WO2002016269A9

WO2002016269A9 - Process and apparatus for blending product liquid from different thin film composite membranes

Info

Publication number: WO2002016269A9
Application number: PCT/US2001/026582
Authority: WO
Inventors: Barry H Lee; Gene Wayman; Newenhizen John Van
Original assignee: United States Filter Corp; Barry H Lee; Gene Wayman; Newenhizen John Van
Priority date: 2000-08-25
Filing date: 2001-08-24
Publication date: 2003-03-20
Also published as: AU8677001A; US6645383B1; AU2001286770B2; JP2004506512A; CA2418469C; IL154322A0; IL154322A; KR20030059112A; CN1449301A; PL365692A1; WO2002016269A2; RU2003107099A; EP1313546A2; CN1241675C; NZ524118A; HK1059060A1; CA2418469A1; MXPA03001255A; WO2002016269A3

Abstract

A process and apparatus for membrane treatment includes feeding a liquid to a membrane. The primary membrane (14) separates the feed into a primary membrane retentate (16) and a primary membrane permeate(18). The primary membrane retentate (16) is fed to supplemental primary membranes (24,34) or to a secondary membrane(54). The primary membrane retentate (16) is separated by the secondary membrane (54) into a secondary membrane retentate(56), and a secondary membrane permeate(58).The secondary membrane retentate (56) may either be discarded, or may be fed to supplemental secondary membranes(64,74). If the secondary membrane retentate (56) is fed to a supplemental secondary membrane(64), the secondary membrane retentate (56) is separated into a supplemental secondary membrane retentate (66) and supplemental secondary membrane permeate(68). The product liquid is formed by blending the primary membrane permeate (18) with the secondary membrane permeate (58) and all supplemental primary membrane permeates (28,38) and supplemental secondary membrane permeates(68,78).

Description

PROCESS AND APPARATUS FOR BLENDING PRODUCT LIQUID FROM DIFFERENT THIN FILM COMPOSITE MEMBRANES

Technical Field

The present invention relates generally to a process and apparatus for the treatment of water using membrane technology to separate the constituents of a feed liquid, and specifically to a process and apparatus for purification and blending of an aqueous solution utilizing one or more first membrane process units having a first permeability connected in series with one or more second membrane process units having a second permeability to produce a desired blended product water thus modified to improve its taste characteristics.

Background Art The following expressions are defined to provide a better understanding of the present specification and claims.

Thin film composite membrane (TFC) process: Purification of liquid occurs through a thin film composite membrane where a feed liquid is separated into retentate and a permeate. Retentate: The portion of a feed liquid which is retained by a membrane.

Permeate: The portion of a feed liquid which passes through a membrane.

Nanofiltration (NF): Filtration of a liquid through a NF-membrane. Such membranes are usually ion-selective and reject ions at varying percentages depending on the total molarity of the feed liquid and the chemistry of the membrane. Further, such filtration membranes typically have a pore size of 0.0007 Φm to 0.007 Φm, such pore sizes corresponding to a molecular cutoff value ranging from 140 A to 15,000 A.

Reverse osmosis (RO): A liquid separation process in which a solution is put through a semi-permeable membrane that excludes most soluble ions thus concentrating undesired soluble and insoluble species in the retentate. Such membranes allow the passage of some ions in the size range of 0 Φm to 0.0015 Φm, which corresponds to a molecular cutoff value of .between 0 A and 300 A. RO separation of solution where water is the solvent typically results in a permeate consisting of only water with most ions being exluded. Permeable solutes: Substances dispersed in the liquid which are capable of passing through the membrane employed. Such substances may be electrolytes, nonelectrolytes, colloidal dispersions, and/or particles.

Feed liquid: Liquid fed to the first of a series of membrane process units. Such a liquid could be a solution wherein the solutes may be dissolved and/or undissolved. Undissolved material may need to be filtered out before the membrane processes.

Hardness: The combined concentrations of magnesium and calcium salts as measured by CaC0₃. Alkalinity: The measure of carbonate, bicarbonate, and hydroxide as

CaC0₃.

When a feed liquid is fed into a membrane process unit, the feed liquid is separated into a retentate and a permeate. The permeate is the portion ofthe feed liquid which passes through a membrane contained within the process unit. Contained within the permeate are permeable solutes. Those solutes which are not capable of passing through the membrane being employed, or non-permeable solutes, are retained within the retentate.

Whether a solute is permeable or non-permeable depends upon the type of membrane used. Certain membranes may be employed which exclude solutes based upon molecular size. As the permeability or pore size increases, so does the passage of the permeable solutes. In addition, an ion selective membrane may be employed which excludes a solute based upon its charge.

Separation by the reverse osmosis process, and more particularly, purification of water by reverse osmosis in order to produce drinkable or potable water, is known. U.S. Patent No. 5,238,574 to Kawashima et al. describes an apparatus for treating salt water using a plurality of reverse osmosis membrane units. However, a disadvantage of these types of membrane systems is that they produce product water which is of such a high quality that its taste characteristics may be unacceptable. These unacceptable taste characteristics result because the permeates produced by such reverse osmosis membrane systems tend to have low alkalinity levels, and significantly reduced levels of dissolved salts. As a result, the product water has an off taste or a flat taste.

The poor taste characteristics of product water produced by reverse osmosis can be overcome by two known post-filtration blending methods. The first method employs blending a portion of the feed liquid or untreated water with the permeate to produce product water having desired levels of alkalinity and dissolved salts.

A disadvantage of this method is that it requires constant adjustment of the volume of untreated water needed for blending. The constant adjustment of the volume of feed water is due to the constantly changing chemical characteristics and pressure ofthe feed water. Also, introduction of untreated water back into the product water reduces the attainable benefits ofthe membrane process in removing unwanted substances from the feed water.

The second method employs the addition of minerals to the permeate to achieve the desired taste characteristics. This latter method is undesirable due to its high cost and inefficiency, since the membrane process removed the existing minerals in the first place.

Therefore, it is a first object of the present invention to provide an improved process and apparatus for treating a feed liquid to produce a product liquid having certain desired physical properties, resulting in improved taste. A second object ofthe present invention is to provide an improved process and apparatus for treating a feed liquid without the necessity of blending a portion ofthe feed liquid with the permeate in order to produce a product liquid having certain desired physical properties.

It is a further object of the present invention to provide an improved process and apparatus for treating drinking water by membrane processes without the necessity of introducing minerals to the permeate to produce a product liquid having desired taste properties.

It is another object of the present invention to provide an improved process and apparatus for treating drinking water using membrane processes having different permeablities or porosities which can be arranged to produce a blended product liquid having certain desired chemical characteristics regardless of the chemical properties ofthe feed liquid.

Disclosure Of The Invention The above-listed objects are met or exceeded by the present process and apparatus for membrane processing of a feed liquid to produce a product liquid. In the present system, at least two distinct membrane types are employed, each type having a distinct permeability. Permeates of the two types are blended to produce a treated product liquid having the desired water quality. Preferably, the permeability ofthe first type of membrane unit has a higher solid content than the second type, where the retentate of the first type is the feed liquid for the second type.

More specifically, to produce the product liquid, a feed liquid, typically an aqueous solution such as tap water, is first fed to a primary membrane type. The primary membrane separates the feed liquid into a primary membrane retentate which is retained by the primary membrane, and a primary membrane permeate. The primary membrane retentate is then fed to a secondary membrane type. The secondary membrane separates the primary membrane retentate into a secondary membrane retentate which is retained by the secondary membrane, and a secondary membrane permeate. The final product liquid is formed by blending the primary membrane permeate with the secondary membrane permeate.

In the prefeπed embodiment, the primary membrane produces water of poorer quality than the secondary membrane. This is because the permeable solute concentration of the primary membrane permeate is greater than the permeable solute concentration ofthe secondary membrane permeate. Thus, the final product liquid is a blend ofthe products of two different levels of membrane treatment. In this manner, the taste of product drinking water can be adjusted without introducing untreated water, and without adding supplemental minerals.

Alternate embodiments include the addition of one or more supplemental primary membranes connected in series with the primary membrane, and also include one or more supplemental secondary membranes connected in series with the secondary membrane. In this case, the primary membrane retentate is fed to a first supplemental primary membrane, and the retentate formed by the first supplemental primary membrane is fed to a second supplemental primary membrane. The retentate formed by the last supplemental primary membrane is then fed to the secondary membrane as feed liquid. The secondary membrane retentate formed by the secondary membrane may either be collected and disposed of, or may be fed to one or more supplemental secondary membranes. If the secondary membrane retentate is fed to a supplemental secondary membrane, the secondary membrane retentate (or retentate from a prior supplemental secondary membrane) is separated into a supplemental secondary membrane retentate and supplemental secondary membrane permeate.

The product water is formed by blending the primary membrane permeate and all permeates formed by the supplemental primary membranes with the secondary membrane permeate and all permeates formed by the supplemental primary membranes. Brief Description Of The Drawing

FIG. 1 is a schematic diagram ofthe present membrane treatment system, which is suitable for use with the present method.

Best Mode Of Carrying Out The Invention

Referring now to FIG. 1 , an apparatus for membrane separation of a feed liquid to form a product liquid is schematically shown. A feed liquid, typically an aqueous solution such as tap water, is introduced into a primary membrane unit 10 through a primary membrane unit feed liquid inlet 12. A primary membrane 14 contained within the primary membrane unit 10 separates the feed liquid into a primary membrane retentate (indicated by arrows 16) which is retained by the primary membrane 14, and a primary membrane permeate (indicated by arrows 18) formed when the feed liquid passes through the primary membrane 14.

From the primary membrane unit 10, the primary membrane retentate 16 is removed through a primary membrane unit retentate outlet 19 and introduced into a first supplemental primary membrane unit 20 through a first supplemental primary membrane unit inlet 22. A first supplemental primary membrane 24 contained within the first supplemental primary membrane unit 20 separates the primary membrane retentate 16 into a first supplemental primary membrane retentate (indicated by arrows 26) which is retained by the first supplemental primary membrane 24, and a first supplemental primary membrane permeate (indicated by arrows 28) formed when the primary membrane retentate passes through the first supplemental primary membrane 24.

The first supplemental primary membrane retentate 26 is removed from the first supplemental primary membrane unit 20 through a first supplemental primary filtration unit retentate outlet 29 and introduced into a second supplemental primary membrane unit 30 through a second supplemental primary membrane unit inlet 32. A second supplemental primary membrane 34 contained within the second supplemental primary membrane unit 30 separates the first supplemental primary membrane retentate 26 into a second supplemental primary membrane retentate (indicated by arrows 36) which is retained by the second supplemental primary membrane 34, and a second supplemental primary membrane permeate (indicated by aπows 38). The second supplemental primary membrane permeate 38 is formed when the first supplemental primary membrane retentate 28 passes through the second supplemental primary membrane 34. The primary membrane permeate 18, first supplemental primary membrane permeate 28, and the second supplemental primary membrane permeate 38 each are fed through a primary membrane unit permeate outlet 42, a first supplemental primary membrane unit permeate outlet 44, and a second supplemental primary membrane unit permeate outlet 46, respectively, and combined or blended together at a primary feed line 48.

In the preferred embodiment, each ofthe primary membranes 14, 24, 34 are identical, although the use of distinct membranes or types of membranes is contemplated depending on the desired characteristics ofthe final product water. More specifically, the primary membrane 14, 24, 34 is a nanofiltration membrane. Various nanofiltration membranes are commercially available and may vary with respect to their performance characteristics. Further, the physical properties ofthe permeate produced depend upon the physical properties ofthe feed liquid. While three nanofiltration units are depicted in FIG. 1 , namely, the primary membrane unit 10, the first supplemental primary membrane unit 20, and the second supplemental primary membrane unit 30, the invention is not so limited. One or more nanofiltration units, each having a housing 41 as well as identical performance characteristics or having varying performing characteristics with respect to each other, may be used to produce a product liquid having the desired physical properties. Variation of the number of nanofiltration units is contemplated where the feed liquid is tap water, because the physical properties of tap water vary worldwide. However, it is contemplated that one with ordinary skill in the art would be able to select and determine, without undue experimentation, number of nanofiltration units necessary to produce a product liquid having the desired physical properties at a sufficient flow rate. Further membrane treatment is performed by feeding the second supplemental primary membrane retentate 36 from the second primary membrane unit 30 through a second supplemental primary membrane unit retentate outlet 39. The second supplemental primary membrane retentate 36 is then introduced through a secondary membrane unit feed liquid inlet 52 into a secondary membrane unit 50. However, where treatment is performed using one or more primary membrane units ( 10, 20, 30), the liquid preferably introduced into the secondary membrane unit 50 will be the retentate formed by the last operating primary membrane unit. For example, if only the primary membrane unit 10 were employed, then the primary membrane retentate would then be introduced into the secondary membrane unit 50 through the secondary membrane unit feed liquid inlet 52.

Contained within the secondary membrane unit 50 is a secondary membrane 54. The secondary membrane 54 separates the second supplemental primary membrane retentate 36 into a secondary membrane retentate (indicated by arrows 56) retained by the secondary membrane 52, and a secondary membrane permeate (indicated by arrows 58). The secondary membrane permeate 58 is formed when the second supplemental primary membrane retentate 36 passes through the secondary membrane 54. From the secondary membrane unit 50, the secondary membrane retentate

56 is removed through a secondary membrane unit permeate outlet 59 and preferably introduced into a first supplemental secondary membrane unit 60 through a first supplemental secondary membrane unit inlet 62. Alternatively, the permeate 56 is disposed of. A first supplemental secondary membrane 64 contained within the first supplemental secondary membrane unit 60 separates the secondary membrane retentate 56 into a first supplemental secondary membrane retentate (indicated by arrows 66) which is retained by the first supplemental secondary membrane 64, and a first supplemental secondary membrane permeate (indicated by aπows 68). The first supplemental secondary membrane permeate 68 is formed when the secondary membrane retentate 56 passes through the first supplemental secondary membrane 64.

The first supplemental secondary membrane retentate 66 is removed from the first supplemental secondary membrane unit 60 through a first supplemental secondary membrane unit retentate outlet 69 and either sent to drain or introduced into a second supplemental secondary membrane unit 70 through a second supplemental secondary membrane unit inlet 72. A second supplemental secondary membrane 74 contained within the second supplemental secondary membrane unit 70 separates the first supplemental secondary membrane retentate 66 into a second supplemental secondary membrane retentate (indicated by arrows 76) which is retained by the second supplemental secondary membrane 74, and a second supplemental secondary membrane permeate (indicated by arrows 78). The second supplemental secondary membrane permeate 78 is formed when the first supplemental secondary membrane retentate 66 passes through the second supplemental secondary membrane 74.

The secondary membrane permeate 58, first supplemental secondary membrane permeate 68, and second supplemental secondary membrane permeate 78 are fed through a secondary membrane unit permeate outlet 82, a first supplemental secondary membrane unit permeate outlet 84, and a second supplemental secondary membrane unit permeate outlet 86, respectively, and combined or blended together at a secondary feed line 88. The liquid contents of the primary feed line 48 and the liquid contents ofthe secondary feed line 88 are then combined or blended together forming the product liquid. The second supplemental secondary membrane retentate 76 is then removed from the second supplemental secondary membrane unit 70 through a second supplemental secondary membrane unit retentate outlet 79 and disposed of.

In the preferred embodiment, the secondary membranes 54, 64, 74 are reverse osmosis membranes. Various types of reverse osmosis membranes are commercially available and may vary with respect to their performance characteristics. The desired physical properties ofthe product liquid and the required production rate will therefore govern the selection of the reverse osmosis membrane and the number of reverse osmosis membranes to be employed. While three reverse osmosis membrane units are depicted in FIG. 1 , namely, the secondary membrane unit 50, the first supplemental secondary membrane unit 60, and second supplemental secondary membrane unit 70, the invention is not so limited. One or more reverse osmosis units, each having a housing 81, as well as identical performance characteristics or having varying performing characteristics with respect to each other, may be used to produce a product liquid having the desired physical properties. It is also contemplated that, while in the preferred embodiment, the secondary membranes 54, 64, 74 have substantially identical separation properties, depending on the desired characteristics ofthe product water, they may be different from each other. One with ordinary skill in the art could select and determine, without undue experimentation, the number of reverse osmosis units necessary to produce a product liquid having the desired physical properties at an acceptable flow rate.

Example 1

The ranges of acceptable hardness and alkalinity concentrations in product water were determined by varying the number of reverse osmosis units and nanofiltration units employed. It is known in the art that the upper limits for both hardness and alkalinity are 100 ppm. After conducting a taste panel, product water having a hardness concentration of at least 20 ppm and an alkalinity concentration of at least 21 ppm was found to be superior to product water having lower concentrations. Example 2

The quality of product water produced as a function of the membrane employed was determined.

The Culligan RO-A6 Series reverse osmosis membrane is available from Culligan International Company of Northbrook, Illinois. The Filmtec NF-255 nanofiltration membrane and the Filmtec NF-45 nanofiltration membrane are available from Flimtec Corporation located in Minneapolis, Minnesota. By definition nanofilters are rated to have greater permeability or porosity, and a corresponding greater solute solids concentration than the RO membranes.

In each test, a total of six membranes were employed to produce the tested product water: two sets or banks of membranes, each set or bank having three identical membranes. Banks were inserted or removed to change the membrane combinations. The feed water used in each test was from a single source. Product water test samples were collected after one hour of continuous service. The feed water and the resulting product water for each combination possessed the following characteristics.

Table 1.

Combination Hardness Alkalinity pH Filtration Pressure Flow Rate (ppm) (ppm) (psig) (gpm)

Untreated water 334 262 7.36

NF-45(3) - NF-255(3) 76 124 7.02 128 4.4

Untreated water 332 256 —

NF-45(3) - RO(3) 6 38 6.64 135 4.4

Untreated water 338 260 -

NF-255(3) -- RO(3) 50 78 7 140 >5

Hardness was determined by endpoint titration using ethylenediaminetetraacetic acid (EDTA) as the titrant, as outlined in Standard Methods 2340C (EDTA Tiration Method). Alkalinity was determined by Standard Methods #2320B (Alkalinity Titration Method). From the results of Table 1 , it will be seen that the use of nanofilters and RO membrane units in combination to create a blended product water provided better results, in that they were closer to the target hardness and alkalinity values, than the exclusive use of nanofilters in series. While a particular embodiment ofthe process and apparatus for blending product from different membrane types has been shown and described, it will be appreciated by those skilled in the art that changes and modifications may be made thereto without departing from the invention in its broader aspects and as set forth in the following claims.

Claims

1. A process for membrane separation of a liquid characterized by: feeding said liquid to a primary membrane, said primary membrane separating said liquid into a primary membrane retentate retained by said primary membrane, and a primary membrane permeate; feeding said primary membrane retentate to a secondary membrane, said secondary membrane separating said primary membrane retentate into a secondary membrane retentate retained by said secondary membrane, and a secondary membrane permeate; and blending said primary membrane permeate and said secondary membrane permeate to form a product liquid.

2. The process according to claim 1 further characterized by said primary membrane having a nanofiltration membrane.

3. The process according to claim 2, characterized by said primary membrane having an ion selective nanofiltration membrane.

4. The process according to claim 1 , characterized by said secondary membrane having a reverse osmosis membrane.

5. The process according to claim 1, characterized by said primary membrane having a nanofiltration membrane, and said secondary membrane having a reverse osmosis membrane.

6. The process according to claim 1, characterized by said primary membrane having an ion selective nanofiltration membrane, and said secondary membrane having a reverse osmosis membrane.

7. The process according to claim 1, characterized by the solute concentration of said primary membrane permeate having greater than the solute concentration of said secondary membrane permeate.

8. The process according to claim 1, characterized further by including sequentially feeding said primary membrane retentate to a supplemental primary membrane for separating said primary membrane retentate into a supplemental primary retentate and a supplemental primary permeate.

9. The process according to claim 8, further characterized by including sequentially feeding said secondary membrane retentate to a supplemental secondary membrane for separating said secondary membrane retentate into a supplemental secondary retentate and a supplemental secondary permeate.

10. The process according to claim 9, characterized by said primary membrane and said supplemental primary membrane having ion selective nanofiltration membranes, and said secondary membrane and said supplemental secondary membrane having reverse osmosis membranes.

11. The process according to claim 9, characterized by the solute concentration of either of said primary membrane permeate or said supplemental primary membrane permeate having greater than the solute concentration of either of said secondary membrane permeate or said supplemental secondary membrane permeate.

12. The process according to claim 8, further characterized by including a plurality of supplemental primary membranes connected in series.

13. The process according to claim 12, further characterized by including a plurality of supplemental secondary membranes connected in series.

14. The process according to claim 8, characterized by the solute concentration of said primary membrane permeate having greater than the solute concentration of said secondary membrane permeate.

15. The process according to claim 1, further characterized by including sequentially feeding said secondary membrane retentate to a supplemental secondary membrane for separating said secondary membrane retentate into a supplemental secondary retentate and a supplemental secondary permeate.

16. The process according to claim 15, characterized by a plurality of supplemental secondary membranes connected in series.

17. An apparatus for purifying a feed liquid characterized by:

(A) At least one primary membrane unit coupled in series to at least one succeeding secondary membrane unit;

(B) each said primary membrane unit having

( 1 ) a primary membrane unit feed liquid inlet for introducing the feed liquid to nanofiltration membrane, the feed liquid being either said feed liquid or a primary membrane unit retentate from a preceding primary membrane unit,

(2) a first membrane for separating said feed liquid into a primary membrane unit retentate and a primary membrane unit permeate,

(3) a primary membrane unit retentate outlet for feeding said primary membrane unit retentate to said secondary membrane unit or to a succeeding primary membrane unit, and

(4) a primary membrane unit permeate outlet for feeding said primary membrane unit permeate to a product liquid flow line;

(C) each said secondary membrane unit having ( 1 ) a second membrane for separating said primary membrane unit retentate into a secondary membrane unit retentate and a secondary membrane unit permeate;

(2) a secondary membrane unit liquid inlet for receiving said primary membrane unit retentate to said second membrane or for receiving a secondary membrane unit retentate from a preceding secondary membrane unit to said second membrane, and a secondary membrane unit permeate outlet for feeding said primary unit permeate to said product liquid flow line;

(D) wherein said product liquid flow line receives and blends said primary membrane unit permeate and said second membrane unit permeate.

18. The apparatus according to claim 17, characterized by said first membrane is a nanomembrane membrane, and said second membrane having a reverse osmosis membrane.

19. The apparatus according to claim 17, characterized by said primary membrane unit permeate having a higher solute concentration than said secondary membrane unit permeate.

20. The apparatus according to claim 17, further characterized by including a plurality of primary membrane units coupled to each other in series to successively receive the retentate from the previous unit and to send the permeate generated to a product flow line.

21. The apparatus according to claim 17, further characterized by including a plurality of secondary membrane units coupled to each other in series to successively receive the retentate from the previous unit and to send the permeate generated to a product flow line.

22. A process for membrane separation of a liquid characterized by: feeding said liquid to a first primary membrane, said first primary membrane separating said liquid into a first primary membrane retentate retained by said first primary membrane, and a first primary membrane permeate; feeding said first primary membrane retentate to a second primary membrane, said second primary membrane separating said first primary membrane retentate into a second primary membrane retentate retained by said second primary membrane, and a second primary membrane permeate; feeding said second primary membrane permeate to a first secondary membrane, said first secondary membrane separating said second primary membrane retentate into a first secondary membrane retentate retained by said first secondary membrane, and a first secondary membrane permeate; feeding said first secondary membrane permeate to a second secondary membrane, said second secondary membrane separating said first secondary membrane retentate into a second secondary membrane retentate retained by said second secondary membrane, and a second secondary membrane permeate; and combining said first primary membrane permeate, said second primary permeate, said first secondary membrane permeate, and said second secondary membrane permeate to form a product liquid.

23. The process according to claim 22 further characterized by including at least one supplemental primary membrane connected in series to said second primary membrane.

24. The process according to claim 22 further characterized by including at least one supplemental secondary membrane connected in series to said second secondary membrane.