US20170226438A1

US20170226438A1 - Membrane Filter Element With Multiple Fiber Types

Info

Publication number: US20170226438A1
Application number: US15/495,611
Authority: US
Inventors: Richard D. Peters; George E. Mahley, III; Atsushi Morisato; Fatimah Binti A. Karim; Hatarmizi Bin Hassan; Zalina Binti Ali; Wan Atikahsari Wan Zakaria; Faudzi Mat Isa; Faizal Bin Mohamad Fadzillah
Original assignee: Petronas Carigali Sdn Bhd; Cameron Solutions Inc
Current assignee: Petronas Carigali Sdn Bhd; Cameron Solutions Inc
Priority date: 2009-02-20
Filing date: 2017-04-24
Publication date: 2017-08-10
Also published as: US20100212501A1; MY164749A; US9630141B2; GB2480218B; TW201039905A; CA2753143C; BRPI1005823A2; JP2012518529A; AR075538A1; GB201115801D0; GB2480218A; CA2753143A1; JP5541636B2; AU2010216092A1; WO2010096455A1; AU2010216092B2

Abstract

A membrane filter element includes at least two cylindrical-shaped, fiber bundles, one of the fiber bundles containing first fibers fabricated to provide a selected first gas selectivity, a selected first gas permeability, or a selected first gas selectivity and permeability performance and arranged so a first gas permeate exits the membrane element; another of the fiber bundles containing second fibers fabricated to provide a selected second, different gas selectivity, a selected second different gas permeability, or a selected second gas selectivity and permeability performance and arranged so a second different gas permeate exits the membrane element. The different performance characteristics can reduce the number of membrane elements required for gas separation and to improve gas separation performance due to changing gas composition as the gas travels through the membrane element.

Description

CROSS-REFERENCE TO PENDING APPLICATIONS

This application is a continuation application of U.S. patent application Ser. No. 12/706,105, filed Feb. 16, 2010, which claimed the benefit of U.S. Provisional Patent Application No. 61/154,219, filed Feb. 20, 2009, the contents of which are hereby incorporated by reference in their entirety.

BACKGROUND

Field
This disclosure relates generally to apparatuses used in the treatment of gas. More particularly, the disclosure relates to semi-permeable membranes used in gas separation processes to remove acid gas and other components from a gas stream so that the gas may be usable for fuel.
Description of the Related Art
Much of the world's produced natural gas contains unacceptably high concentrations of acid gas—primarily CO₂and H₂S—which must be removed before the gas is usable for fuel. The utilization of semi-permeable membranes for CO₂/natural gas separation is well known and spiral wound and hollow fiber membrane configurations have been used for this purpose.
Commonly used membrane configurations include fiber materials made of organic polymers and copolymers including polysulfones, polycarbonates, cellulose acetates, cellulose triacetates, polyamides, polyimides, and mixed-matrix membranes. Regardless of the fiber material used, the membrane elements are fabricated with the same type of fiber material throughout. Therefore, these membranes are limited to a single and set range of performance characteristics even though gas properties and volumes change throughout the membrane as permeation occurs. Additionally, current technology may require the operation of the membrane elements in multiple stages, so that gas is passed through multiple groups of membranes in series to partially compensate for the inefficiencies in the performance of each individual membrane stage. The result is additional equipment requirements and less than optimal membrane separation performance.
For applications that require a significant amount of CO₂removal, membrane element performance can be restricted by these uniform performance characteristics. For example, a membrane fiber that performs well in higher CO₂conditions may be less effective at lower CO₂concentrations (and vice versa). As a result, system design is often based on a compromise limited by the performance characteristics of the membrane fiber. Because of less than optimal membrane separation performance, additional equipment and additional stages of membrane elements are required to remove high percentages of CO₂. In addition, the membrane separation performance achieved with a single fiber type may be less efficient overall, resulting in higher hydrocarbon losses to permeate.
In many applications, the inlet gas has a high percentage (generally 10-95%) of inlet CO₂and membrane elements are used to bulk remove CO₂. As discussed previously, for high CO₂applications, the membrane elements often are configured to operate in series with multiple stages of membranes in operation. This can result in an inefficient configuration for equipment, which requires interconnect piping between stages, thereby creating a larger overall equipment footprint and higher equipment cost. Having multiple stages of membranes may also result in difficulty in balancing the flow rates and CO₂removal duties for each stage of membranes, as the amount of membrane surface area installed in each stage may have to be individually adjusted in order to maintain the desired separation performance characteristics.
Recent improvements in membrane manufacturing have led to significant increases in membrane fiber surface area in a single membrane element. For example, FIG. 1 shows older, prior art 5-inch and 12-inch diameter CYNARA® membrane elements 10 (Cameron International Corporation, Houston, Tex.) which have 500 and 2,500 square feet of active membrane fiber area, respectively. In comparison, newer larger 16-inch and 30-inch diameter membranes have been developed that have between 9,000 and 40,000 square feet of active fiber area, respectively. In the prior art—and unlike the embodiments disclosed herein—these larger diameter membranes are single fiber type membranes. The shear surface area of these larger diameter membranes provides greater capacity and allows for fewer stages of processing when compared to the number of processing stages needed when smaller diameter membranes are used. However, these larger membranes experience a larger gradient in, for example, CO₂concentration between the inlet and outlet side of the membrane when compared to the smaller diameter membranes. This larger gradient can reduce the effectiveness of these larger diameter, single fiber type membrane elements.
For membrane gas separation applications, the relative composition of the gas changes as the gas travels through the membrane bundle and permeable components are separated from the non-permeate components. At the same time, the inlet to non-permeate gas volume is reduced as gas passes through the membrane bundle and permeation occurs, with the inlet gas first entering the membrane being higher in volume and permeable components than the non-permeate gas exiting the membrane bundle. In other words, the gas oftentimes undergoes significant and non-uniform compositional changes as it travels through the membrane. Therefore, a need exists for a membrane element that has the requisite performance characteristics for improved gas separation even as the gas volume and composition change as the gas travels through the membrane.

SUMMARY

In general, disclosed herein are methods, systems, and apparatuses for a membrane fiber element. In some embodiments, the membrane element includes at least two concentric, cylindrical-shaped zones spanning a total height of the membrane element and extending around the membrane element. One of the zones is defined by first fibers fabricated to provide a selected first gas selectivity, a selected first gas permeability, or a selected first gas selectivity and permeability performance and arranged so a first gas permeate exits an end of the membrane element. Another of the zones defined by second fibers fabricated to provide a selected second, different gas selectivity, a selected second different gas permeability, or a selected second gas selectivity and permeability performance and arranged so a second different gas permeate exits an end of the membrane element. A method of treating a gas using the membrane element includes flowing the gas through the membrane element in a single stage of processing.
In other embodiments of a membrane filter element at least two different hollow fiber types are used. The hollow fiber types are wrapped about a perforated non-permeate pipe located at the center of the filter element to provide at least two circumferential zones. The first circumferential zone includes the first hollow fiber type and is located toward the inlet gas stream (or feed) side of the element. The second (or any subsequent) circumferential zone includes the second (or subsequent) hollow fiber type and is located between the first zone and the perforated non-permeate pipe. Because the hollow fiber types are fabricated to differ from one another in targeted acid-gas selectivity and permeability performance, and because the first and second hollow fiber types are arranged in their respective zones, the selectivity and permeability performance characteristics in the first zone differ from those of the second zone as does the composition and volume of the natural gas stream to which each zone is exposed.
The different performance characteristics may be a function of intentional differences in bore size, wall thickness, material, manufacturing process, or some combination thereof between the multiple hollow fiber types. For example, in an embodiment, the hollow fiber types differ in permeability (capacity or flux) and selectivity (separation or alpha). Or, the hollow fiber types may differ in CO₂and H₂S removal capacity or hydrocarbon removal capacity. Additionally, the hollow fiber types may differ in water dew pointing or hydrocarbon dew pointing performance.
Embodiments include a single membrane filter element that effectively accomplishes a range of separation from high CO₂to low CO₂(or vice versa). The membrane filter element can be optimized to two or more distinct separation functions including but not limited to CO₂and H₂S separation or CO₂and hydrocarbon dewpointing to the membrane filter element can provide for improved membrane efficiency and a better overall separation and capacity and simplify process control by reducing the number of filtering stages that require monitoring and eliminating the need for plant operators to rebalance flow rates between multiple stages of membrane filter elements or to change the relative loading between these stages. to the membrane filter element may provide for increased flexibility in accommodating changes in inlet gas composition over time. The membrane filter element can create more resistance to bypass or gas channeling and, therefore, eliminate the need for internal baffles or other gas distribution mechanisms.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features can be understood in detail, a more particular description may be had by reference to embodiments, some of which are illustrated in the appended drawings, wherein like reference numerals denote like elements. It is to be noted, however, that the appended drawings illustrate various embodiments and are therefore not to be considered limiting of its scope, and may admit to other equally effective embodiments.

FIG. 1 compares membrane filter element sizes—ranging in diameter from about 5 to 30 inches. For the purpose of this disclosure, the two smaller diameter membrane filter elements 10 are examples of prior art single fiber type filter elements. In many applications, several of these single fiber elements must be deployed in series or stages to treat an incoming natural gas stream. In some embodiments, a membrane element with a diameter greater than 12 inches is used for producing the multiple fiber membrane filter element of this disclosure. However, because of the greater bundle depth recently provided by large membrane elements, multiple fiber types may be used effectively in a single filter element, eliminating the need for several single fiber filter elements and multiple processing stages. Therefore, for the purpose of this disclosure, the two larger diameter membrane filter elements 20 are non-limiting examples of a multiple fiber type filter element.

FIG. 2 is a graphical depiction of the hollow fibers that make up the multiple fiber membrane filter element 20 of FIG. 1. The hollow fibers are arranged about a perforated non-permeate pipe. Optionally, the fibers may be arranged in bundles and then wrapped about the pipe.

FIG. 3 is a graphical depiction of the several hollow fibers of one of the bundles of FIG. 2. The fibers are isolated to indicate the size of the individual fibers.

FIG. 4 is an end view of one of the hollow fibers of FIG. 3 as it might appear under magnification. The multiple fiber membrane filter element includes many hundreds of thousands of these hollow fibers.

FIG. 5 is an end view of the multiple fiber membrane filter element 20 of FIG. 1 as it experiences an outside-in gas flow. The fiber types are generally arranged in two circumferential zones. Bundles located in the first circumferential zone include hollow fibers of one type and bundles located in the second zone hollow fibers of another type. Because the hollow fiber types are intentionally fabricated to differ from one another and provide a different target selectivity and permeability, the first zone exhibits different performance than does the second zone. Alternatively, gas flow could occur “inside out,” flowing first through the second zone and then through the first zone.

FIG. 6 is a schematic illustrating a prior art process that makes use of single fiber filter elements arranged in series, or two different single fiber type membranes with one fiber type used in Stage 1 and the second fiber type used in Stage 2.

FIG. 7 is a schematic illustrating a process that makes use of a filter element embodiment. The multiple fiber type filter element allows for single-stage processing.

DETAILED DESCRIPTION

In the following description, numerous details are set forth to provide an understanding of some embodiments of the present disclosure. However, it will be understood by those of ordinary skill in the art that the system and/or methodology may be practiced without these details and that numerous variations or modifications from the described embodiments may be possible.
In the specification and appended claims: the terms “connect”, “connection”, “connected”, “in connection with”, and “connecting” are used to mean “in direct connection with” or “in connection with via one or more elements”; and the term “set” is used to mean “one element” or “more than one element”. Further, the terms “couple”, “coupling”, “coupled”, “coupled together”, and “coupled with” are used to mean “directly coupled together” or “coupled together via one or more elements”. As used herein, the terms “up” and “down”, “upper” and “lower”, “upwardly” and downwardly”, “upstream” and “downstream”; “above” and “below”; and other like terms indicating relative positions above or below a given point or element are used in this description to more clearly describe some embodiments of the disclosure
Embodiments of a membrane element that has multiple hollow fiber types will now be described by making reference to the drawings and the following elements illustrated in the drawings:


10	Single fiber membrane element
20	Multiple fiber membrane element
21	Hollow fiber
23	Wall of 21
25	Bore of 21
27	Fiber bundle
29	Bundle depth
31	First circumferential zone of fibers
33	Second circumferential zone of fibers
35	Perforated non-permeate pipe
37	Central longitudinal axis of 20 & 35
41	Gas inlet or feed side of 20
43	Outlet or non-permeate side of 20
45	Membrane division

Referring now to FIG. 1, two prior art, single fiber membrane elements 10 are shown. Because membrane elements that have a diameter greater than 12 inches are useful for producing a multiple fiber membrane element, the larger diameter membranes of FIG. 1 are labeled as membrane 20. Membrane element 20 takes advantage of manufacturing improvements that have enabled the production of much larger diameter semi-permeable membrane filter elements for CO₂/natural gas separation. Single fiber membrane elements 10 are available in sizes similar to that of membrane element 20, but membrane element 20 as disclosed herein is not a prior art membrane element. The cylindrical-shaped membrane 10, 20 is typically housed within a pressure vessel connected by way of piping to an inlet gas stream (not shown) and may be configured for an “outside in” flow or “inside out” flow. Regardless of the direction of flow, as the inlet gas stream travels through the membrane 10, 20, acid gas and other undesirable components are removed to the permeate.
For the purpose of comparison with multiple fiber membrane element 20, single fiber membrane element 10 may be generally less than 15 inches in diameter and from about 24 inches to about 48 inches in height. Because membrane 10 does not have sufficient depth to minimize bypass—and because it employs a single fiber type that cannot account for the changes in gas volume and composition as the gas stream travels through the membrane 10—two or more membranes 10 must be arranged in series (see FIG. 6) with separation being performed in at least two stages. Selection of the fiber type for use in membrane 10 at each stage typically involves a trade-off between permeability (known as flow capacity or flux) and selectivity (called permeation rate or alpha). By way of example, as permeability increases in a polymeric membrane fiber, selectivity decreases (and vice versa).
Because of the trade-off between permeability and selectivity, some membrane fibers are better suited to higher concentrations of permeable components, while others are better suited to higher grade separations at lower concentrations of permeable components. Membrane fibers that exhibit better hydrocarbon separation attributes (higher selectivity) and lower permeability may be selected for use in membrane 10 at the first stage of processing. Conditions at this stage are typically characterized by higher gas flow rates and higher CO₂concentrations. For hydrocarbon/CO₂separation applications, the majority of CO₂is permeated in this first stage, and the majority of “hydrocarbon losses” occur in this stage. Although the higher alpha fibers selected for use have a slightly lower flux, the fibers still operate efficiently due to the high CO₂concentrations. At the second stage, however, membrane fibers that exhibit higher permeability and lower selectivity may be used. Conditions at this stage are typically characterized by lower gas flow rates and lower CO₂concentrations. Therefore, element 10 can exhibit higher permeability at this stage in order to minimize the amount of membrane area and associated equipment required.
Turning now to FIGS. 5 & 7, a multiple fiber membrane element 20 replaces multiple single fiber membranes 10 and multiple stages of separation processing. The improved processing performance provided by membrane 20 is due in part to the use of different types of hollow fibers 21 in different zones 31, 33 of the membrane 20 and the increased surface area and bundle depth 29 provided by membrane 20. For example, in one embodiment membrane 20 is about 30 inches in diameter and 72 inches in height. Compared to a 12-inch diameter single fiber membrane 10, multiple fiber membrane filter element 20 generally has about 10 times the surface area and about 3 times the bundle depth 29 as that of membrane 10.
Referring now to FIGS. 2 to 5, membrane 20 includes hundreds of thousands of two or more different types of hollow fibers 21. The fibers 21 are wrapped about a perforated non-permeate tube or pipe 35 that shares a central longitudinal axis 37 with membrane 20. Alternatively, the fibers 21 may be arranged in bundles 27 and wrapped about pipe 35. Fibers 21 are arranged so permeate that permeates the wall 23 and enters the bore 25 of the hollow fibers 21 may exit through the top and bottom of membrane 20. Membrane 20 is fabricated as a divided membrane element with two distinct circumferential zones 31, 33, with line 45 indicating the division between the two zones. Fibers 21 located in a first circumferential zone 31 of the membrane 20 have a different type (or types) of hollow fibers 21 than fibers 21B located in a second circumferential zone 33. The performance characteristics of each zone 31, 33 differ because the hollow fibers 21 or combination of hollow fibers 21 fabricated and selected for use in zone 31 have been fabricated to achieve, for a composition and volume of the natural gas stream flowing through the zone 31, a different selectivity and permeability than the hollow fibers 21B or combination of hollow fibers 21B in zone 22 for the composition and volume of the natural gas stream flowing through the zone 33.
The hollow fibers 21 in each zone 31, 33 are selected in order to maximize the overall capacity and separation performance of membrane 20 as a gas stream passes through it, thereby reducing or eliminating the need for multiple processing or separation stages (see FIG. 7). For example, a higher separation, lower permeability hollow fiber 21 may be located nearest to the inlet or feed side 41 of the membrane 20, in circumferential zone 31, where maximum permeation flow volumes occur, in order to reduce the hydrocarbon losses to the permeate. A higher permeability but lower separation hollow fiber 21 may be located nearest to the outlet or non-permeate side 43 of the membrane 20, in circumferential zone 33, to improve capacity where CO₂is lower. Alternatively, a first hollow fiber 21 having a higher permeation of one component (e.g. H₂S) may be bundled with a second hollow fiber 21 having higher permeation of another component (e.g. CO₂or hydrocarbon dewpointing) or vice versa.
Configuring membrane 20 with multiple types of hollow fibers 21 can optimize performance by taking advantage of the performance characteristics of the different types of hollow fibers 21 included in each zone 31, 33 relative to the gas composition and more than two zones 31, 33 may be deployed. For example:

- 1. Combining larger bore hollow fibers 21 on the high CO₂zone nearest the feed gas side 41 of element 20 and smaller bore fibers 21 on the low CO₂zone nearest the non-permeate side 43 of element 20 to add more relative surface area in low CO₂conditions.
- 2. Combining hollow fibers 21 that have greater CO₂partial pressure resistance in the zone nearest the feed gas side 41 with hollow fibers 21 having higher flux in the zone nearest the non-permeate side 43.
- 3. Combining hollow fibers 21 that exhibit different separations, such as combining a hollow fiber 21 for dehydration with a fiber 21 for CO₂/hydrocarbon separation or combining a fiber 21 for CO₂removal with a fiber 21 for H₂S removal or for hydrocarbon dewpointing.

Membrane 20 results in fewer stages of membrane elements because it performs a much greater CO₂removal duty than its single fiber predecessor membrane 10. A greater amount of CO₂can be removed in membrane 20 because there is more permeation of CO₂, which results in a greater differential between inlet CO₂and exiting non-permeate CO₂inside of membrane 20. Because of this, the gas passing through membrane 20 now has a higher percentage of CO₂on the feed side 41 of membrane 20 than it does in the middle or on the exiting non-permeate side 43.
By way of example, consider an inlet gas stream entering membrane 20 that contains about 50% inlet CO₂. As the gas passes through membrane 20 and travels toward the inner core or central longitudinal axis 37, CO₂is permeated. As a result, the hollow fibers 21 located closer to the central longitudinal axis 35 of element 20 (that is, the non-permeate side 43) are presented with gas having successively lower and lower amounts of CO₂. For example, depending on the type of hollow fibers 21 selected for use, non-permeate gas may exit the membrane 20 with about 10% CO₂. In this example, although the removal of CO₂through the membrane 20 is a continuous process, for simplification purposes zone 31 is a labeled a high-CO₂zone where CO₂is removed from about 50% to 25%. The hollow fibers 21 located farther away from the feed side 41 and toward the non-permeate side 43 reside in zone 33 or the low-CO₂zone, where CO₂is removed from about 25% to 10%. Again, these values are simply illustrative ones.
A membrane 20 can provide a number of benefits. Because of the increased fiber bundle depth 29, the larger membrane 20 may replace two stages of smaller conventional membranes 10. Equivalent scale-up is not possible with spiral wound membrane elements due to the restriction in gas flow paths between layers of the membrane. CO₂is selectively separated within the membrane element 20 as the flowing mixed CO₂/hydrocarbon gas comes in contact with the fibers 21. CO₂passes through the wall 23 of each fiber 21 into the bore 25 of each fiber 21 and exits through the ends of the membrane element 20 as permeate gas. The inlet gas is reduced in CO₂as the gas travels through membrane 20, resulting in the exiting non-permeate gas having a lower CO₂concentration than the inlet gas.
As gas passes through membrane element 20, each successive array of fibers 21 actually processes gas with progressively lower and lower CO₂content. The actual CO₂content that each individual hollow fiber 21 is exposed to depends on the position of the fiber 21 in the membrane 20 relative to the feed gas side 41, with fibers 21 located near the inlet operating on higher CO₂gas than fibers 21 that are located downstream, nearer to the gas outlet or non-permeate side 45. The larger bundle depth 29 thus enables the use of multiple fiber types in a single membrane element 20 and provides separation performance similar to that which previously required gas to pass through two or more membranes 10 in series. Furthermore, within membrane 20 there is a greater change in gas volume and composition due to permeation than with previous smaller membranes 10. Therefore, membrane 20 is not only processing more gas but is also operating with a greater differential in gas composition between the feed gas side 41 and the non-permeate side 43 enabling the use of multiple fiber types. With current single fiber membranes 10, the resulting membrane performance over the range of gas conditions present in the membrane 10 may be sub-optimal.
While a membrane filter element having multiple fiber types and a method for its use has been described with a certain degree of particularity, many changes may be made in the details of construction and the arrangement of components and steps without departing from the spirit and scope of this disclosure. A filter element and method according to this disclosure, therefore, is limited only by the scope of the attached claims, including the full range of equivalency to which each element thereof is entitled.

Claims

What is claimed is:

1. A membrane element comprising:

at least two concentric, cylindrical-shaped zones spanning a total height of the membrane element and surrounding a central longitudinal axis of the membrane element;

one of the zones defined by first fibers fabricated to provide a selected first gas selectivity and arranged so a first gas permeate exits an end of the membrane element;

another of the zones defined by second fibers fabricated to provide a selected second, different gas selectivity so a second different gas permeate exits an end of the membrane element.

2. A membrane element according to claim 1 wherein the first fibers are fabricated to provide a selected first gas permeability and the second fibers are fabricated to provide a second, different gas permeability.

3. A membrane element according to claim 2 wherein the first and second fibers are fabricated to provide, relative to one another, a different target CO₂permeability.

4. A membrane element according to claim 2 wherein the first and second fibers are fabricated to provide, relative to one another, a different target H₂S permeability.

5. A membrane element according to claim 1 relative to one another, a different target CO₂selectivity.

6. A membrane element according to claim 1 wherein the first and second fibers are fabricated to provide, relative to one another, a different target H₂S selectivity.

7. A membrane element according to claim 1 wherein the first and second fibers are fabricated to provide, relative to one another, a different target water dew pointing performance.

8. A membrane element according to claim 1 wherein the first and second fibers are fabricated to provide, relative to one another, a different target hydrocarbon dew pointing performance.

9. A membrane element according to claim 1 wherein depth of the zones differs from one another.

10. A membrane element according to claim 1 wherein at least one of zones is an innermost zone or an outermost zone of the membrane fiber element.

11. A membrane element according to claim 1 wherein the two zones are located adjacent one another.

12. A membrane element according to claim 1 further comprising the first and second fibers including hollow fibers.

13. A membrane element according to claim 1 wherein the first and the second different gas permeates exit a same end of the membrane element.

14. A membrane element according to claim 1 wherein the first and second different gas permeates mix with one another after exiting the same end.

15. A method of treating a gas, the method comprising:

flowing the gas through a membrane element containing at least two concentric, cylindrical-shaped zones spanning a total height of the membrane element and extending around the membrane element;

wherein one of the zones is defined by first fibers fabricated to provide a selected first gas selectivity and arranged so a first gas permeate exits an end of the membrane element; and

wherein another of the zones is defined by second fibers fabricated to provide a selected second, different gas selectivity and arranged so a second different gas permeate exits an end of the membrane element.

16. A method according to claim 15 wherein the first and second fibers are fabricated to provide a selected first gas permeability and the second fibers are fabricated to provide a second, different gas permeability.

17. A method according to claim 15 wherein the first and second fibers are fabricated to provide, relative to one another, a different target water dew pointing performance.

18. A method according to claim 15 wherein the first and second fibers are fabricated to provide, relative to one another, a different target hydrocarbon dew pointing performance.

19. A method according to claim 15 wherein the first and second fibers include hollow fibers.

20. A method according to claim 15 further comprising mixing the first and second different gas permeates with one another after exiting a respective end of the membrane element.