-squared may be considered only as a caution in extrapolation to high pressures without further data.999. -. or if a more professional program was useful it could be restructured in another language. R* = 0. Second order curve fit: reject ppT = 0.351*MPa. or “I _ “. 1.989. R* = 0. a: brine ^ flow = 21 ml/min.996.845 + 10.6689’MPa + 1. R2 0.l30*MPa + 2.1247 (MPa)*.703 + 14.282 The data-collection program was expected to be simple. 1 as a function of applied pressure. for 5 brine flow rates. --. more accurately quadratic. 0. Linear regression: reject ppT = 0.5 mUmin. The program listing is available on request. A: brine flow = 2. R* = 0. R* = 0. and to somewhat higher pressures.989. Second order curve fit: reject ppT = 1.0 0. so was written in BASIC.5 ml/min.4352 (MPa)‘.4735 (MPa)!.703 + 16.4209 (MPa)*. RL = 0. Second order curve fit: reject ppT = 0. .824 + 7. pressure at 5 brine flow rates. 0: brine flow = 1.2 ml/mln. .944 + 4.009 + ll.514’MPa.989.5 MPa Fig.897 + 9. Linear re- gression: reject ppT = 0.224*MPa.3671WPa+ 1. R2 = 0.999. Current usage is one sampling cycle per minute (with 660 sampling cycles per daily run).9874*MPa + 0. EXAMPLES OF RESULTS: SINGLE MEMBRANE STUDES Brine concentrations resulting from 1 ppT sodium chloride feed are plotted on Fig. A: brine flow = 15 ml/min.5 1. 1 ppT sodium chlo- ride feed. Linear regression: reject ppT = 0.4321 (MPa)*.a brme .989. with the reservation that if speed were needed it could be compiled. Second order curve fit: reject ppT = 1.7738’MPa. Within this range.019 + 12.998. R2 = 0. The relation for this inlet concentration can be approximated by linear.4639’MPa. but to require changes during preparation. Second order curve fit: reject ppT = 0.0 I.999. the linear approximation is within experimental error. Brine concentrations vs. R * = 0. Linear regression: reject ppT = 0. Linear regression: reject ppT = 0. Aow = 7.997. R2 = 0.766 + 6. equations.964 + 6.

8 + 1.65*B)*(MPa)*. 283 The slopes of these equations. At a feed concentration of 3. .2076’log (brine ml/min). reject flow. brine flow values. or concentration factors. The same empirical strategy produces a working expression for the permeate flow: P = 6. The result is that a 0 5 10 IS 20 Brine ml/mn Fig.16 .4*B*MPa + (35. vs. and an equation is found to fit these values.99. (2) And for the permeate concentration: [P] = 0.2 .44 . combined equation can be formed to predict brine concentration from the pump pressure applied. vs.8. 1 ppT sodium chloride feed. 2. they are sufficiently complex that tested practical approximations are often useful in simulation modelling.28 log(B) (3) The same data can be expressed and used in terms of membrane rejec- tions.16 .79* log(B))*MPa. 2. can be plotted as in Fig. for a given feed concentration (1 ppT NaCl): ppT(brine) = [B] = (18.2076* log(B))*MPa (1) This expression of course has a limited range of validity. While equations with theoretical validity can be formed for these purposes.0.7.8. Curve fitting: (ppT/MPa) = 18. Slopes of reject concentration/pressure. reduced by the osmotic pressure of the feed (MPa) and the brine flow B chosen (in ml/min). R2 = 0.53 ppT this expression becomes: (24.

.. who used a computer program to calculate the optimum number of stages. along with decrease in permeate flow.. with extraction of additional first stage product and final waste brine. the differ- ence of osmotic pressure may be 60 to 80% of the total value of the osmotic pressure.. with restriction of the brine flow..1 MPa.. Furthermore...... The effective pumping power required for a given initial feed is increased by the amount of the recycle stream.... and this difference subtracts from the applied pressure to form . Permeate = Recycle Brine 1 RO Stage 1 Pump ’ Permeate = Product Fig. for low differences between the applied pressure and the solution osmotic pressure difference across the membrane........ RO with recycle of partially desalted permeate for enhanced water recovery. however. the permeate concentration also increases. 3... a similar fraction of it is recovered..... The extension is that.. with the final brine increasing in con- centration.. 3.. The pressure requirement is not increased.\\\\\\\\\\\\\.. because salt rejection is poor at very low pressures. for some selectable pressure and brine output the permeate concentration of a final segment of an RO flow path is similar to that of an initial feed.. A multistage extension was described by Perona [ 131.284 THE RECYCLING LOOP As the salt concentration of the reject stream increases...... as permitted by the osmotic pressure difference across the final membrane.... the concentration of this recycle stream is similar to that of the feed....... This is the configuration of Fig. and an optimum pressure for each stage........ achieving a final concentration of 100 ppT at 3.... A similar approach was taken by Spatz [ 121 in a reverse-osmosis nickel-reclamation system. to meet product and reject specifications. so it can appropriately be added to that feed and recycled.... Since RO Stage 2 Reject brine out < I Membrane r. \...... the permeate concentration fur- ther increases.. Because such a final element permeate retains substantial salt......

. The experimental and practical value for a two-membrane system with recycling is the control of brine flow. Reject concentration (0) and reject-to-product concentration ratio (A). reject flow from two-stage membrane system with recycle. 285 the effective driving force for permeation.---* -300 --.5' -250 ZO. for a 1 ppT feed. as is seen in Fig. IO.-+ 0 5 IO 15 20 25O Brine mllmn Fig. Since at very high final brine concentrations the feedback does degrade the feed and hence the product.. the final brine concentration can rise to that permitted by the osmotic pressure difference between the source and permeate sides of the membrane. the product permeate is degraded at highest volume recoveries. the feed concentration becomes augmented by a few percent in exchange for substantial increase in final brine concentration. That final brine concentra- tion easily approaches that achieved by tighter membranes at higher pump pressures (the normal multi-stage operation). 1 ppT NaCI feed. 8 5. 1.'-'. -WI R 2._ f A 7. One can allow the final-stage permeate to increse in concentration beyond the feed concentration because there is not much of it.. -50 Oi'-. the brine flow setting. -350 30' ‘.) With feedback of poor quality permeate from the second membrane..'. The brine concentration obtained. The amount .'.65 MPa pressure applied. 35. (Concentration polarization on the feed side of the membrane remains significant. 4..'. vs. ‘ml Is. is a measure of performance. The effective volume recovery is the fraction of the feed that appears in the first-membrane permeate. and a maximum is found.'. 5. Since at the lowest brine flows the permeate from the second membrane may be more concentrated than the initial feed.._. 4)... as in the single membrane experiments plotted above. -Isu f. and can be plotted vs. the effective rejection of the system may be plotted as the ratio of brine to product concentrations (Fig.

1 ppT NaCl feed.65 MPa pressure applied. 1. Final-stage permeate concentration (A) and flow (Cl) in recycle mode. The permeate flow from the second membrane. membrane system with recycle. 1 ppT NaCl feed concentration.65 MPa pressure applied. principal membrane. reject flow from two-stage Fig. 6 form a basis for calculation of the effective first membrane inlet concentration. vs. 6. brine flow. 1. 12 6 % a s 4 0 5 IO I. 0 5 10 15 20 25 Brine ml/mn 5. which is added to the input feed. Product recovery fraction (A) and concentration (Cl). The experimental measurements plotted in Fig. is of considerable interest. The influence of the recycled configuration on water quality can be seen . of degradation tolerated by water quality standards and limits [ 141 may be chosen from such a figure.5 20 Brine ml/mn Fig. and used in selecting the optimum brine flow. vs. since its volume flow and salinity are included in the inlet conditions for the first.

---. . and the single membrane under the same conditions of pressure and brine flow. in Fig..-. 0 5 10 15 20 2s Brine ml/mn Fig. 287 in a comparison of product salt content of the two membrane system. 1 ppT NaCl feed. Product salinity from single membrane (H) and from recycling membrane pair (Cl) at 1. In Fig. Brine/product salinity ratio from single membrane (H) and from recycling membrane (Cl) at 1. 8 the resulting concentration ratio between product and brine represents the separation achieved by the single membrane in comparison with the recycling configuration. ... 400.-. 8. o-... with recycle of the second permeate. .65 MPa. 0 5 IO I5 20 u Brine ml/mn Fig.---.65 MPa.. 7. . 7.

12. This approach was used by Van Wijk et al. in Figs. (Fl . the per- meate concentration is close to the NF membrane’s feed concentration. and the water recovery fraction is compared with the permeate quality in Fig. it is of interest to determine the rate of salt recycled as the product of concentration and flow in Fig. The recycle stream itself shows the water and salinity transport of Fig. 9-l 1. Performance can be plotted as practical functions of pump flow. were of interest in that their nominal rejection of about 2/3 (for sodium chloride) may be quite appropriate for a second-stage membrane to produce increased brine concentration and a permeate of in- termediate osmotic pressure to be recycled. 2. Operating at permeate flows much higher than brine flows. To examine perfor- mance of the recycle configuration at a concentration similar to seawater. the first-stage membrane was replaced with a next-size-larger seawater membrane (Filmtec SW30-2521). FI)*Vb .288 SEAWATER MEMBRANE RESULTS Theabove membranes were “brackish water” membranes. [PI)*Vp = ([RI . with curve-fitting equations approximating the data over the range of measurement. lower-flux seawater car- tridge as the second stage. and (2) to produce a higher-concentration recycle permeate than was found with a higher-rejection. [15] to concentrate glucose from 5% to 20% at a pressure of 4 MPa. 11.3*[R] for the case of 70% rejection and. The corresponding concentrations found are plotted in Fig. Since the recycle volume decreases as the recycle concentration increases. appropriate for wastewater in the part-per-thousand salinity range. Experiments with a nanofiltration membrane (NF-70) in the same cartridge size as the brackish-water RO membrane tested produced the following results: 1. as is predicted by a mass-balance relationship: [P] = 0. Substantial increase in brine concentration was confirmed. 13. PARTIALLY REJECTING MEMBRANES The membranes of intermediate permeability often called “nanofiltra- tion” (NF) membranes. The brackish-water second-stage mem- brane was retained (1) to provide a larger first-stage reject (=second-stage permeate+reject) flow. 10.

Reject g/l = 70.708’ (pumped ml/min) -0. 3. 10.956.5 MPa. reject and recycle flows: 5. Second order curve fit: Recycle flow = O. flow = 15. ml/mm. Cl : brine flow. from 3. 9.1+0.910.41. R2 = 0. R2 = 0.00071’ (pumped ml/min)2. Linear regression: Recycle flow = -5.463*(pumped ml/ruin). Second order curve fit: Brine flow = 0.7 + 0.964.8*log (pumped ml/mm).6+ O. A longer first- membrane desalination path would be expected to yield a product within drinking-water salinity limits. ml/mm. Permeate g/l = 175 . A : perme- ate flow.5 MPa.967. R2 = 0.5% NaCl feed.978.10.00022*(pumped ml/min)2.918.280’ (pumped ml/min) + O.5% NaCl feed. Permeate (A). Linear regression: Brine flow = . R2 = 0.3 PumpeZ ml/mLte Fig. R2 = 0. .3 .O0049*(pumped ml/min)2.2*log (pumped mllmin).981. 289 Pumped ml/minute Fig. 11.O1257*(pumped ml/min) + 0.25. reject (Cl) and recycle (m) concentrations: 5. Second order curve fit: Perm. = 0.I 0 $3 x. R2 = 0. Linear regression: Perm. 2 1 Fig. R2 = 0. n : recycle flow. ml/min. Permeate.902.960.441 *(pumped mVmin).5% NaCl feed. Water quality (Cl) and recovery (H). flow = 0. R2 = 0. 3.O96O*(pumpedml/ml). .

Slope: (ppT*ml/min. Cl : from 1 ppT feed data.5 E : E Pumped ml/minute Fig. recycled = 0. 3. Slope: (ppT*ml/min. Amount of salt recycled.5% NaCl feed.5% feed data. ml/minute Fig. recycled) = 065*(pumped ml/min). . n : from 3. 13.3*(pumped ml/min). Y ’ zoo- . Recycle stream concentration (0) and flow (m): 5. 12. Pumped.5 MPa.

. and permeating constituents (volatile organics and a few inorganics). solubility limits in the final brine could be exceeded. and [R] respectively. Processes other than RO are to be addressed on the issues of: membrane fouling (by inorganic precipitates or organic accumulations). The tech- nical assistance of student interns Eric Litwiller and David English is appreciated. With sodium chloride feed of 1. bacterial attack or contamination. CONCLUSIONS Simple empirical equations can be fitted to experimental measurements on RO membrane cartridges. the rejection of the NF mem- brane drops. At very high recoveries. [PI. Enhancement of final brine concentration by such a NF membrane. When placed after a first-stage brackish-water membrane of similar size. ACKNOWLEDGEMENTS This work was supported by NASA contract NAS 2-13273. permeate. 291 where concentrations of feed. recoveries of 50% to 70% have been achieved using a single pump at 5. however. and reject brine are [F]. if significant concentrations of more strongly retained molecules are present. With restriction -of the NF permeate flux. recoveries of 9S-97% are achieved at a pressure of 1. and volumes per unit time of permeate and brine are Vp and Vb. the permeate flux of the nanofiltration membrane is too high.65 MPa. 000 ppM con- centration. respectively.would be effective following an RO membrane of 10 to 100 times the size of the NF cartridge. Enhanced brine concentration as well as enhanced product/feed water recovery fraction can be obtained by recycle of a second-stage permate of intermediate quality. solubility limitations of the feed water con- stituents becomes a principal caution. With feed of seawater concentration. from which RO system performance can be predicted. 3. or simulated as part of a system performance model. This rejection becomes too low to offer significant enhancement of the final brine concentration.5 MPa. as the rejection of the brackish-water RO membrane was shown to decrease.

Phys. 12 D.. pp. Kulkarni. Sauer and RI? Reysa. Van Wijk.L. D.J.V. Dubrovnik. July 1983. Test results of a shower water recovery system. 45-48. Newbold and H. Sauer. Spatz. C. Linton and T. 17th Intersociety Conference on Environmental Systems. J. Kosmicheskaya Biologiyai Aviakosmicheskaya Meditsina. 2 C.E. San Diego. Hyperfiltration wash water recovery subsystem .F. Water quality program el- ements for Space Station Freedom. 3.. Chem. Jansen and R.Yu. S. McCray. Creusen. Seattle. Paper #911400.L. Renfro.design and test results. July 1987.H. Hitt. 92 (1988) 1981-1985. 11 R. 15th Intersociety Conference on Environmental Systems. K.E. Volgin. J. July 1985. Membrane-based water. 8th Yugoslav Symposium of Electrochemistry. Ye. R.. 19th Intersociety Conference on Environmental Systems. Olcott. Sinyak.J. Pierson. Straub and J.F.F. J. Perona and R. paper #871512. New York.D. 5 1 (1984) 103-l 12.and energy-recovery systems for the manned space station. Critera definition and performance testing of a space station experiment water management system. R. 6 RI! Reysa. Test results on reuse of reclaimed shower water -A summary. paper #83 1112. E. Streams.H. 8 S. 14 R. Ray. Balaban. T. Ray. paper #881019. Madsen. Peters.M.S. Ramanathan. Verostko. LeskovSek. Sauer. Funk and R. p. Polyakov. R./Feb. San Francisco. 7 A.L. 1983. 4 S. R. Schien and E. in: Desalination and Water Reuse. Schultz. 4 (Jan. Gaddis. 13 J. paper #881032. Desalination. Elms. A. Novikov. Ye. ed.J. D. 10 D. Hemisphere Publ. 3 A. 13th Intersociety Conference on Environmental Systems. 18th Intersociety Conference on Environmental Systems.A.F. R. Vial and R. 11 (1972) 149-163.F. San Francisco. A.J. Garcia. 1972) 24-26..E. . Stewart and C. Dillon. Develop- ment of a non-phase-change waste-water treatment subsystem. July 1991. Co.S. D. San Francisco. 18th Intersociety Conference on Environmental Systems. Recovery of space station hygiene water by membrane technology. Vol.T. 21 st International Conference on Environmental Systems..D. Osmotic coefficients and molar conductivities of aqueous solutions of NaCl at 25’ C.X.D. 20(2) (1986) 78. July 1989. D.E. M.W.P. paper #891443. paper #871514. 9 R. Binot. 15 H. July 1988.A. paper #851345. Swamikannu. The proposal for the com- pletely closed system in the Columbus space station. Maksimov and VI. Price.F. Reysa. PollutionEnS.R. Garcia. Price and J. Thomassen. D. Thornton. R.292 REFERENCES 1 C.A. Desalination. III. D.B. 17th Intersociety Conference on Environmental Systems. 123. Seattle.. R. V. Zener. 5 R. July 1988. R. Reclamation of water used for washing by means of reverse osmosis during long- term spaceflights. July 1987. 1991. Verostko. Madsen.R.