(19)
(11)EP 3 450 001 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
05.10.2022 Bulletin 2022/40

(21)Application number: 18190238.8

(22)Date of filing:  22.08.2018
(51)International Patent Classification (IPC): 
B01D 67/00(2006.01)
B01D 69/10(2006.01)
B01D 19/00(2006.01)
B01D 69/08(2006.01)
B01D 69/12(2006.01)
B01D 69/02(2006.01)
(52)Cooperative Patent Classification (CPC):
B01D 19/0036; B01D 67/0018; B01D 69/02; B01D 69/08; B01D 69/10; B01D 69/12; B01D 71/34; B01D 71/64; B01D 2323/08; B01D 2325/023; F23K 2900/05082; B01D 19/0031; B01D 71/36

(54)

HOLLOW-FIBER MEMBRANE FOR FUEL DEGASSING

HOHLFASERMEMBRAN ZUR KRAFTSTOFFENTGASUNG

MEMBRANE À FIBRES CREUSES DE DÉGAZAGE DE CARBURANT


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 22.08.2017 US 201715682588

(43)Date of publication of application:
06.03.2019 Bulletin 2019/10

(73)Proprietor: Hamilton Sundstrand Corporation
Charlotte, NC 28217-4578 (US)

(72)Inventor:
  • CORDATOS, Haralambos
    Colchester, CT Connecticut 06415 (US)

(74)Representative: Dehns 
St. Bride's House 10 Salisbury Square
London EC4Y 8JD
London EC4Y 8JD (GB)


(56)References cited: : 
EP-A1- 1 677 888
WO-A1-2016/168644
EP-B1- 1 677 888
US-A1- 2003 094 409
  
  • MAY MAY TEOH ET AL: "Dual-layer PVDF/PTFE composite hollow fibers with a thin macrovoid-free selective layer for water production via membrane distillation", CHEMICAL ENGINEERING JOURNAL, vol. 171, no. 2, 1 July 2011 (2011-07-01), pages 684-691, XP055544712, ISSN: 1385-8947, DOI: 10.1016/j.cej.2011.05.020
  • LIU MIN ET AL: "Formation of microporous polymeric membranes via thermally induced phase separation: A review", FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING, HIGHER EDUCATION PRESS, HEIDELBERG, vol. 10, no. 1, 22 February 2016 (2016-02-22), pages 57-75, XP035946670, ISSN: 2095-0179, DOI: 10.1007/S11705-016-1561-7 [retrieved on 2016-02-22]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

BACKGROUND OF THE INVENTION



[0001] This application relates to hollow fibers which provide a gas separation function in a fuel supply system.

[0002] Gas turbine engines are known and typically include a fuel supply for supplying fuel to a combustor. The fuel is mixed with air and ignited.

[0003] It is known that if oxygen is dissolved in the fuel when its temperature exceeds approximately 250F (121°C), carbonaceous deposits will form. This is undesirable.

[0004] Thus, it is known to provide oxygen removal systems in a fuel supply system, such as for a gas turbine engine. While various geometries of oxygen removal systems are known, one that has promise is a bundle of hollow tubes. The fuel is passed over the hollow tubes and dissolved gases pass through the tubes into an interior of the tubes. The dissolved gases are then removed from the interior, such as through a vacuum.

[0005] The hollow tubes may be formed of various plastics. The tubes which are utilized may have application in other gas removal systems. As an example, one major manufacturer of such gas removing hollow tube membranes is directed to water purification purposes. For water purification purposes, there may be low porosity at the outer surface, but much greater porosity radially inwardly. The radially inward structure of the hollow tube provides support for the outer surface. Due to the structure, the support may be inadequate for water purification.

[0006] Such structures may not be suitable for gas turbine engine fuel supply systems. This is particularly true with regard to modern gas turbine engines. The fuel systems of modern gas turbine engines operate at high temperature and high pressure. If used in gas turbine engine applications, the inward support on the known tubes may result in collapse of the tubes, which is, of course, undesirable.

[0007] EP 1 677 888 discloses a system for the management of thermal transfer in a gas turbine engine. WO2016/168644 relates to the gasification of a liquid, i.e. and thus can be implicitly used for degasification. It discloses a hollow fiber membrane with a PVDF support coated with non-porous PTFE perfluorinated film (film thickness 50-200 nm= 0.05-0.2 micron), wherein the hollow fiber has an inner diameter of 75-200 micron, an outer diameter of 150-400 micron and a wall thickness of 25-100 micron, i.e. a ratio of thickness to outer diameter 0.06-0.57; average pore size of 0.05-3 micron. (1 micron corresponds to 1 micrometer). May May Teoh et al., Chemical Engineering Journal, 171, 2011, 684-691, DOI:10.1016/j.cej.2011.05.020 discloses the use of a polyvinylidene fluoride (PVDF)/polytetrafluoroethylene (PTFE) composite to fabricate hollow fiber membranes for seawater desalination.

SUMMARY OF THE INVENTION



[0008] A system for degassing a hydrocarbon fluid (e.g. from a hydrocarbon liquid) has a plurality of hollow tube membranes. The hollow tube membranes are formed of a plastic providing an inner support body and an outer selective layer which is denser than the inner support body. The inner support body is formed of spherulitic structures. The spherulitic structures have a size that is less than or equal to 0.3 micron. The inner support body is formed of one of PVDF, one of its co-polymers, polyimides, or a polyetherimide. The inner support body has radially outer areas with pores between 10 and 20 nm. The porosity of the inner support body is between 30 and 50 percent. A thickness of the inner support body is at least 0.25 times an outer diameter of said inner support body. The outer selective layer is an oxygen-permeable fluoropolymer. The diameter of the hollow tube is between 0.5 and 2.0 mm. A thickness of said outer selective layer (30) is between 0.25 and 0.75 micron. A fuel supply system (e.g. comprising the system for degassing a hydrocarbon fluid described herein) is also disclosed.

[0009] A fuel supply system and a method (e.g. comprising use of the system for degassing a hydrocarbon fluid described herein) are also disclosed.

[0010] These and other features may be best understood from the following drawings and specification.

[0011] A fuel supply system for a gas turbine engine comprises a pump, an oxygen removal system and a combustor, said pump configured to move fuel through said oxygen removal system and to said combustor; said oxygen removal system having a plurality of hollow tube membranes as defined herein.

[0012] A method of degassing hydrocarbon fluid comprises the steps of operating a fuel pump on an aircraft to supply the hydrocarbon fluid to a combustor on a gas turbine engine and passing the hydrocarbon fluid through a plurality of hollow tube membranes as defined herein to degas the hydrocarbon fluid.

BRIEF DESCRIPTION OF THE DRAWINGS



[0013] 

Figure 1 schematically shows a fuel supply system for a gas turbine engine.

Figure 2A shows a fiber bundle which may be utilized in the Figure 1 system.

Figure 2B shows one hollow tube in the fiber bundle.

Figure 3 shows a detail of a tube as manufactured in view of this disclosure.


DETAILED DESCRIPTION



[0014] Figure 1 schematically shows a fuel supply system 20 for a gas turbine engine 27. A pump 22 delivers fuel through an oxygen removal system 24. A vacuum pump 25 is shown schematically removing the oxygen from the oxygen removal system 24.

[0015] The fuel is then delivered into a combustor 26 of a gas turbine engine 27, shown schematically.

[0016] One type of oxygen removal system 24 is illustrated in Figure 2A. As shown, there is a bundle of wrapped hollow fiber membranes 28 inward of a canister 29. The membranes can be otherwise called hollow tube membranes 28, and are formed of an appropriate plastic. The fuel is passed over the bundle 24 and oxygen, or other gases, are removed from the fuel by passing through the wall of the tubes, as shown schematically in Figure 2B. Once in the interior of the tubes, the vacuum pump 25 removes the oxygen.

[0017] Figure 3 shows a tube 28. As shown, there is an outer selective layer 30 which is relatively dense compared to the inner support body 32. The dense outer layer 30 may be formed of a material such as Teflon AF. The layer is very thin.

[0018] The inner support body 32 is formed as a porous structure with a plurality of voids.

[0019] While Teflon AF (tetrafluoroethylene containing 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole at various levels depending on the grade) is disclosed other materials such as an oxygen-permeable fluoropolymer may be utilized (e.g. as the outer selective layer). Another coating example is Solvay's Hyflon AD (tetrafluoroethylene (TFE)-2,2,4-trifluoro-5-tri-fluorometoxy-1,3-dioxole).

[0020] Figure 3 shows a tube 28 as manufactured under this disclosure. There is the outer layer 30. The outer selective layer 30 is between .25 and .75 micron in thickness. Preferably, the outer selective layer 30 is approximately .5 micron and in embodiments. The thickness tL of the outer selective layer 30 is measured between a radially inner point 50 and a radially outer point 52. The entire tube 28 may be between 0.5 and 2.0 millimeter in diameter.

[0021] As shown at 40, the inner support body is formed as spherulitic structures.

[0022] The inner support body may be formed of PVDF (polyvinylidene fluoride) or its copolymers. Alternatively, polyimides or polyetherimides may be utilized. The most common method currently employed to form these porous structures is "phase inversion," which is the practice of precipitating a polymer from its solution such that it is phase-separated into a polymer-rich and a polymer-lean phase, while the solvent is being removed. This process ultimately leads into a porous structure having morphology that can be affected by process parameters. Most common morphologies involve macrovoids, which afford large permeance of water for example, but other morphologies such as a spherulitic structure can be the result of process parameter selection under the general phase inversion technique.

[0023] As known, to form the spherulitic structure, an exothermic reaction should be utilized. Crystals are formed during crystallization of the selected polymers e.g. PVDF. These initial crystals are called the primary nuclei. The primary nuclei will grow into spherulites. If the formation rate of the primary nuclei is low, heat generated in the growth of the primary nuclei inhibits further formation of primary nuclei and facilitates further growth of the generated primary nuclei. The crystal growth will continue until the spherulites collide with each other. Since the growth of the crystals terminates by collision, the final spherulite size depends on the number of the primary nuclei's generated first.

[0024] A common method to form the spherulitic microstructures desired for this application is "thermally induced phase separation," a special case of the phase inversion technique, whereby the polymer (e.g. PVDF) is dissolved in a high-boiling solvent at a temperature near the melting point of the polymer. Then, it is cooled at a controlled rate such as to induce phase separation by precipitation that is partly due to cooling. This happens since the polymer would be nearly insoluble to the high-boiling solvent at ambient temperature. Also, this is partly due to solvent extraction, which is the standard phase separation technique. This combination of polymer-solvent interaction and cooling rate provides additional degrees of freedom in a phase inversion process to allow for the formation of crystallites as described in this section.

[0025] The spherulites have a size that is less than or equal to 0.3 microns, e.g. they will be 0.3 microns or less in diameter. As explained above, this is achieved by increasing the number of primary nuclei initially.

[0026] A worker of ordinary skill in this art would be able to achieve these ranges using known tube formation techniques.

[0027] Radially outer portions of the inner support body 32 preferably have pores less than 50 nanometers, and preferably 10 to 20 nanometers or between 10 and 20 nanometers to provide support for the outer selective layer 30.

[0028] The size and morphology of the spherulitic structure is optimized for maximum creep resistance at temperature. When utilized in a fuel supply system, the tubes may see temperatures on the order of 200°F (93°C), and pressures on the order of 150psi (1034 kPa). The disclosed embodiment is well-suited to survive such challenging conditions.

[0029] Referring again to Figure 3, a thickness tp of the inner support body 32 is defined as the outside radius r2 to points 44 minus the inside radius r1 to points 42. The greater the thickness, the stronger the fiber - but the lower its permeance, especially for the typical water purification applications. For this disclosure, permeance is not as important. Instead, it is desirable to maximize resistance to creep at temperature. Thus, it is desirable to increase/maximize the thickness. A thickness of said inner support body is at least 0.25 times an outer diameter of said inner support body.

[0030] The porosity of the inner support body is between 30 and 50 percent. A permeability may be between 1 and 50 ml/min (at STP) per psi of pressure and per in2 of porous support structure surface area.

[0031] In very general terms, one can think of the thermally-induced phase separation process as two broad categories: one where the initial concentration of the polymer (e.g. PVDF) is relatively low (under 30%) and one where it is relatively high (over 30%). In the first case, the polymer-solvent mixture becomes a metastable liquid-liquid phase that ultimately results in a honeycomb-like porous structure. In the second case (high initial concentration) the polymer crystallizes directly from the solution, forming sphere-like nuclei; it is therefore the latter that we want for our application.

[0032] In a method of forming such tubes, the plastic is initially heated and extruded into the tubes or fibers. It is then cooled and desirably cold quite fast.

[0033] A system for degassing a hydrocarbon liquid has a plurality of hollow tube membranes. The hollow tube membranes are formed of a plastic providing an inner support body and an outer selective layer which is denser than the inner support body. The inner support body is formed of spherulitic structures. A fuel supply system is also disclosed.

[0034] A method of degassing hydrocarbon fluid could be said to include the steps of operating a fuel pump on an aircraft to supply the hydrocarbon fluid to a combustor on a gas turbine engine, and passing the hydrocarbon fluid through a plurality of hollow tube membranes to degas the hydrocarbon fluid. The hollow tube membranes are formed of a plastic providing an inner support body and an outer selective layer which is denser than the inner support body, and the inner support body being formed of spherulitic structures.

[0035] The methods and systems described herein for degassing may be for degassing a hydrocarbon fluid, e.g. a liquid or a gas, e.g. from a hydrocarbon liquid. The methods and systems described herein for degassing may be for removing oxygen, e.g. from fuel, e.g. oxygen removal systems and methods.


Claims

1. A system for degassing a hydrocarbon fluid comprising:

a plurality of hollow tube membranes (28), said hollow tube membranes (28) being formed of a plastic providing an inner support body (32) and an outer selective layer (30) which is denser than said inner support body (32), and said inner support body (32) formed of spherulitic structures,

wherein said spherulitic structures have a size that is less than or equal to 0.3 micron;

said inner support body (32) is formed of one of PVDF, one of its copolymers, polyimides, or a polyetherimide;

said inner support body (32) has radially outer areas with pores between 10 and 20 nm;

a porosity of said inner support body (32) is between 30 and 50 percent;

a thickness of said inner support body (32) is at least 0.25 times an outer diameter of said inner support body (32);

said outer selective layer (30) is an oxygen-permeable fluoropolymer;

the diameter of the hollow tube is between 0.5 and 2.0 mm; and

a thickness of said outer selective layer (30) is between 0.25 and 0.75 micron.


 
2. The system as forth in claim 1, wherein the oxygen-permeable fluoropolymer is polytetrafluoroethylene 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole or polytetra-fluoroethylene (TFE)-2,2,4-trifluoro-5-tri-fluorometoxy-1,3-dioxole.
 
3. A fuel supply system (20) for a gas turbine engine (27) comprising:

a pump (22), an oxygen removal system (24) and a combustor (26), said pump (22) configured to move fuel through said oxygen removal system (24) and to said combustor (26); and

said oxygen removal system (24) having a plurality of hollow tube membranes (28) according to claim 1 or claim 2.


 
4. A method of degassing hydrocarbon fluid comprising the steps of:

operating a fuel pump (22) on an aircraft to supply the hydrocarbon fluid to a combustor (26) on a gas turbine engine (27);

passing the hydrocarbon fluid through a plurality of hollow tube membranes (28) according to claim 1 or claim 2 to degas the hydrocarbon fluid.


 


Ansprüche

1. System zum Entgasen eines Kohlenwasserstofffluids, das Folgendes umfasst:

eine Vielzahl hohler Röhrenmembranen (28), wobei die hohlen Röhrenmembranen (28) aus einem Kunststoff gebildet sind, der einen inneren Stützkörper (32) und eine äußere selektive Schicht (30) bereitstellt, die dichter als der innere Stützkörper (32) ist, und der innere Stützkörper (32) aus sphärolithischen Strukturen gebildet ist,

wobei die sphärolithischen Strukturen eine Größe aufweisen, die kleiner oder gleich 0,3 Mikrometer ist;

der innere Stützkörper (32) aus einem von PVDF, einem seiner Copolymere, Polyimide oder einem Polyetherimid gebildet ist;

der innere Stützkörper (32) radial äußere Bereiche mit Poren zwischen 10 und 20 nm aufweist;

eine Porosität des inneren Stützkörpers (32) zwischen 30 und 50 Prozent liegt;

eine Dicke des inneren Stützkörpers (32) mindestens das 0,25-Fache eines Außendurchmessers des inneren Stützkörpers (32) beträgt;

die äußere selektive Schicht (30) ein sauerstoffdurchlässiges Fluorpolymer ist;

der Durchmesser der hohlen Röhre zwischen 0,5 und 2,0 mm liegt; und

eine Dicke der äußeren selektiven Schicht (30) zwischen 0,25 und 0,75 Mikrometer liegt.


 
2. System nach Anspruch 1, wobei das sauerstoffdurchlässige Fluorpolymer Polytetrafluorethylen-2,2-bistrifluormethyl-4,5-difluor-1,3-dioxol oder Polytetrafluorethylen (TFE)-2,2,4-trifluor-5-trifluormethoxy-1,3-dioxol ist.
 
3. Kraftstoffzufuhrsystem (20) für ein Gasturbinentriebwerk (27), das Folgendes umfasst:

eine Pumpe (22), ein Sauerstoffentfernungssystem (24) und eine Brennkammer (26), wobei die Pumpe (22) dazu konfiguriert ist, Brennstoff durch das Sauerstoffentfernungssystem (24) und zu der Brennkammer (26) zu bewegen; und

wobei das Sauerstoffentfernungssystem (24) eine Vielzahl hohler Röhrenmembranen (28) nach Anspruch 1 oder Anspruch 2 aufweist.


 
4. Verfahren zum Entgasen von Kohlenwasserstofffluid, das die folgenden Schritte umfasst:

Betreiben einer Kraftstoffpumpe (22) in einem Luftfahrzeug, um das Kohlenwasserstofffluid einer Brennkammer (26) in einem Gasturbinentriebwerk (27) zuzuführen;

Leiten des Kohlenwasserstofffluids durch eine Vielzahl hohler Röhrenmembranen (28) nach Anspruch 1 oder Anspruch 2, um das Kohlenwasserstofffluid zu entgasen.


 


Revendications

1. Système de dégazage d'un fluide hydrocarboné comprenant :

une pluralité de membranes tubulaires creuses (28), lesdites membranes tubulaires creuses (28) étant formées d'un plastique fournissant un corps de support interne (32) et d'une couche sélective externe (30) qui est plus dense que ledit corps de support interne (32), et ledit corps de support interne (32) étant formé de structures sphérulitiques,

dans lequel lesdites structures sphérulitiques ont une taille inférieure ou égale à 0,3 micron ;

ledit corps de support interne (32) est formé de l'un parmi le PVDF, l'un de ses copolymères, les polyimides ou un polyétherimide ;

ledit corps de support interne (32) a des zones radialement externes avec des pores entre 10 et 20 nm ;

une porosité dudit corps de support interne (32) est comprise entre 30 et 50 % ;

une épaisseur dudit corps de support interne (32) est au moins 0,25 fois un diamètre externe dudit corps de support interne (32) ;

ladite couche sélective externe (30) est un fluoropolymère perméable à l'oxygène ;

le diamètre du tube creux est compris entre 0,5 et 2,0 mm ; et une épaisseur de ladite couche sélective externe (30) est comprise entre 0,25 et 0,75 micron.


 
2. Système selon la revendication 1, dans lequel le fluoropolymère perméable à l'oxygène est le polytétrafluoroéthylène 2,2-bistrifluorométhyl-4,5-difluoro-1,3-dioxole ou le polytétrafluoroéthylène (TFE)-2,2,4-trifluoro-5-tri-fluorométoxy-1,3-dioxole.
 
3. Système d'alimentation en carburant (20) pour un moteur à turbine à gaz (27) comprenant :

une pompe (22), un système d'élimination d'oxygène (24) et une chambre de combustion (26), ladite pompe (22) étant configurée pour déplacer le combustible à travers ledit système d'élimination d'oxygène (24) et vers ladite chambre de combustion (26) ; et

ledit système d'élimination d'oxygène (24) ayant une pluralité de membranes tubulaires creuses (28) selon la revendication 1 ou la revendication 2.


 
4. Procédé de dégazage de fluide hydrocarboné comprenant les étapes de :

l'actionnement d'une pompe à carburant (22) sur un aéronef pour fournir le fluide hydrocarboné à une chambre de combustion (26) sur un moteur à turbine à gaz (27) ;

la circulation du fluide hydrocarboné à travers une pluralité de membranes tubulaires creuses (28) selon la revendication 1 ou la revendication 2 pour dégazer le fluide hydrocarboné.


 




Drawing











Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description




Non-patent literature cited in the description