Author’s Accepted Manuscript

Fabrication of defect-free Matrimid® asymmetric

membranes and the elevated temperature
application for N2/SF6 separation

Yan Dai, Qing Li, Xuehua Ruan, Yong Hou,

Xiaobin Jiang, Xiaoming Yan, Gaohong He,
Fanqing Meng, Zhiyu Wang www.elsevier.com/locate/memsci

PII: S0376-7388(18)33176-4
DOI: https://doi.org/10.1016/j.memsci.2019.01.050
Reference: MEMSCI16820
To appear in: Journal of Membrane Science
Received date: 15 November 2018
Revised date: 26 January 2019
Accepted date: 29 January 2019
Cite this article as: Yan Dai, Qing Li, Xuehua Ruan, Yong Hou, Xiaobin Jiang,
Xiaoming Yan, Gaohong He, Fanqing Meng and Zhiyu Wang, Fabrication of
defect-free Matrimid® asymmetric membranes and the elevated temperature
application for N2/SF6 separation, Journal of Membrane Science,
https://doi.org/10.1016/j.memsci.2019.01.050
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 Fabrication of defect-free Matrimid® asymmetric membranes and the

elevated temperature application for N2/SF6 separation

Yan Dai1§, Qing Li1§, Xuehua Ruan1*, Yong Hou1, Xiaobin Jiang1, Xiaoming Yan1, Gaohong He1*,
Fanqing Meng2, Zhiyu Wang2
1
State Key Laboratory of Fine Chemicals, School of Petroleum and Chemical Engineering,
Liaoning Province Engineering Laboratory for Petrochemical Separation Technologies,
Dalian University of Technology at Panjin, Panjin 124221, P. R. China
2
Department of Environmental Protection, Henan Pinggao Electric Co., Pingdingshan 467001, P. R. China

Abstract:

N2/SF6 mixtures have been widely used in gas-insulated equipment. Highly efficient separation

approaches are urgently required to recycle SF6 from the mixtures during equipment maintenance.

Gas separation with glassy polymeric membranes is regarded as a promising approach due to the

great size difference between SF6 and N2 molecules. However, the common membranes are quite

low permeable for N2/SF6 mixtures. In this research, the dry-wet phase inversion was customized

with sectionalized air gap, i.e., dried air at upper section and humidified air at lower section, to

manufacture Matrimid® asymmetric membranes in bulk with an ultrathin and defect-free selective

layer. After optimization, the defect-free selective layer could be thinned to 80 nm. The pure gas

test at 25 °C revealed that JN2 was increased to 2.58 GPU, and αN2/SF6 was approximately 41, very

close to the value in the literature [J. Membr. Sci., 2014, 452, 311]. Without the restriction from

the usual PDMS coating layer for defect-blocking, the elevated temperature operation was able to

be employed to further enhance gas permeation. At 128 °C, the selectivity αN2/SF6 was maximized

to 115, and the relevant JN2 is 9.0 GPU. At 200 °C, the temperature close to the allowable upper

limit, JN2 was increased to 15.9 GPU, and the relevant αN2/SF6 was 97. Furthermore, the mixed-gas

test demonstrated the favorable long-term stability of the customized membranes, even under the

extreme running condition with pressure up to 2.0 MPaG and temperature up to 200 °C. With high

*
Corresponding author at: School of Petroleum & Chemical Engineering, Dalian University of Technology at Panjin, Panjin
124221, PR China. E-mail address: xuehuaruan@dlut.edu.cn (X. Ruan) and hgaohong@dlut.edu.cn (G. He).
§
Y. Dai and Q. Li contributed equally to this work.
1
efficiency and throughput under elevated temperature operation mode, the Matrimid® asymmetric

membrane with ultrathin and defect-free selective layer is a promising approach for the separation

and recycle of SF6 from the N2/SF6 mixtures.

Graphical abstract:

Keywords: Gas membrane separation; N2/SF6 mixture; defect-free selective layer;

elevated temperature operation; Matrimid® polyimide

1. Introduction

Sulfur hexafluoride (SF6), by virtue of the excellent dielectric and arc-quenching capability, has

been widely utilized for high-voltage electrical apparatuses [1-3]. In recent years, N2/SF6 mixtures,

possessing similar or slightly inferior electrical properties to pure SF6, but much lower in cost and

incondensable under low temperature, become the favored insulation agent in large-scale projects,

e.g., underground/underwater transmission lines, substations, as well as the arctic projects [4-5].

The environmental problems about climate change and global warming become more and more

pressing. As the most potent greenhouse gas, SF6 is estimated to be 23500 times greater than CO2

in global warming potential [6-7]. What’s more, its lifetime is estimated to be at least 3200 years

under atmospheric condition [8]. Owing to the long-term negative impact on the environment, it is

expected that any possible SF6 emissions should be avoided. Thus, it is important to recycle SF6
2
during high-voltage electrical equipment maintenance. In comparison to the pure SF6 agent, it is

more difficult to recycle N2/SF6 mixtures, because an efficient technique is needed to separate SF6

from N2 [9]. According to the latest environmental standard in China, SF6 should be reduced to

less than 800 ppmv in the N2-enriched discharge stream. The feasible techniques to achieve this

goal include cryogenic liquefaction, adsorption, gas membrane separation, and so on [2, 10-15].

SF6 and N2 are significantly different in molecular size. The diameter of SF6 is 0.502 nm and

that of N2 is 0.359 nm [16-17]. Glassy polymeric membranes, featuring a diffusion-controlled gas

permeation, have high separation selectivity for gases largely different in molecular size. [18-20].

Yamamoto et al. [21] revealed that the perm-selectivity, αN2/SF6, was higher than 50 in polyimide

membrane at 40 °C. Lee et al. [22] reported that αN2/SF6 was up to 23.6 in polysulfone membrane

(MF1008P, AIRRANE) and 43.8 in commercial polyimide hollow fiber module (PA4050-P3, Air

Products & Chemicals, Inc) at 25 °C, respectively. More striking, Wolińska-Grabczyk et al. [23]

reported that the selectivity in isotactic poly(4-methyl-1-pentene) membrane is up to 476 at 30 °C.

It is evident that glassy polymeric membranes have great potential for highly selective separation

of N2/SF6 mixtures.

The challenge to launch glassy polymeric membranes for N2/SF6 separation is to enhance their

processing ability. According to the general applications, e.g., H2 recovery and O2 enrichment, N2

permeation rate, JN2, is extremely low in commercial glassy polymeric membrane modules [24].

In AIRRANE's polysulfone module, JN2 is 4.83 GPU at 25 °C [25]. In Permea's polyimide hollow

fiber module, well known as PRISM® brand, JN2 is 2.60 GPU at 60 °C [26]. In Mitsui's isotactic

poly(4-methyl-1-pentene) TPX membrane, JN2 is about 0.25 GPU at 25 °C [27]. Owing to the low

permeation ability, more than 1000 m2 membrane area would be demanded in an industrial N2/SF6

separation unit to scale its capacity up to 50 Nm3/h, to match with the representative gas-insulated

equipment in large-scale projects. Overall, membranes with both high permeation ability and high

selectivity are urgently needed to reduce equipment investment.

3
 According to the above-mentioned data, isotactic poly(4-methyl-1-pentene) is high selective for

N2/SF6 separation. However, its solubility is poor in the polar solvents usually used for membrane

production [28]. It is difficult to fabricate highly permeable poly(4-methyl-1-pentene) asymmetric

membranes with dry-wet phase inversion. In this instance, poly(4-methyl-1-pentene) membranes,

e.g., Mitsui's TPX membrane, are usually produced by melt-casting process in homogeneous film

form and extremely low in gas permeation ability [27, 29].

In the present work, Matrimid® 5218, a commercial polyimide material with PN2 = 0.25 Barrer,

is selected to prepare membrane for N2/SF6 separation. Besides relatively high permeation ability

and selectivity, this material has excellent mechanical properties and solubility in organic solvents

for membrane fabrication [30]. Based on this excellent material, two approaches are employed to

enhance gas permeation: fabricating asymmetric membrane with ultrathin selective layer [31-35],

and conducting the elevated temperature operation [36]. For Matrimid® 5218 polyimide, the glass

transitional temperature is up to 317 °C [37]. Nevertheless, the membrane is required to be tailored

without PDMS defect-blocking coating layer to increase its allowable operation temperature. Early

in 2000s, Clausi et al. reported the lab-scale production of Matrimid® hollow fiber membranes with

defect-free and ultrathin skin layer [31]. However, the large-scale production hasn't been reported

to date. It is speculated that some fluctuant conditions might result in the formation of pinhole

defects on the skin layer. For example, the nascent dense layer after solvent vaporization, which is

very thin and semi-liquid state, is easy to be punctured by the intensive solvent exchange in

coagulation bath. Accordingly, the dry-wet phase inversion is further customized in this research

with sectionalized air gap and changeable humidity in vertical direction to fabricate asymmetric

membrane with ultrathin and defect-free selective layer to avoid coating for defect-blocking.

2. Problem and customized membrane fabrication

In general, the commercial glassy polymeric membranes are fabricated through two procedures,

i.e., the dry-wet phase inversion and the dip-coating process [38-39]. The former is to construct a

4
monolithic but asymmetric structure, in which a thin but dense skin layer is supported by a porous

substrate. The skin layer thickness dominates the mass transfer across membrane. The thinner the

skin layer, the higher the permeation ability. However, pinhole defects on the skin layer abruptly

increase and seriously impair permeation selectivity once the skin thickness is lower than a bound.

Some lab-scale cases with meticulous manipulation demonstrated that the minimum thickness for

a defect-free skin layer could be reduced to about 100 nm [31, 40-41]. However, in the large-scale

products, e.g., PRISM® membrane, the skin layer could not be guaranteed to be defect-free even

though the thickness is controlled to be about 500 nm [42]. Although the PRISM® membrane is in

hollow fiber form, the dry-wet phase inversion and the mechanism resulting in the pinhole defects

on skin layer are similar for all membrane forms. In this instance, the dip-coating procedure with

PDMS solution is required to eliminate the pinhole defects and make the dense skin layer behave

like a defect-free selective layer [43-44].

Fig. 1. General dry-wet phase inversion technique and analytic membrane formation steps.

PDMS defect-blocking coating layer, subject to its softening behavior, will seriously reduce the

allowable operation temperature [45], and consequently limit the elevated temperature operation

to enhance gas permeation. In order to avoid the dip-coating process, the dry-wet phase inversion

technique should be retrofitted with intent to generate ultra-thin skin layer in bulk without pinhole

defects continuously and conveniently.

5
 Before the modification, the crucial details likely to induce pinhole defects on skin layer should

be found out. In this instance, the general dry-wet phase inversion process is dissected into several

membrane formation steps, as shown in Fig 1. According to the graphic representation, membrane

formation can be broken down into four steps: 1. Polymer solution is spreading on the non-woven

fabric evenly; 2. Solvent is vaporized gradually in the air gap, in the meantime polymer on liquid

film surface is concentrated to create the dense skin layer; 3. The thin film of polymer solution on

the non-woven fabric, together with the nascent dense layer, is immersed into the coagulation bath,

in which solvent and nonsolvent are exchanged rapidly to form the continuous polymer-rich phase

and the discrete polymer-poor phase in liquid film, i.e., the nascent morphologies of asymmetric

substrate and porous structure, respectively; 4. Solvent exchange is going on and the polymer-rich

phase is solidified as the asymmetric substrate [46-48]. Hereinto, STEP-2 is significant to control

the skin layer thickness. By reducing the residence time, with shorter air gap and/or faster shift of

solution film cast on the non-woven fabric, we could make the dense skin layer thinner. STEP-3 is

the critical point to form pinhole defects on skin layer. In its initial stage, i.e., the moment that the

solution film enters coagulation bath, the nascent dense layer in STEP-2 is under semi-liquid state

and very thin to generate highly permeable membrane, which is extremely lacking in strength and

easy to be punctured by the intensive solvent exchange from solution film to coagulation bath.

Fig. 2. Customized dry-wet phase inversion technique and analytic membrane formation steps.
6
 According to the mechanism mentioned above, there are two means available to reduce pinhole

defects on membrane skin layer, i.e., tuning thickness accurately to strengthen the nascent dense

layer, and slowing down solvent/nonsolvent exchange partially to decrease puncture phenomenon.

The former is negative to enhance gas permeation ability and therefore not considered. Based on the

latter guideline, the membrane fabrication technique is retrofitted with a joint step between the dry

step (STEP-2) and the wet step (STEP-3), as exhibited in Fig. 2. Within the joint step, the polymer

solution thin film is immersed in the humidified air rather than the coagulation bath. Similar to

what happens in STEP-2, solvent in the solution film is removed via vaporization, but some water

molecules could slowly enter the solution film and create the discrete polymer-poor phase before

STEP-3. The transitional microstructure under the dense skin layer is conceived and exhibited in

Fig. 2. It is seen that the semi-solid thickness to withstand solvent/nonsolvent exchange impact in

STEP-3 is no longer subject to the thickness of nascent dense layer formed in STEP-2. In other

words, the conflict between the defect-free and the ultra-thin requests can be resolved facilely.

3. Experimental

3.1 Materials and reagents

The Matrimid® 5218 polyimide was purchased from Huntsman (Basel, Switzerland) and used

as received. Its chemical structure is exhibited in Fig. 3. The good solvent, N-methyl-2-pyrrolidone

(NMP), and the additive, n-BuOH, were purchased from Kemiou (Tianjin, China), both analytical

grade and directly utilized without further purification. PET nonwoven fabric with high thermal

stability was purchased from Ahlstrom (Helsinki, Finland). Deionized water for coagulation bath

was generated by laboratory water purification unit (LTLD-P50, RIGHTLEDER, Beijing, China).

Anhydrous ethanol and isohexane for solvent exchange, both are chemical grade, were purchased

from Kemiou (Tianjin, China). For gas permeation test, N2 and H2 (99.99 vol%) were supplied by

JIAHE (Yingkou, China), SF6 (99.99 vol%) was purchased from FEILIER (Luoyang, China).

3.2 Membrane fabrication

7
 For various membrane forms, the casting solution composition should be tuned. Early in 2000s,

Clausi et al. reported the lab-scale production of asymmetric Matrimid® hollow fiber membranes

with defect-free and ultrathin skin layer [31]. Subject to our membrane fabrication equipment, the

casting solution in this work is referring to the classic cases for membrane fabrication in flat sheet

form [30, 39]. In detail, Matrimid® (15.0 wt%) and n-BuOH (9.0 wt%) were dissolved in NMP to

prepare casting solution. After vacuum degassing, the solution was piped into a pilot-scale casting

machine and spread on the non-woven fabric evenly. The minimum distance between non-woven

fabric and casting knife was controlled to be about 200 μm, while the casting speed was fixed to

be about 2.0 m/min. The air gap was variable according to the membrane fabrication techniques.

For the normal process, the environment is the dried air with RH < 20 % at 25 °C. For the

customized route, the air gap would be divided into two portions, in which the upper part is the

dried air as usual, while the lower part is the humidified air with RH > 80 % at 25 °C. The dried air

and the humidified air would be blown into the gap lightly to control the conditions. In order to

fabricate an ultrathin and defect-free selective layer, the total air gap height and the division ratio

between dried and humidified sections were carefully tuned.

Fig. 3. Chemical structure of Matrimid® 5218 for membrane fabrication [39].

After passing through air gap, the polymer solution film led by non-woven fabric was immersed

into the coagulation bath filled with renewal deionized water at 20 °C. After being coagulated

completely, the obtained membrane was immersed in the aqueous bath for at least 24 h to remove

solvent thoroughly by renewal deionized water. In the following, the solvent exchange was made

with anhydrous ethanol (0.0221 N/m) and isohexane (0.0167 N/m) successively to replace water

(0.0721 N/m) reserved in membrane porous structure, because the high surface tension of water

8
may break microstructure down during baking operation. In the end, membrane sample was dried

in air naturally at 25 °C, followed by thermal annealing at 200 °C in N2 stream for 24 h (Physical

aging) to make membrane samples stable in performance.

3.3 Membrane microstructure characterization

Membrane morphology was characterized with a regular SEM (KYKY-2800B, Beijing, China.

The sectional morphology close to the surface, which might be changed by membrane fabrication

techniques, was characterized via a high-resolution FE-SEM (NOVA NanoSEM 450, USA). Prior

to the observation, a thin layer of highly conductive gold was coated on membrane sample surface

through the ion sputtering deposition.

3.4 Gas permeation tests

A small plate-and-frame module with two membrane leaves was assembled for gas permeation

test. Its schematic structure and supporting test flowsheet are exhibited in Fig. 4. The permeation

cavity is circular and the diameter is 16.0 cm. Accordingly, the total effective area used in the test

is about 400 cm2. The two key factors to characterize membrane performance, i.e., permeance rate

and selectivity, would be systematically tested by this apparatus.

Fig. 4. Plate-and-frame membrane module and gas permeation test flowsheet [39].

The test temperature was given as 25 °C, except the cases for elevated temperature application.

The feed-side pressure could be adjusted between 0.1 and 2.0 MPaG, while the permeated stream

9
was exiting under atmospheric pressure. In addition, the permeation apparatus should be running

for at least 30 min to achieve the steady-state permeation before recording stream pressures, flow

rates, and extracting stream samples. The gas chromatography (8610C, TechComp, Beijing, China)

equipped with the GDX-105 packed column (40 °C) and the thermal conductivity detector (60 °C)

was employed to analyze the mixture samples.

In order to examine the condition to fabricate defect-free membranes, gas permeation tests with

pure H2 and N2 were conducted in the laboratory at first. Their intrinsic permeation coefficients in

Matrimid® 5218 have been widely reported in the literature, e.g., PH2 = 24 Barrer, PN2 = 0.25 Barrer,

and αH2/N2 = 96 at 25 °C [30]. In this work, the membrane would be considered as defect-free once

the tested value of αH2/N2 is larger than 95 % of the intrinsic value. For the membranes approved to

be defect-free, permeation tests with pure SF6 and N2 were conducted to obtain the ideal selectivity.

Afterwards, the tests with mixture, containing 30 vol% of SF6 and 70 vol% of N2, would be done

for the elevated temperature application to examine long term stability.

4. Results and Discussion

4.1 Air gap optimization for defect-free membrane fabrication

In order to achieve defect-free and ultrathin-skinned asymmetric membranes, the air gap has to

be optimized. In this research, the height of humidified air gap (H-Gap) was arranged to be 0.0 m,

0.2 m, 0.4 m, and 0.6 m, respectively. Hereinto, the level of 0.0 m is corresponding to the general

membrane fabrication technique without the H-Gap. Under each H-Gap height, the height of dried

air gap (D-Gap) would be regulated with the step length of 25 mm meticulously.

10
Fig. 5. Effects of air gap arrangement on defect-free membrane fabrication.

The asymmetric membranes yielded under various air gap conditions have been systematically

tested. The data about JH2 and αH2/N2 were summarized and compared in Fig. 5. Each fabrication

condition would take at least five membrane samples for gas permeation test. On the whole, along

with the increase in D-Gap height, membrane selectivity is gradually upgrading but the permeation

ability is lowering gradually. Before the selectivity highly close to the intrinsic value, membranes

yielded under the same condition are varied in performance, which is attributed to the fact that the

formation of pinhole defects is random on membrane skin layer. The more the defects exist in a

membrane sample, the lower the selectivity, the higher the permeation ability, and vice versa. In

addition, the increase in H-Gap height is helpful to achieve a defect-free membrane skin layer and

to shorten the D-Gap height simultaneously. In other words, it is promising to fabricate defect-free

and ultrathin-skinned membranes in bulk continuously and conveniently.

According to the membrane selectivity curves in Fig. 5, we could determine the proper D-Gap

height in match with H-Gap height to achieve a defect-free skin layer. For the general fabrication

technique, the suitable D-Gap height is about 0.260 m, and the value of JH2 is realized to be about

11
129.8 GPU. Along with the increase in H-Gap height, the proper D-Gap height is reduced. Owing

to the thinner defect-free skin layer, gas permeation rate is enhanced. Nevertheless, the increase in

H-Gap height is gradually coming to be inefficient to enhance gas permeation. As shown in Fig. 5,

gas permeation can be enhanced by no more than 5 % while the H-Gap height is further increased

from 0.40 to 0.60 m. In this respect, the optimized H-Gap height is confirmed to be 0.40 m, while

the proper D-Gap height is reduced to be 0.155 m. Correspondingly, the value of JH2 is increased

to be about 235.1 GPU for the defect-free and ultrathin-skinned asymmetric membranes.

4.2 Membrane microstructure analysis

Microstructure is essential to enhance membrane performance. Membrane morphology yielded

under the optimized fabrication condition is exhibited in Fig. 6. Although the non-woven fabric is

stripped in sample preparation, the cross-section structure is a desirable asymmetric structure. The

cross-section bulk is highly porous and connective with the mean pore size close to 0.1 μm, which

is stable to withstand high pressure difference and effectual to reduce gas transport resistance. The

cross-section outer edge is dense relatively with the mean thickness equal to 0.4 μm. Its surface is

confirmed to be defect-free through the morphology image, which is effectual to guarantee highly

selective ability for mass permeation. It should be mentioned that the outer edge does not become

dense thoroughly. According to the phase inversion feature in humidified air, microscopic pores

should be widespread at the location close to the real dense layer. The ratio between the intrinsic

permeability and the tested permeance (H2, 24 Barrer, and 235.1 GPU) reveals that the real dense

layer is about 100 nm in thickness. On the condition that the porous substrate has a little resistance

to mass transfer across membrane, the real dense layer thickness should be thinner than 100 nm to

a certain extent. Therefore, the sublayer with microscopic pores is about 300 nm in thickness.

12
Fig. 6. Morphology of the asymmetric membrane formed by customized technique.

In order to illustrate the effect of the humidified air gap, the comparison between the membrane

samples formed by the common and the customized routes is conducted with their high-resolution

images for the cross-section outer edge, as shown in Fig. 7. Both these two membrane samples are

defect-free to achieve high selectivity. For the common route, we could distinguish the dense layer

from the unconsolidated layer distinctly in membrane outer edge. The dense layer is about 170 nm

in thickness. With the intent to fabricate defect-free membrane in scale production, the dense layer

is much higher than the minimum thickness (100 nm) reported in the literature [31, 40-41]. For the

customized fabrication route, membrane outer edge is going to be a different morphology. Between

the unconsolidated layer and the dense layer, there is an ambiguous transitional layer. The overall

skin thickness, including the dense surface layer and the transitional layer, has been increased to

about 420 nm, which is sufficient to achieve defect-free membrane in scale production. In contrast,

the dense layer has been thinned to 80 nm dramatically, and it is naturally that gas permeation rate

through the customized membrane can be nearly 0.8 times higher than that through the membrane

fabricated by the general technique.

13
Fig. 7. Morphology comparison of the defect-free membrane skin layers formed by (a) general
technique and (b) customized technique.

4.3 Membrane operation temperature optimization

The elevated temperature operation is an approach to enhance permeation. In order to determine

the optimal condition, pure gas permeation tests were conducted with temperature ranged between

25 °C and 200 °C. Pure N2 or SF6 entered at 1.0 MPaG, while the permeate exited at atmospheric

pressure. Owing to membrane skin's structure feature, the temperature upper limit was given much

lower than Matrimid® 5218's glass transitional temperature (~317 °C).

Pure gas permeation data under different temperature are summarized in Fig. 8. N2 permeation

rate is monotonically increasing along with the elevation in temperature. The increase tendency is

in good agreement with the Arrhenius correlation in the whole temperature range. In other words,

N2 permeation in Matrimid® 5218 was mainly controlled by the diffusion. Unlike this monotonic

variation, SF6 permeation rate decreased at first and then increased along with the further elevation

in temperature. With the critical temperature up to 45.6 °C, SF6 can be regarded to be condensable

under mild temperature, but changed to permanent gas under higher temperature. In this instance,

this unique phenomenon can be explained through the solution-diffusion mechanism. The decline

within the lower temperature range could be attributed to the variation in SF6 solution coefficient,

while the upgrade within the higher temperature range can be analogously attributed to the change

in SF6 diffusion coefficient in glassy membrane material. Owing to the unique variation tendency

for SF6 permeation rate, the perm-selectivity αN2/SF6 has an extreme value. According to the curve
14
shown in Fig. 8, the maximum αN2/SF6 value is about 115, which occurred with the temperature at

128 °C, and the relevant N2 permeation rate JN2 is about 9.0 GPU. In addition, the maximum JN2

value, subject to membrane samples' allowable temperature, is about 15.9 GPU at 200 °C, and the

relevant selectivity αN2/SF6 value is 97.

Fig. 8. Effects of operation temperature on customized defect-free membrane performance.

From the view of commercial application, membrane feed can be easily heated to 120 °C along

with the compression, and further heated to 200 °C by the 2.0 MPaG saturated steam. In addition,

membrane material Matrimid® 5218 is stable in the long term with the service temperature under

200 °C. All in all, the elevated temperature operation improved the performance of the defect-free

and ultrathin-skinned asymmetric membranes. In comparison with the operation under ambient

temperature, both selectivity and permeation rate were significantly enhanced through the elevated

temperature operation.

4.4 Pressure sensitivity analysis

The ultrathin-skinned membranes, subject to skin's structural and mechanical features, might be

partly ineffective under high trans-membrane pressure difference. In this instance, gas permeation

results under various feed input pressure are given in Fig. 9 to analyze the pressure sensitivity. On

the whole, both permeance JN2 and selectivity αN2/SF6 slightly declines along with the upgrade in

input pressure. After elevating pressure from 0.1 MPaG to 2.0 MPaG, the attenuation in permeance
15
is no more than 10 %, and the attenuation in selectivity is less than 5 %. It can be derived that the

customized defect-free membranes are reliable for high temperature operation at high pressure.

Fig. 9. Effects of feed input pressure on customized defect-free membrane performance.

More than the downward tendency on the whole, the effects of gas input pressure are different

from each other under various temperature conditions, as indicated by the difference in the slope.

The decline in permeance is larger at high temperature, e.g., 200 °C, which can be attributed to the

fact that polymeric membrane materials become flexible at high temperature and are more likely

to be compacted. Instead, the attenuation in selectivity is more apparent at low temperature, e.g.,

50 °C, because low temperature and high pressure are working in opposite to impair N2 permeation

(via decreasing diffusion), but in parallel to enhance SF6 permeation (via increasing dissolution).

Accordingly, high temperature could slightly offset the negative effects of high operation pressure

and maintain high separation efficiency.

4.5 Long-term performance and stability

The long-term exposure of membrane modules in high temperature and high pressure system is

likely to impair separation efficiency. In order to analyze the long-term performance and stability,

the relevant mixed-gas permeation tests were carried out and the results are shown in Fig. 10. For

these tests, the mixed gas (SF6, 30 vol% and N2, 70 vol%) is entering at a commonly used pressure

level, i.e., 2.0 MPaG. The permeation stage cut, i.e., the molar flow rate ratio of the permeate to the

16
feed, was controlled almost constantly at 20 %. Membrane unit temperature was elevated step by

step from 25 °C to 200 °C, with the increment equal to 25 °C. Before the temperature was raised

up to 200 °C, the duration in each step was about 20 h to confirm that the membrane module can

withstand this condition. In addition, the overall time last for the long-term test is more than 720 h

to confirm membrane stability.

Fig. 10. Long-term permeation results with N2/SF6 mixture under extreme condition.

The long-term stability is reflected by the permeate stream's flow rate and N2 molar fraction, as

exhibited in Fig. 10. In each temperature step, the permeate flow rate was essentially constant, but

N2 molar fraction is fluctuating to some extent. According to our meticulous data checking, such a

fluctuation can be attributed to the unstable control for residual flow rate. Along with the increase

in residual flow rate, N2 content in the residue was increased in direct proportion, which denoted

the increase in N2 permeation driving force, and correspondingly N2 content was increased in the

permeate stream, and vice versa. In addition, the unstable control for system temperature and the

consequent variation in selectivity could also contribute to this N2 fraction fluctuation in permeate.

The statistical results of permeance JN2 and selectivity αN2/SF6 under different temperature levels

are listed in Table 1. On the whole, the customized defect-free and ultrathin-skinned membrane

was excellent without visible distinction between the pure-gas and the mixed-gas permeation tests.

Although N2 fraction in the permeate stream has a slight reduction while the membrane unit has

17
been continuously running under the extreme condition for 720 h, a highly efficient separation can

be achieved with the perm-selectivity αN2/SF6 close to 90. It can be concluded that our customized

membrane sample has a favorable long-term performance and stability even though the operation

pressure is up to 2.0 MPaG and meanwhile the temperature is up to 200 °C.

Table 1 Performance of customized defect-free membrane tested by mixed-gas at 2.0 MPaG.

T, °C 25 50 75 100 125 150 175 200

JN2, GPU 2.5 3.6 4.9 6.3 8.4 10.6 13.2 15.7
αN2/SF6 38.7 62.2 90.8 110.3 114.5 112.0 103.6 96.1
Note: the performance at 200 °C is the average level for the initial 20 h.

All these test results demonstrated that the customized asymmetric membrane is high efficiency

and throughput for N2/SF6 separation. It is suitable to retrofit the dry-wet phase inversion process

with sectionalized air gap. However, the customized asymmetric membrane, subject to the casting

equipment in our lab, was fabricated in flat sheet form. Such a membrane formation is inefficient

for module packing density, i.e., membrane area per unit volume, and consequently the membrane

plant is large in footprint for N2/SF6 mixture. Membrane manufacture in a hollow fiber form is an

available solution. Module packing density with hollow fiber membrane can be 100 times higher

than that with flat sheet membrane. Accordingly, this customized dry-wet phase inversion process

would be attempted to fabricate hollow fiber membrane in our following work.

5. Conclusions

In order to achieve N2/SF6 separation and recycle with both high efficiency and high processing

ability, Matrimid® asymmetric membranes were fabricated in bulk with a defect-free but ultrathin

selective layer using the customized dry-wet phase inversion with sectionalized air gap, in which

the upper section was the dried air gap and the lower section was the humidified air gap. With the

heights of the dried and humidified air gaps optimized to be 0.40 m and 0.155 m respectively, the
18
defect-free selective layer could be thinned to about 80 nm. The pure gas permeation tests at 25 °C

and 1.0 MPaG revealed that JN2 was increased to 2.58 GPU and αN2/SF6 was maintained at 41, very

close to the value in the literature [22].

Without the restriction from PDMS defect-blocking coating layer, commonly existing in those

commercial membranes, the elevated temperature application was conducted for our customized

asymmetric membranes to further enhance gas permeation ability. The maximum αN2/SF6 value was

about 115, occurring at 128 °C, and the relevant JN2 was about 9.0 GPU. With the temperature up

to the allowable upper limit at 200 °C, JN2 was extremely increased to 15.9 GPU, and the relevant

αN2/SF6 value was about 97. Moreover, the mixed-gas test revealed that the customized membranes

had a favorable long-term performance and stability even under the extreme work condition with

pressure up to 2.0 MPaG and the temperature up to 200 °C simultaneously.

On the whole, the customized Matrimid® asymmetric membranes with defect-free and ultrathin

selective layer and elevated temperature operation mode could be a promising technique with both

high efficiency and throughput to separate and recycle SF6 from the N2/SF6 mixtures.

Acknowledgements

The authors acknowledged the financial supports from the National Natural Science Foundation

of China (Grant No. 21606035, U1663223, 21527812, 21676043), Changjiang Scholars Program

(T2012049), the Fundamental Research Funds for Central Universities (DUT18JC24), Liaoning

Province S&T Department (Grant No.201601037) and Education Department (LT2015007).

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Highlights:

 Phase inversion is retrofitted to fabricate high-flux defect-free membrane in bulk.

 Defect-free dense layer is thinned to 80 nm by modified dry-wet phase inversion.
 Customized membrane behaved excellent with αN2/SF6 = 115 & JN2 = 9.0 GPU at 128 °C.
 Customized membrane has favorable long-term stability under 2.0 MPaG and 200 °C.
 Customized membrane with high temperature mode is promising for N2/SF6 separation.

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