Mixed-conducting-ceramic-membranes-for-high-efficiency-power-generation-with-CO2-capture_2012_Current-Opinion-in-Chemical-Engineering.pdf

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Mixed conducting ceramic membranes for high efficiency powergeneration with CO2 captureXueliang Dong and Wanqin Jin

Because of the emission of larger amount of CO2, power

generation from fossil fuel has resulted in serious environmental

problems. Integrating dense mixed-conducting membranes

(MCMs) into power cycles with CO2 capture has been

considered as the most advanced technology for high

efficiency and clean power production. This paper presents an

update of MCMs development efforts, including the recent

progress in membrane materials and their chemical resistance;

the membrane architecture especially the tubular asymmetric

membranes and hollow fiber membranes; and the pilot-scale

planar and membrane modules. The oxyfuel technique using

MCMs for oxygen production and its commercial prospects are

discussed. Finally, current challenges related to the

industrialization of MCMs are addressed and possible future

research is also outlined.

Address

State Key Laboratory of Materials-Oriented Chemical Engineering,

Nanjing University of Technology, 5 Xinmofan Road, Nanjing 210009, PR

China

Corresponding author: Jin, Wanqin ([email protected])

Current Opinion in Separation engineering 2012, 1:163–170

This review comes from a themed issue on

Separation engineering

Edited by W.S. Winston Ho and K. Li

Available online 23rd March 2012

2211-3398/$ – see front matter

# 2012 Elsevier Ltd. All rights reserved.

DOI 10.1016/j.coche.2012.03.003

IntroductionThe enormous potential consequences of global warming

due to increasing CO2 concentrations has been recog-

nized as one of the main environmental challenges of this

century. The development of breakthrough technologies

is therefore essential for dramatic decrease of the CO2

emission during the conversion of fossil fuels to other

forms of energy, for example, electricity or hydrogen.

Three main routes for mitigation of CO2 emission in

power plants can be defined as: first, post-combustion

process: the fuel is combusted in air and CO2 is captured

from the low pressure flue gases. Second, pre-combustion

process: the fuel is converted into H2 and CO2. The CO2

is separated and H2 is combusted in a gas turbine. Third,

oxyfuel process: fuel combustion is carried out using pure

oxygen, resulting in a flue gas that mainly contains H2O

www.sciencedirect.com

and CO2 [1]. Membrane separation plays an important

role in these technologies for CO2 mitigation. Especially,

the dense mixed-conducting membranes (MCMs) have

shown new possibilities of integration in power gener-

ation cycles because of their better thermal and chemical

stability, and typically higher selectivity [2–4]. This fact

has directed global research to inorganic membranes,

such as the public programs of DOE Vision 21 in the

US, the EU seventh Framework Programmes, the Japa-

nese NEDO programs, the National High Technology

Research and Development Programs and the National

Basic Research Program in China.

This review mainly focuses on the state of the art of

MCMs and their application in energy production system

with CO2 capture. First, the recent progress in MCM

materials is illustrated. Subsequently, the membrane

architecture and membrane modules in recent research

are discussed. Finally, the applications of MCMs in

oxyfuel processes were presented. The MCMs for cata-

lytic membrane reactors is not the topic of this article and

this area has been reviewed in our recent work [5]. The

general outline of this review is illustrated in Figure 1.

Mixed conducting ceramic membranematerialsMCM materials are categorized into two types based on

their transport properties: one shows mixed oxygen-ionic

and electronic conductivity (MIEC), while the other

exhibits mixed protonic and electronic conductivity

(MPEC).

MIEC materialsOxygen permeability and structural stability are two key

factors of MIEC materials. Generally, material stability is

opposite to the oxygen flux value. The MIEC material

with high oxygen vacancy concentration always results in

high oxygen ion transport rate and high oxygen per-

meability, however, leading to high thermal and chemical

expansion and poor structural stability especially at high

temperature and under low oxygen partial pressure.

Therefore, to seek the tradeoff between the two factors

according to the requirements of the application environ-

ment is crucial. Compared with membrane reaction pro-

cess, oxygen production puts a much smaller demand on

the material stability. Although the operation tempera-

ture is always higher than 6008C, the oxygen partial

pressure gradient across the membrane is only about

one order of magnitude. Furthermore, the impurities that

may cause membrane degradation in the feed and sweep

Current Opinion in Chemical Engineering 2012, 1:163–170

mailto:[email protected]

http://dx.doi.org/10.1016/j.coche.2012.03.003

164 Separation engineering

Figure 1

Power PlantApplications

Zero Emissions

MembraneModules

MembraneArchitecture

MCMMaterials

Current Opinion in Chemical Engineering

Schematic diagram of the general outline of this review.

gases are likely to be limited to H2O and CO2. Therefore,

the development of MIEC materials with high stability

under low oxygen partial pressure especially CO2 atmos-

phere and considerable oxygen permeation flux has been

the common goal of researchers in this area.

For oxygen production, one of the most widely used

MIEC materials is perovskite phase (A, A0)BO3 oxides,

in which A is a lanthanide, A0 is an alkaline earth metal,

and B is a transition metal. The average valence and radii

of A-site cations will affect the oxygen vacancy concen-

tration and chemical and structural stability of perovskite

materials. Meanwhile, the valence and valence variation

ability of B-site cations will determine both oxygen ion

and electron transmission rate and material stability.

These relationships between A-site and B-site cations

and material performance have been well discussed in

recent reviews [6,7]. Compared with the alteration of A-

site cations, most of the recent work focuses on the choice

of B-site cations because they have a closer relationship to

the performance. An effective method to improve the

performance of perovskite materials is cation substitution.

Recently, aluminum [8], gallium [9,10], niobium

[11��,12,13], tantalum [14,15], titanium [16], yttrium


[17], and Zinc [18] have been used as main B-site substi-

tution cations. Work on the development of a niobium-

based BaCo0.7Fe0.2Nb0.1O3�d (BCFN) perovskite

membrane was pioneered by Harada and coworkers

[11��]. The high performance of BCFN membrane was

further confirmed by Chen et al. [12] and Yi et al. [13] in

their recent papers. A tantalum-based perovskite mem-

brane Sr(Co0.8Fe0.2)0.9Ta0.1O3�d (SCFTa) and a titanium-

based perovskite membrane Sr(Co0.8Fe0.2)0.9Ti0.1O3�d

(SCFTi) were reported recently by Chen et al. [15] and

Zeng et al. [16], respectively. These membranes showed

high structural stability and high oxygen permeation flux

under CO2 atmosphere at the temperature above 9008C.

The good performance of SCFTi membrane was further

confirmed by Schulz et al. [19] in a recent paper. These

studies gave us an important reference for the develop-

ment of new perovskite materials.

Besides the single phase MIEC membranes, dual-phase

membranes have attracted considerable attentions

recently because of their high stability especially under

CO2 atmosphere. Most of the researches focused on the

development of new electronic conducting phase

materials [20��,21,22,23�], which came from noble metals


Mixed conducting ceramic membranes for high efficiency power generation with CO2 capture Dong and Jin 165

first, and then were replaced by pure electronic conduct-

ing oxides, subsequently by perovskite MIEC materials,

and very recently by alkaline earth metal-free non-

perovskite oxides. Zhu and Yang [20��] first proposed a

dual-phase membrane, comprising a fluorite oxide

Ce0.8Gd0.2O1.9 for oxygen ionic transport and a perovskite

MIEC oxide Gd0.2Sr0.8FeO3�d for both oxygen ionic and

electronic transport. This membrane exhibited good ox-

ygen permeation flux and stability. In their recent work,

another new dual-phase membrane Ce0.8Sm0.2O1.9–Sm0.8Ca0.2Mn0.5Co0.5O3�d was proposed for CO2 capture

via an oxyfuel route [21]. Recently, Luo et al. [23�]reported a new dual-phase membrane with NiFe2O4

and Ce0.9Gd0.1O3�d as the electronic and oxygen ionic

conducting phases, respectively. This membrane showed

high stability under CO2 atmosphere but relatively low

oxygen permeability. In addition, a new dual-phase mem-

brane consisting of mixed-conducting oxide and molten

carbonate phases was developed by Lin’s group in recent

years for CO2 separation [24,25�,26]. This type of mem-

brane shows potential application in CO2 capture.

MPEC materialsAs plans for fossil-fuel-based power plants incorporating

MIEC membranes have been developed, it became clear

that MPEC hydrogen-permeable membranes might find

use as well. In particular, this would be the case if the

operation temperature was high (>6008C) and the MPEC

membranes could be thermally integrated with other

processes, such as pre-combustion process. Presently,

the general formula of MPEC materials can be written

as ACe1�x�yBxMyO3�d, where the A is an alkaline earth

metal, most commonly strontium or barium, B is a tran-

sition metal, most commonly Zr or Ti as they provide

stability towards CO2 and other acidic gases, and M is a

lanthanide. A prerequisite for a candidate for a good

MPEC membrane material is a combination of both high

electronic and protonic conductivity, but to date few

materials are known to meet this criteria. Generally,

MPEC materials show high proton conductivity, how-

ever, their electronic conductivity is relatively low.

Therefore, different aliovalent dopants were used to

improve the electronic conductivity. Among them, euro-

pium [27], neodymium [28], thulium [29], terbium [30],

yttrium [31], and ytterbium [32] were demonstrated as

promising dopants.

Although the aliovalent dopants made some contri-

bution to enhance the electronic conductivity in MPEC

materials, their hydrogen permeation flux was still too

low for practical application. Another effective approach

to increase the electronic conductivity of MPEC

materials is to add a metal phase. Recently, nickel

[33–35] has been used as promising metal phase in

proton conducting membranes. The nickel-based

dual-phase membranes showed relatively high hydrogen

permeation flux. However, their structural stability in


CO2 or H2S contained atmospheres still needed to be

improved [33,34].

Membrane architectureMembrane architecture is as important as the membrane

materials in determining the performance of MCMs. The

architecture can be considered either from a membrane

configuration standpoint (planar and tubular membranes)

or from a symmetry standpoint (symmetric or self-sup-

ported, and asymmetric or supported membranes).

Symmetric planar and tubular are important structures for

the practical application of MCMs. Because of the limited

space their pros and cons will not be discussed here (see

recent book chapter [36] for details). In general, the

transport performance of the MCMs can be greatly

improved by reducing their thickness. A supported

MCM, which consists of a thin and dense membrane

layer on a porous support was therefore considered as a

promising membrane geometry. The concept of thin

supported ion transport membranes for air separation

was reported in 1990s by the groups of Twente, Cincin-

nati and Air Products [37–39]. In 2001, Jin et al. [40��]proposed a versatile co-sintering technique to prepare a

crack-free supported membrane. This is an important

technique for the fabrication of supported ceramic mem-

branes and is suited not only for planar but also for tubular

membranes. For practical applications, the tubular design

has obvious advantages, such as higher surface area/

volume and ease of high-temperature sealing. Therefore,

tubular and in particular asymmetric tubular MCMs have

been developed for oxygen and hydrogen separation in

recent years [27,41–43]. Yoon et al. [41�] prepared a 30 mm

SrCe0.9Eu0.1O3�d membrane on tubular porous Ni–SrCeO3 support. A high hydrogen permeation flux of

0.6 ml cm�2 min�1 was obtained at 9008C. In a recent

article, Liu et al. [44�] reported a high performance

SrCo0.4Fe0.5Zr0.1O3�d (SCFZ) asymmetric tubular mem-

brane fabricated by a spin-spray technique. A thin sup-

ported SCFZ dense membrane with the thickness of

20 mm was successfully prepared by coating a slurry

containing SCFZ powder directly onto the surface of

a green tubular support of the same composition, followed

by sintering. This work provided a simple but robust

strategy for the preparation of asymmetric tubular

membranes.

Currently, hollow fiber ceramic membranes with special

asymmetric structures have been successfully prepared

using a phase inversion spinning/sintering technique.

This type of membrane configuration shows obvious

advantages over the conventional planar or tubular con-

figurations: first, much larger membrane area per unit

volume; second, the asymmetric structure with a thin

separating dense layer; third, the integrated porous layers

on either side or both sides of the membrane provide

much larger gas–membrane interfaces. Pioneering work



Figure 2

(a) (b)

(c)

Air

Pure oxygen


(a) The oxygen separation membrane module of a demonstration plant

with 19 tubular BSCF membranes; [54]. (b) The hollow fiber LSCF

membrane module with the effective membrane area of about 1.0 m2;

[55��]. (c) Commercial-scale mixed-conducting membrane modules

developed by Air Products, each module is capable of producing

0.5 tons per day of oxygen; [56��].

on the preparation and application of hollow fiber MCMs

was performed by Li’s group [45��,46] and Caro’s group

[47,48]. Currently, more and more articles have reported

the application of hollow fiber MCMs for oxygen and

hydrogen separation [49–51]. It is no doubt that hollow

fiber is a promising membrane configuration and may play

an important role in promoting the commercial appli-

cation of MCMs. The only drawback of hollow fiber

ceramic membranes may lie in the relatively low mech-

anical strength due to the thin fiber wall. Therefore,

during the application process, incidental forces acting

on the membrane may be sufficient to cause its failure.

In a recent work, Wu et al. [52��] made a great progress in

the preparation of hollow fiber membranes by fabricating

novel dual-layer ceramic hollow fiber membrane reactors

for methane conversion using a single-step co-extrusion

and co-sintering technique. This membrane consists of a

thin outer oxygen separation layer (�75 mm) supported

on an inner substrate, which possesses a highly porous

structure. An obvious advantage of this configuration is

that different materials can be used for the separation

layer and porous support, therefore, the transport per-

formance and mechanical strength of the fiber can be

greatly improved. In a recent paper, Wei et al. [53] stated

that the linear hollow fiber membrane had the sealing

problem at varying temperatures. When both ends of the

linear hollow fiber are tightly fixed on the outer host tubes

at room temperature, the fiber will be broken due to the

expansion at high temperature. Therefore, they prepared

the U-shaped hollow fiber membranes. In the permeation

module, two ends of the fiber can be fixed on the same

side by ceramic sealant, and the hollow fiber can expand

and shrink freely during increasing and decreasing

temperature.

Membrane modulesThe goal of the MCM technology R&D efforts is to

develop and scale-up the technology to tonnage-quantity

scales for stand-alone plants and integration with

advanced power generation systems. For the realization

of this goal, one of the key issues is the design of

membrane modules. However, few works focused on this

issue in recent years.

The researchers within the Helmholtz Alliance MEM-

BRAIN under leadership of the Forschungszentrum

Julich together with colleagues from the Fraunhofer

IKTS developed MCMs and built a oxygen production

demonstration plant [54]. Ba0.5Sr0.5Co0.8Fe0.2O3�d

(BSCF) material was selected for the proof of technical

feasibility of the separation process. The membrane

module of this plant is shown in Figure 2a, which consists

of 19 membrane tubes with the length of 470 mm or

550 mm, the outer diameter of 10 mm, and the wall

thickness of 1 mm. One end of the tube was sealed by

Reactive Air Brazing (RAB) and another end connected to


the vacuum pump to produce pure oxygen. A stable

oxygen flux around 2.8 L(STP) min�1 of the plant was

reached at 8508C.

In a recent paper, Tan et al. [55��] reported a first pilot-

scale hollow fiber MCM plant. The membrane module of

this plant is shown in Figure 2b, which consists of 889

La0.6Sr0.4Co0.2Fe0.8O3�d (LSCF) hollow fibers with the

effective membrane area of about 1 m2. At 10708C and

under 98.5 kPa vacuum degree, the oxygen production

rate of this module reached 3.1 L(STP) min�1 with the

purity of 99.9%. When operated at around 9608C,

the plant exhibited more than 1100 h longevity with

the oxygen production rate of 0.84 L(STP) min�1 and

oxygen purity of 99.4%.

From the late 1980s, along with partners and through

partnership with the U.S. Department of Energy, Air

Products has made substantial progress in developing

MCM technology into a cost-effective method of oxygen

production. The team has successfully demonstrated

expected performance of commercial-scale modules in



a prototype facility that produces up to 5 tons per day

(TPD) of oxygen. As shown in Figure 2c [56��], each

module consists of multiple planar wafer MCMs. Four

wafers are shown joined to a common oxygen withdrawal

tube. Each wafer consists of two thin outer membrane

layers which are supported by a porous layer. Hot, high-

pressure air flows between the wafers. Oxygen is col-

lected at the center of each wafer in a tubular region and

passes out of the module through a ceramic tube. This

oxygen production technology integrates well with power

generation cycles, and studies have shown that it will

result in 25–35% reduction in the cost of oxygen

compared to conventional cryogenic oxygen plants. Air

Products currently focused on construction of an inter-

mediate-scale test unit (ISTU), sized for a nominal 100

TPD of oxygen production. Design of the ISTU is

complete and operation is planned in 2012. The ISTU

will provide design and scale-up data necessary for a

nominal 2000-TPD test facility by the middle of the

decade. The world-scale MCM-based oxygen plants for

IGCC and other large clean energy applications would be

available by around 2017.

Application in power generation system withCO2 captureThe integration of MCMs in pre-combustion process

shows promising industrial prospects, however, few

examples were reported. Therefore, this section focuses

mainly on the oxyfuel combustion process with CO2

capture, which has already been tested at pilot-plant scale

[57��].

Oxyfuel is a process of burning fuel, such as coal, oil, gas

and other hydrocarbons in a mixture of oxygen and

recirculated flue gas, thus eliminating the presence of

Figure 3

10 x M33 screw

flancebrazing

casing

high pressure

perovskite

air

baseplate

flance brazing

low pressurebrazingsocket MembO2

N2

120 kW oxycoal pilot plant developed by RWTH Aachen University; Membran

the length of 500 mm and diameter of 15 mm, 150 kg HT-Steel, Tmax = 8508


nitrogen in the flue gas and avoiding the formation of NOx

[1,3,4]. The resulting flue gas is comprised primarily of

CO2 and water vapor. Therefore, CO2 can be easily

enriched to the content of 96–99%. The purified CO2

stream is then compressed and condensed to produce a

manageable effluent of liquid CO2, which can be seque-

strated for storage or for use in subsequent processes.

Therefore oxyfuel combustion is a potential and envir-

onmentally friendly technique for heat and power gener-

ation. However, this process needs pure oxygen as a

feedstock. An alternative option is the utilization of

MIEC membranes for oxygen production. One of the

core requirements lies in the construction of a MCM-

based oxygen separation unit. The targets include

materials development, ceramic processing, mechanical

design, integration of membrane systems with combustor,

ceramic and system reliability, and process safety.

Lab-scale studies of oxyfuel process with MCMs for

oxygen production were attempted by many researchers

[21,58–60]. However, no commercial examples were

reported to date. To promote the commercialization of

the oxyfuel technique, a cooperative project, OXYCOAL-

AC [57��], was funded by the German Federal Ministry of

Economics and Technology (BMWi), the Ministry of

Innovation and Technology of North-Rhine Westphalia

(MIWFT), among others. This project aims at the de-

velopment of a zero-CO2-emission coal combustion pro-

cess for power generation. Within this project, researchers

from RWTH Aachen University developed the oxycoal

technique and a 120 kW pilot-plant has been constructed,

as shown in Figure 3. Taking all the necessary elements

(membrane area/volume ratio, sealing and external con-

nections, etc.) into account, tubular membrane module

concept was adopted. A series of MIEC materials such as

rane module Oxycoal-AC furnace


e module: outer heating, 1 m2 membrane area, 42 perovskite tubes with

C, Pmax = 20 bar.



Sr0.5Ca0.5Mn1�xFexO3�d, Ba0.5Sr0.5Co1�xFexO3�d and

BaCoxFeyZrzO3�d were tested. A vertical cylindrical fur-

nace with a combustion chamber length of 2100 mm and

an inner diameter of 400 mm was applied. The economic

evaluation indicated that oxyfuel combustion was an

economically viable technology for coal boilers. Super-

critical boilers have proven reliability and may show much

higher efficiency when used in ultra-supercritical steam

cycle conditions.

Conclusions and remarksIntegrating MCMs into power generation system is a

energy efficient process for carbon capture and storage

in power plants. Oxyfuel combustion is a potential and

environmentally friendly technique for heat and power

generation. This technique is most likely to be realized

industrially in the near future. The operation environ-

ment of MIEC membranes in oxyfuel process is relatively

mild and the only requirements are CO2 tolerance and

high permeability. Therefore, the long-term stable oper-

ation is feasible.

To promote the commercialization process of MCMs,

future work should focus on the following points: first,

membrane materials, dual-phase membranes made of

natural abundant elements with low cost are interesting;

second, membrane configuration, hollow fiber mem-

branes especially dual-layer hollow fibers with different

materials are desired; third, membrane module, pilot-

scale tubular design is promising; fourth, applications,

oxyfuel and coal gasification (IGCC) show promising

industrial prospects.

Great efforts from the scientific and engineering com-

munity are required before the implementation of MCMs

atan industrial level. Many issuesstillneedtobe addressed,

including the membrane reliability, high temperature

sealing, membrane production in quantity, and the mem-

brane cost. However, the substantial progress that has been

made by Air Products gives us great confidence and we

believe that the challenges for the commercial applications

of MCMs will be met in the near future.

AcknowledgementsThis work was financially supported by the National Basic ResearchProgram of China (no. 2009CB623406); National Natural ScienceFoundation of China (no. 20990222, no. 21006047); China PostdoctoralScience Foundation (no. 201003581).

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� of special interest�� of outstanding interest

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28. Cai MY, Liu S, Efimov K, Caro J, Feldhoff A, Wang HH:Preparation and hydrogen permeation of BaCe0.95Nd0.05O3Sd

membranes. J Membr Sci 2009, 343:90-96.

29. Matsuka M, Braddock RD, Matsumoto H, Sakai T, Agranovski IE,Ishihara T: Experimental and theoretical studies of hydrogenpermeation for doped strontium cerates. Solid State Ionics2010, 181:1328-1335.

30. Wei XT, Kniep J, Lin YS: Hydrogen permeation through terbiumdoped strontium cerate membranes enabled by presence ofreducing gas in the downstream. J Membr Sci 2009,345:201-206.

31. Bentzer HK, Bonanos N, Phair JW: EMF measurements onmixed protonic/electronic conductors for hydrogenmembrane applications. Solid State Ionics 2010, 181:249-255.

32. Mather GC, Poulidi D, Thursfield A, Pascual MJ, Jurado JR,Metcalfe IS: Hydrogen-permeation characteristics of aSrCeO3-based ceramic separation membrane: thermal,ageing and surface-modification effects. Solid State Ionics2010, 181:230-235.

33. Fang SM, Bi L, Wu XS, Gao HY, Chen CS, Liu W: Chemicalstability and hydrogen permeation performance of Ni–BaZr0.1Ce0.7Y0.2O3Sd in an H2S-containing atmosphere.J Power Sources 2008, 183:126-132.

34. Fang SM, Bi L, Yan LT, Sun WP, Chen CS, Liu W: CO2-resistanthydrogen permeation membranes based on doped ceria andnickel. J Phys Chem C 2010, 114:10986-10991.

35. Song SJ, Moon JH, Lee TH, Dorris SE, Balachandran U:Thickness dependence of hydrogen permeability forNi–BaCe0.8Y0.2O3Sd. Solid State Ionics 2008, 179:1854-1857.

36. Sirman J: The evolution of materials and architecture foroxygen transport membrane. In Nonporous Inorganic


Membranes. Edited by Sammells AF, Mundschau MV. Wiley-VCHVerlag GmbH & Co. KgaA; 2006:165-184.

37. Lin YS, de Vries KJ, Brinkman HW, Burggraaf AJ: Oxygensemipermeable solid oxide membrane composites preparedby electrochemical vapor deposition. J Membr Sci 1992,66:211-226.

38. Han J, Zeng Y, Xomeritakis G, Lin YS: Electrochemical vapordeposition synthesis and oxygen permeation properties ofdense zirconia–yttria–ceria membranes. Solid State Ionics1997, 98:63-72.

39. Carolan MF, Dyer PN: Ion transport membranes with catalyzedmixed conducting porous layer. US Patent 5534471; 1996.

40.��

Jin WQ, Li SG, Huang P, Xu NP, Shi J: Preparation of anasymmetric perovskite-type membrane and its oxygenpermeability. J Membr Sci 2001, 185:237-243.

This work provided a versatile co-sintering technique, which was widelyused by researchers in the subsequent works for the fabrication ofsupported ceramic membranes.

41.�

Yoon H, Oh T, Li JL, Duncan KL, Wachsman ED: Permeationthrough SrCe0.9Eu0.1O3Sd/Ni–SrCeO3 tubular hydrogenseparation membranes. J Electrochem Soc 2009, 1576:B791-B794.

In this paper, 30 mm SrCe0.9Eu0.1O3�d membrane was fabricated on theNiO–SrCeO3 tubular support. NiO was used not only to create porositybut also to provide catalytic activity by reduction to Ni when the mem-brane was subsequently exposed to H2 in operating process.

42. Yin X, Hong L, Liu ZL: Asymmetric tubular oxygen-permeableceramic membrane reactor for partial oxidation of methane.J Phys Chem C 2007, 111:9194-9202.

43. Kawahara A, Takahashi Y, Hirano Y, Hirano M, Ishihara T: Highoxygen permeation rate in La0.6Sr0.4Ti0.3Fe0.7O3 thinmembrane on a porous support with multichannel structurefor CH4 partial oxidation. Ind Eng Chem Res 2010, 49:5511-5516.

44.�

Liu ZK, Dong XL, Jin WQ: Elaboration of asymmetric tubularmixed-conducting dense membranes by spin-spraying andco-sintering process. AIChE Annual Meeting; Salt Lake City, UT,USA, session 340: 2010. paper 340a.

In this paper, a combined spin-spray and co-sintering technique wasproposed for the fabrication of 20 mm SCFZ mixed-conducting densemembrane. This work provided a simple but robust strategy for thepreparation of asymmetric tubular ceramic membranes.

45.��

Liu SM, Tan XY, Li K, Hughes R: Preparation andcharacterization of SrCe0.95Yb0.05O2.975 hollow fibremembranes. J Membr Sci 2001, 193:249-260.

This is a pioneer work for the preparation of mixed-conducting hollowfiber membranes using a phase inversion spinning/sintering technique.After that the membrane with this special asymmetric structure attractedextensive attentions. Hollow fiber is a promising membrane configurationand may play an important role in promoting the commercial applicationof mixed-conducting membranes.

46. Tan XY, Liu YT, Li K: Mixed conducting ceramic hollow-fibermembranes for air separation. AIChE J 2005, 51:1991-2000.

47. Tablet C, Grubert G, Wang HH, Schiestel T, Schroeder M,Langanke B, Caro J: Oxygen permeation study of perovskitehollow fiber membranes. Catal Today 2005, 104:126-130.

48. Caro J, Wang HH, Tablet C, Kleinert A, Feldhoff A, Schiestel T,Kilgus M, Kolsch P, Werth S: Evaluation of perovskites in hollowfibre and disk geometry in catalytic membrane reactors and inoxygen separators. Catal Today 2006, 118:128-135.

49. Smart S, Lin CXC, Ding L, Thambimuthu K, Diniz da Costa JC:High performance BaBiScCo hollow fibre membranes foroxygen transport. Energy Environ Sci 2011, 4:2516-2519.

50. Liu N, Tan XY, Meng B, Liu SM: Honeycomb-structuredperovskite hollow fibre membranes with ultra-thin densifiedlayer for oxygen separation. Sep Purif Technol 2011,80:396-401.

51. Buysse C, Kovalevsky A, Snijkers F, Buekenhoudt A, Mullens S,Luyten J, Kretzschmar J, Lenaerts S: Fabrication and oxygenpermeability of gastight, macrovoid-freeBa0.5Sr0.5Co0.8Fe0.2O3Sd capillaries for high temperature gasseparation. J Membr Sci 2010, 359:86-92.



52.��

Wu ZT, Wang B, Li K: A novel dual-layer ceramic hollow fibremembrane reactor for methane conversion. J Membr Sci 2010,352:63-70.

For the first time, a novel dual-layer ceramic hollow fiber membrane wasdeveloped using a single-step co-extrusion and co-sintering technique.This membrane consists of a thin outer separation layer supported on aninner porous substrate. This type of fiber shows potential applications incatalytic membrane reactors and solid state electrochemical areas. Thisis a great progress of ceramic membrane preparation technique.

53. Wei YY, Liu HF, Xue J, Li Z, Wang HH: Preparation and oxygenpermeation of U-shaped perovskite hollow-fiber membranes.AIChE J 2011, 57:975-984.

54. Voigt I, Kriegel R, Adler W, Sommer E: Vacuum driven oxygenseparation with BSCF membranes. NAMS/ICIM 2010;Washington, DC, USA: 2010. poster 1319.

55.��

Tan XY, Wang ZG, Meng B, Meng XX, Li K: Pilot-scale productionof oxygen from air using perovskite hollow fibre membranes.J Membr Sci 2010, 352:189-196.

In this paper, a first pilot-scale mixed-conducting hollow fiber membranemodule with the effective membrane area of 1 m2 was established. This isa key step on the development of mixed-conducting membranes fromlab-scale to commercialization.

56.��

Anderson LL, Armstrong PA, Repasky JM, Stein VE: Enabling cleancoal power generation: ITM oxygen technology. InternationalPittsburgh Coal Conference; Pittsburgh, PA, USA: 2011.


This paper presented an overview of the ITM oxygen development effortsmade by Air Products, in which commercial-scale ceramic modules withthe oxygen production rate of 5–10 tons per day was shown. Theexcellent work from Air Products gives us great confidence and webelieve that the challenges for the commercialization of mixed-conduct-ing membranes will be met in the near future.

57.��

Kneer R, Toporov D, Forster M, Christ D, Broeckmann C, Pfaff E,Zwick M, Engelsc S, Modigell M: OXYCOAL-AC: towards anintegrated coal-fired power plant process with ion transportmembrane-based oxygen supply. Energy Environ Sci 2010,3:198-207.

The first demonstration plant of oxycoal process for power generationwith CO2 capture was established. This work is a milestone for thecommercialization of mixed-conducting ceramic membranes.

58. Tan XY, Li K, Thursfield A, Metcalfe IS: Oxyfuel combustion usinga catalytic ceramic membrane reactor. Catal Today 2008,131:292-304.

59. Engels S, Markus T, Modigell M, Singheiser L: Oxygenpermeation and stability investigations on MIEC membranematerials under operating conditions for power plantprocesses. J Membr Sci 2011, 370:58-69.

60. Stadler H, Beggel F, Habermehl M, Persigehl B, Kneer R,Modigell M, Jeschke P: Oxyfuel coal combustion by efficientintegration of oxygen transport membranes. Int J Greenh GasCon 2011, 5:7-15.


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