FINAL REPORT Ed1 MCS

Membrane Reactors and Three-Phase Hydrogenation P a g e | 1

Levulinic Acid Hydrogenation Reaction using a

Polymeric Catalytic Membrane Reactor

By

Michelle C. Soto Hernández

NSF REU Program in Sustainable Bioenergy 2015

Department of Chemical Engineering

Kansas State University

Final Research Report

This material is based upon work supported by National Science Foundation Grant: REU Site: Summer Academy

in Sustainable Bioenergy; NSF Award No.: SMA-1359082, awarded to Kansas State University.


Abstract

The environmental degradation caused by the consumption of fossil and the increasing energy

demand is of great concern when taking in account social welfare. It is forecast that fossil fuel will not

be able to defray society’s demands. Efforts are being placed in the study of lignocellulose-biomass

conversion, which represents a possible solution to this problem since platform molecules can be

obtained from it. These type of molecules can be used to produce fuels and fuels additive.

Hydrogenation reactions are industrially relevant in petrochemical and petroleum refining and in

emerging biorefining. The reaction that was studied was the hydrogenation of levulinic acid (LA) to

produce gamma-valerolactone (GVL), a chemical platform. Previous studies had conducted this reaction

in a packed bed reactor. One of the problems presented in this kind of reactor is the mass transfer

limitation, hydrogen delivery to the catalyst sites. Membrane reactors can lessen the mass transfer

limitations by supplying hydrogen to the catalytic sites on the membrane surface. The main objective of

this project was to develop a polymeric membrane for the hydrogenation of LA.

Polytetrafluoroethylene (PTFE) was used as the support of the polymer Matrimid. Among the different

types of membranes developed, we focus on the reaction conducted with a membrane that consisted of

0.25wt% and 1.0wt% Matrimid dissolved in methylene chloride (DCM) and spin-coated onto the PTFE

membrane. Also, different types of solvents for the LA hydrogenation were evaluated such as glycerol,

water and gamma-butyrolactone (GBL). At constant temperature of 70oC, glycerol did not show any

yield of GVL after13-15 hours of reaction. When GBL was used as solvent for LA, a bronze colored

liquid was obtained. Since this chemical has similar properties to GBL, it was not able to be analyzed by

simple means. Water showed to be the most efficient solvent to produce GVL. Also, the PTFE

permeability for water and GBL was evaluated. GBL has a lower vapor pressure in comparison to water,

therefore allowing the reaction to be conducted at higher temperature without extreme permeability of

the liquid phase, as expected due to its high boiling point. In the case of water, 70C was chosen as

reaction temperature for further experiments, because produced a manageable water permeance through

the PTFE membrane.

The hydrogenation of LA was conducted supplying hydrogen from the lower side of the

membrane and from the upper side (in a continuous loop flow). Results have shown that the most

https://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=2&cad=rja&uact=8&ved=0CCkQFjABahUKEwiQtp2xu-rGAhUUMIgKHYtFB_k&url=https%3A%2F%2Fen.wikipedia.org%2Fwiki%2FPolytetrafluoroethylene&ei=s06tVdCQMpTgoASLi53IDw&usg=AFQjCNG70yIkHl_DwAYNFQlFujbXSgLdFA&bvm=bv.98197061,d.cGU


efficient way to supply hydrogen is from below the membrane surface since supplying it from the upper

side resembles a more traditional three-phase reactor such as a packed bed reactor.

Comparing the PTFE layer that was coated with 0.2wt% RuCl3 dissolved in ethanol (catalyst

solution) with the one that consisted of PTFE with a polymeric layer of Matrimid, greater GVL results

were obtained with the one that consisted of unmodified PTFE with catalyst. The presence of a

polymeric layer on the PTFE lowered the GVL yield due to the inefficiency of delivery of hydrogen to

the catalyst sites. An increase in pressure and temperature helped to lessen this effect.


Table of Content Abstract………………………………………………………………………………….…………..1

1. Background………………………………………………………………………….……………4

1.1 Research justification

1.2 Lignocellulose to produce levulinic acid and GVL

1.3 Utilizing membranes as phase contactors for three-phase hydrogenation

1.4 Research objective and goals summarize

2. Research methodology…………………………………………………………………...............10

2.1 Membrane fabrication

2.2 Calibration samples

2.3 Catalyst solution

2.4 GBL and water permeability

2.5Levulinic acid solution

3. Results and discussion……………………………………………………………………………12

4. Conclusion………………………………………………………………………….…………….16

5. Supporting information…………………………………………………………….…………….18

6. References………………………………………………………………………………………..21


1. Background

1.1 Research Justification

The fast growing population, rapid modernization and industrialization have increased the

demand in energy and this demand is mostly met from a non-renewable resource such as fossil fuel. The

dependence on fossil fuel has serious implications in the economy and in the environment. We are

entering an era of diminish availability of petrochemical resources used to produce energy and chemical

materials needed by society [1].

The growing environmental degradation is observed locally, nationwide and globally, and has

attracted the attention and concern in the scientific environment. Policies for reducing energy use may

not ensure the desired level environmental quality along with the desired level of economic growth and

social welfare. The energy sector is dominated by the direct combustion of fuels, a process leading to

large emissions of CO2, making carbon dioxide (CO2) one of the most foremost greenhouse gases in the

atmosphere (Figure 1). CO2 produced by the burning of fossil fuel is of great concern in view of its

impact on global warming, which

concentration in the atmosphere is

increasing at a rate of 0.4% per year [4,

8]. Seeking improvement and developing

an alternative sustainable method of

producing energy is imperative. Abundant

biomass resource are a promising

alternative for the sustainable supply of

energy. Biomass is a renewable carbon

source that can be processed in an

integrated bio-refinery, in a manner

similar to petroleum in conventional refineries, to produce fuels and chemicals [2].

1.2 Lignocellulose to produce levulinic acid and GVL

Lignocellulosic biomass is an alternative renewable source of carbon that has potential to be

converted to a variety of fuels (Figure 2). Two of three components are cellulose which accounts for

Figure 1. Shares of global anthropogenic greenhouse

gas emission [4].


30-50 wt% of lignocellulose biomass and hemicellulose with 15-30 wt%. Cellulose can be converted to

glucose that can be used to produce platform chemicals, such as 5-hydroxumethyl furfural (HMF). HMF

can then be converted to levulinic acid (LA) and then to gamma-valerolactone (GVL). GVL is a

promising renewable platform molecule that can help replace petroleum derived chemicals [10].

HMF can then be converted to LA and then to GVL. GVL has excellent properties as solvent, is a

precursor of high value chemicals, fuels, is

consider a green solvent, plus it’s not

decomposed nor degraded with time and has

high boiling point. A green solvent is said to

be a substance that reduces environmental

hazard and posed less health risks. One of the

criteria that one must take in account when

producing a solvent by means of a chemical

reaction are its intermediates products. For

GVL, starting from cellulose, some of its

intermediate products are glucose, HMF, LA, and

formic acid, which are miscible in water, which facilitate its biodegradability. In addition, GVL can be

used as solvent to produce HMF, LA, and GVL from fructose. One possible pathway to produce GVL

are hydrogenation or dehydration of LA. In this case, we focus on the process of hydrogenation of LA

(figure 3) that produces an intermediate product call gamma-hydroxyvaleric acid, which ring-closes by

intermolecular esterification and loses a H2O molecule to produce GVL. [10]

Figure 3. Levulinic acid transformation to GVL.

Figure 2. Roadmap for the conversion of lignocellulose [11].

4-hydroxypentanoic acid


In order for this reaction to proceed, a catalyst must be used. It’s important to take in account the

nature of the solvent, and the support of the catalyst. Many catalyst have been used to produce GVL, but

the one that achieve the highest yield was Ru-based catalyst [10, 11]. As mentioned before, considering

GVL from the sustainable perspective, GVL is a chemical of great value. This chemical can be used in a

similar manner as ethanol, and can be hydrogenated to produce fuel additives (Figure 4) such as MTHF

with a 93% of selectivity at 98% GVL conversion using Cu catalyst, or 1,4 pentanodiol.

1.3 Utilizing membranes as phase contactors for three-phase hydrogenation

It’s imperative that every chemical reaction is carried out with high selectivity and high

Figure 4. Reaction pathways for the conversion of GVL into fuels, fuel additive and chemicals [10]. Figure 4. Reaction pathways for the conversion of GVL into fuels, fuel additive and chemical [10].


Polymer

Layer Membrane

Cell

conversion towards the desired product. In order for this to happen, we seek our reaction to be selective

towards

Figure 5. Matrimid chemical structure [12].

hydrogen, and that also removes selectively H2O. To accomplish such task, it was proposed the

development of a polymeric membrane based on the polymide polymer Matrimid (Figure 5). The

Matrimid solution was made and poured on a thin layer of polytetrafluoroethylene (PTFE) with pores of

a size of 0.05 micrometers. PTFE serves as the support for the polymer. The PTFE helps the membrane

be selective toward gas and liquid separation, which is one of the properties that we seek in our

membrane to have.

We were seeking to increase the temperature to a range of 120-150oC, since this will help us

increase the rate of reaction. Currently, the only temperature that it could be reached with PTFE layer

coated with catalyst for the hydrogenation reaction was between the range of 70-80oC because the liquid

phase started permeating trough the membrane as the temperature increase, in other words, as the vapor

pressure increased. Figure 6 shows the basic idea of how the membrane would look like inside the

membrane cell. For the three phase reaction of levulinic acid (LA), the liquid side will come in contact

with dense layer of the polymer, and the gas phase will be exposed to the porous side of the membrane.

Liquid Phase

Gas Phase

Porous

side

Polymer layer

PTFE layer

Dense

side

Figure 6. Matrimid membrane inside the membrane cell.

Membrane cell


Different procedure were executed when seeking to produce a more efficient membrane. One of

them, for example, was dissolving the Matrimid polymer in methylene chloride (DCM) solvent and

letting it dry overnight to form a dense layer (Figure 7). DCM solvent was replaced by GBL and since

GBL don’t have the same volatility as DCM, the membrane was put in different bath, which consisted of

water and ethanol. When the membrane was submerge in ethanol, the polymeric layer detached. The

membrane also tended to become wrinkled, and if the catalyst solution was poured, it tended to gain a

rough surface (Figure 8). The best fluid to harden the membrane was water. During the trials, I observed

that when the membrane was submerge in water without the catalyst solution, the desired structure was

obtained (Figure 10), the shiny dense layer. A problem notice when submerging it coated with catalyst

was that the dense layer was lost along with some of the catalyst which was dissolved in water (Figure

9). A possible solution to this problem was to make a mixture of the catalyst solution with the polymer

solution. Throughout the research one of my focused was developing and improving the performance of

such membranes. The only problem developing the desired membrane (with the shiny dense layer) was

the thickness of the polymeric layer which represents a problem when trying to supply hydrogen.

Figure 8. PTFE coated with Matrimid polymer

dissolved in GBL. Membrane soaked with

ethanol. Left membrane was coated with catalyst

solution and the right one only contains the

polymer solution.

Figure 10. PTFE coated with Matrimid polymer dissolved

in GBL. Catalyst solution was mixed with the polymer

solution. Membrane was soaked with water.

Figure 7. PTFE coated with Matrimid polymer

dissolved in DCM. Membrane was left to dry

overnight.

Figure 9. PTFE coated with Matrimid

polymer dissolved in GBL. Catalyst solution

was poured throughout the polymer solution.

Membrane was soaked with water.


The last type of membrane developed consisted of Matrimid dissolved in DCM and instead of

letting the solution dry overnight, it was spin coated into the PTFE (Figure 11). It is important to be able

to detect any degree of defect of the membrane. An imperfection in a membrane can cause a

nonselective convective flow pathways for gases or liquids through the membrane.

1.5 Research objectives summary

Traditional three-phase reactors often present mass transfer limitations, in other words hydrogen

delivery to the catalyst through the liquid phase. Hydrogen availability at the catalytic sites is often the

rate limiting step for hydrogenation reactions, which are industrially relevant in petrochemical and

petroleum refining and in emerging biorefining. Membrane reactors can lessen the mass transfer

limitations by directly and selectively supplying hydrogen to the catalytic sites on the membrane

surface. Therefore, the focus of this research was on developing and improving membranes for the

hydrogenation of LA.

Figure 11. PTFE coated with Matrimid

dissolved in DCM. Spin coater was used to dry

the solution on the surface.

Figure 12. Membrane Reactor Scheme [Image provided by John P. Stanford].


2. Research Methodology

2.1 Membrane Fabrication

Method 1. This type of membrane was made by crushing the pores of the PTFE. Catalyst solution

consisted of 0.2wt% RuCl3 dissolved in ethanol. This solution was poured on top of the membrane and

was then left to hydrogenate for two hours to ensure that the only substance on the surface was Ru.

Method 2. A polymeric solution consisting of 34g Matrimid, 74g THF, 74g GBL and 18g of butanol

was poured on top of the PTFE layer and a casting knife was used to ensure a smooth and even surface.

Then, it was submerge in water until the polymer harden. After the water treatment, a catalyst solution

consisting of 0.2wt% RuCl3 dissolved in ethanol was poured on top and the membrane was

hydrogenated for two hours.

Method 3. Two solutions of Matrimid dissolved in DCM were made. One consisted of 1wt% and the

other of 0.25wt%. They were poured on the PTFE layer and were spin coated at a 2500rpm for 60s. The

amount of 20uL, 50uL and 100uL were poured on the PTFE/Matrimid membrane. Each one of them was

hydrogenated for two hours.

Method 4. This type of membrane was made by preparing a 20wt% solution of Matrimid dissolved in

GBL mixed with a 0.5wt% RuCl3 catalyst solution dissolved in GBL. A casting knife was used to ensure

a smooth, tin and even surface. The membrane was submerge in water until the polymer harden. It was

then coated with 0.2wt% RuCl3 dissolved in ethanol and it was hydrogenated for two hours.

Method 5. This membrane consisted of PTFE coated with the catalyst solution which consisted of

0.2wt% RuCl3 dissolved in ethanol.

2.2 Calibration Samples

GBL calibration sample was prepared by mixing GBL with water. The following approximate

concentration were used: 0.10, 0.25, 0.5, 0.75, 1.0 and 1.5wt%. LA calibration samples were also

prepared by mixing LA with water using the following concentrations: 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0wt

%.


2.3 Catalyst solution

The catalyst solution consisted of 0.2wt% RuCl3 dissolved in ethanol. The other catalyst solution

consisted of 0.5wt% RuCl3 dissolved in GBL.

2.4 GBL and water permeability

GBL and water permeability was tested in the membrane reactor to determine which fluid is

more convenient to use for the reaction. PTFE layer was placed in the membrane cell and was exposed

to the liquid for approximately 12 hours. Different temperature were tested, such as 60o, 70o and 80oC.

2.5 Solvent solutions

2.1g of Levulinic acid was dissolved in 70g of the following solvents: water, GBL and glycerol.

2.6 Levulinic acid hydrogenation reaction procedure

PTFE layer was coated with the catalyst solution (or the PTFE covered with the polymer was

coated with catalyst) and hydrogen was supplied constantly for approximately 2 hours, until the

following reaction was completed:

2RuCl3(s) + 3H2 (g) 6HCl (g) + 2Ru(s)

Once Ru was the only element deposit on the PTFE layer, it was placed on the membrane cell. The

reaction was carried out at 70oC for approximately 22-24 hours. Samples were collected at different

hours in order to fallow the rate of the progress at which GVL was formed. Membranes developed in

methods 1, 2, 3, 4 and 5 were analyzed in the reactor using the same procedure.


3. Results and Discussion

Different types of membranes described in methods 1, 2, and 4 are going to be briefly discussed

but the main focus will be on the one developed in method 3 and 5. The first type of membrane that is

going to be discuss is the one described in method 1. The idea was that this method would allow the

catalyst to have a greater exposure to the liquid face because the crushed pores wouldn’t allow the

catalyst to deeply penetrate the PTFE pores.

The membrane did not yield good

results. A possible cause for this could

have been that the crushed pores

prohibited the gas phase from

penetrating the membrane, therefore,

reaching the catalyst. The second type of

membrane analyzed was the one

described in method 2. This membrane

did not yield good results even though

the membrane layer was made thin as

possible in order to diminish the

difficulty in which the hydrogen

passes through the pores. An

explanation for this result is that the

thickness of polymer on the PTFE diminish the ability in which the hydrogen gas pass through the

membrane.

In order to analyze the most efficient way in which the gas phase can be supply, hydrogen was

supply into the liquid side (upper side) and from under the membrane cell (lower side), as shown in

Figure 13. The membrane used for this analysis is the one described in method 5. Results have shown

that the most efficient way of supplying hydrogen in order to obtain a higher GVL yield was supplying it

from underneath the membrane cell since supplying it from the upper side resemble a packed bed

reactor. This is due to the fact that the liquid phase acts as some sort of boundary, like a membrane,

making it difficult for the H2 to reach the catalyst surface. Figures 14, 15 and 16 illustrate this fact.

Liquid circulation loop

Lower side H2 delivery

Upper side H2 delivery

Membrane Cell

Figure 13. Membrane reactor. When using the upper side valve to

deliver hydrogen, the lower part of the membrane cell is close to

prohibit the liquid phase from permeating the membrane and to let it

circulate in a loop. The lower valve was used to apply hydrogen from

the lower side of the membrane trough the catalyst and into the liquid

phase [Image provided by John P. Stanford].


Based on this, the rest of the analysis were

conducted supplying hydrogen from this side.

The orange dots represent the hydrogen flow

from the upper side of the membrane and the

blue dots represent the hydrogen flow from

underneath the membrane. Another important

point to notice is how the GVL production was

affected by the increase in pressure. Comparing

the blue dots of each graph, an increase in

pressure cause an increase in the GVL yield. For

example, there are 0.2g of GVL at 60psig, 0.07g

approximately at 20psig and 0.012

approximately for 5psig.

The idea behind the development of the

membrane described in method 3 was that the presence of the polymeric layer on the PTFE would help

expose the catalyst to the liquid phase, increasing the GVL yield. The only problem presented again was

the inefficiency in the delivery of hydrogen to the catalyst sites. It can be seen that 0.25wt% PTFE-

Figure 15. LA hydrogenation using water as

solvent. PTFE membrane coated with ruthenium

dissolved in ethanol. Temperature of reaction is

70oC at 20psig. Blue dots represent hydrogen

flowing from below the membrane cell and orange

dots represent the experiment in which hydrogen

was supply into the liquid phase.

Figure 14. LA hydrogenation using water as solvent.

PTFE membrane coated with ruthenium dissolved in

ethanol. Temperature of reaction is 70oC at 5psig. Blue

dots represent hydrogen flowing from below the

membrane cell and orange dots represent the experiment

in which hydrogen was supply into the liquid phase.

Figure 16. LA hydrogenation using water as solvent. PTFE

membrane coated with ruthenium dissolved in ethanol.

Temperature of reaction is 70oC at 60psig. Blue dots

represent hydrogen flowing from below the membrane cell

and orange dots represent the experiment in which hydrogen

was supply into the liquid phase.

0

0.05

0.1

0.15

0.2

0.25

0.3

0 10 20 30

GV

L m

ass

(g

)

Time (hrs)

60psig LA hydrogenation

Membrane

Control

0

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0 10 20 30

GV

L m

ass

(g

)

Time (hrs)

5psig LA Hydrogenation

Membrane

Control

0

0.02

0.04

0.06

0.08

0.1

0.12

0 10 20 30

GV

L m

ass

(g

)

Time (hrs)

20psig Hydrogenation

Membrane

Control


Matrimid membrane produce more GVL than the 1wt% membrane. The less dense the polymer, more

efficiently the hydrogen pass through a membrane at the same temperature and pressure. An increase in

temperature and pressure can diminish this effect. The denser the polymer layer, the slower the reaction.

Different quantities such as 100uL, 50uL and 20uL of catalyst (RuCl3 dissolved in ethanol) were added

to the membrane surface. As expected, the greater the amount of catalyst, the greater the GVL yield.

The optimum temperature in which this

The reaction was run was at 70oC due to the analysis of the water-PTFE permeability. Apart from water,

GBL permeability was also calculated when analyzing which chemical was the optimum to use as

solvent for LA (lower vapor pressure). As expected, GBL showed lower permeance due to its high

boiling temperature compared to water at the following temperatures: 60oC to 70oC and 80oC. Glycerol

permeability was not analyzed.

Figure 17. 100uL of catalyst were used (RuCl3 dissolved in

ethanol). Temperature of reaction was 70oC.

y = 0.0112x

y = 0.0019x

0

0.1

0.2

0.3

0.4

0.5

0.6

0 10 20 30 40 50

GV

L m

ass

(g)

Time (hrs)

PTFE-Matrimid 0.25wt% membrane at 20 psig

y = 0.1883x - 0.5705

R² = 0.8727

-0.5

0

0.5

1

1.5

2

2.5

-2.0 3.0 8.0 13.0

Wate

r (g

)

Time (h)

PTFE Water Permeance at 60C

Figure 19. PTFE water permeance at 60oC.

y = 0.0081x

y = 0.0019x

0

0.05

0.1

0.15

0.2

0 5 10 15 20 25G

VL

mass

(g

)

Time (hrs)

PTFE-Matrimid 1 wt%membrane at 20psig

Figure 18. 100uL of catalyst were used (RuCl3 dissolved

in ethanol). Temperature of reaction was 70oC.


Among the fluids analyzed for the

hydrogenation of LA, the most efficient one to

use was water. The different types of solvents

that were analyze were: glycerol, water and

GBL. Glycerol as solvent was discarded since

after 22h of reaction the presence of GVL was

not detected (using liquid chromatography). The

samples collected using GBL as solvents

analyzed but separating the produced GVL

from the GBL solvent was difficult to

quantitatively do. The fluid obtained from this reaction experienced a physical change, instead of been

transparent like GVL, it turned bronze as shown in Figure 23.

Figure 23. Levulinic acid dissolved in GBL. Liquid

phase after hydrogenation reaction.

y = 0.2009x + 1.0768

R² = 0.9645

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0.0 5.0 10.0 15.0 20.0

Wate

r (g

)

Time (h)

PTFE GBL permeance 80C

y = 0.6742x + 1.3177

R² = 0.9868

0.0

2.0

4.0

6.0

8.0

10.0

0.0 5.0 10.0 15.0

wa

ter

(g)

Time (h)

PTFE water permeance 80C

Graph 22. PTFE GBL permeance at 80oC.

Graph 21. PTFE water permeance at 80oC.

y = 0.2378x + 0.047

R² = 0.9303

0

0.5

1

1.5

2

2.5

3

0.0 2.0 4.0 6.0 8.0 10.0 12.0

Wa

ter

(g)

Time (h)

PTFE water permeance at 70C

Graph 20. PTFE water permeance at 70oC.


4. Conclusion & Future Scope

Conclusion

• The presence of the polymer on the PTFE decrease the yield of GVL because it acted as another

layer, blocking the hydrogen flow.

• The higher the weight percent of the Matrimid solution, less GVL yield, therefore, the slower the

rate of reaction.

• The higher the weight percent of the Matrimid on the PTFE, the greater temperature and pressure

can be reached to diminish its negative effect.

• Membrane reactors compared to packed bed reactors lessen the mass transfer limitations,

providing more efficiently and selectively hydrogen to the catalyst sites.

• A membrane based on PTFE works efficiently for this reaction because of its repulsiveness

towards water, diminishing the ability of the levulinic acid solution from permeating the

membrane as the vapor pressure (caused by an increase in temperature).

• A factor that could have affected the production of GVL throughout time could be that the

increase in vapor pressure from the upper side of the membrane and the pressure supply by the

hydrogen gas from the lower side of the membrane could have compacted the pores. This could

diminish the ability of the hydrogen to pass through the pores.

• The catalyst could have started to decay or it could have been dissolve in the solvent, limiting the

ability of the hydrogen to come in contact with it.

Future Scope

• The permeability of the different weight percent of Matrimid used on the membranes for this

study must be tested at different temperatures to obtain the optimum temperature at which the

reaction can be run.

• The deactivation rate of the catalyst on the PTFE should be analyzed.

• When the membrane is coated with the catalyst solution, the time in which is expose to hydrogen

can be varied. The membrane can be tested in the production of GVL to ensure the optimum time

interval in which hydrogen can be supply before running the reaction.

• Different solvents could be analyze for the catalyst solution to evaluate how GVL production

varied.


• The bronze colored fluid obtained when GBL was used as solvent for levulinic acid must be

more fully analyzed.


5. Supporting Information

Table 1. Hydrogen flow analysis experimental data using PTFE-catalyst membrane.

Table 2. 0.25wt% PTFE-Matrimid membrane using 100uL catalyst solution at 20psig of H2. Catalyst

solution consisted of 0.2wt% RuCl3 dissolved in ethanol.

5psig 20psig 60psig

Time

(hrs)

Membrane Control Time

(hrs)

Membrane Control Time

(hrs)

Membrane Control

0 0.007422 0 0 0.025772 0 0 0.075455 0

2.25 0.010056 3 0.031009 3 0.095622

3.75 0.011117 3.5 0.000409 3.25 0.002634

7.75 0.001151 5 0.035104 4.75 0.107617

9.75 0.001547 6.75 0.003043 6.5 0.010174

12.25 0.001851 10 0.010583 16.5 0.244266

15.25 0.002272 20.5 0.090866 19 0.265356

15.75 0.017909 25 0.110558 20 0.045871

19.75 0.019112 28 0.130726 21.25 0.04846

21.75 0.020633 23.5 0.334254

Expt

Time

(hrs)

H2

Pressure

(psig)

Sample

vol.

(mL)

Cumulative

sample vol.

(mL)

Calc.

retentate

vol.

(mL)

GVL LA GVL

SIM

GVL

wt%

GVL mass

(vol.

corrected)

0 20 0.2 0.2 57.8 1639487 3.69E+08 57068 0.004651 0.00268803

5 20 0.2 0.4 56.62174 25780182 3.71E+08 887814 0.074798 0.04235189

18 20 0.2 0.6 53.87826 1.07E+08 3.5E+08 3559575 0.333736 0.17981116

21 20 0.2 0.8 53.0913 1.24E+08 3.36E+08 4124385 0.392285 0.2082691

23.5 20 0.2 1 52.40217 1.4E+08 3.36E+08 4589704 0.447745 0.23462817

28.5 20 0.2 1.2 51.22391 1.84E+08 3.28E+08 6336612 0.613828 0.31442692

30.25 20 0.2 1.4 50.68152 1.95E+08 3.31E+08 6551528 0.654828 0.33187655

39.75 20 0.2 1.6 48.62283 2.57E+08 2.98E+08 8717831 0.904401 0.43974519

41.75 20 0.2 1.8 48.03152 2.95E+08 2.57E+08 10132196 1.070195 0.51403075

46.5 20 0.2 2 46.90217 3.05E+08 2.79E+08 10276853 1.111365 0.52125423


Table 3. 1wt% PTFE-Matrimid membrane using 100uL catalyst solution at 20psig of H2. Catalyst

solution consisted of 0.2wt% RuCl3 dissolved in ethanol.

Table 4. Water permeance at 60oC. PTFE membrane.

Table 6. Water permeance at 80oC. PTFE membrane. Table 7. GBL permeance at 80oC. PTFE membrane.

Expt

Time

(hrs)

H2

Pressure

(psig)

Sample

vol

(mL)

Cumulative

sample vol.

(mL)

Calc.

retentate

vol.

(mL)

GVL LevA GVL

SIM

GVL

wt%

GVL mass

(vol.

corrected)

0 20 0.2 0.2 57.8 0 363308203 0 0 0

2.25 20 0.2 0.4 57.38049 8035114 354034443 286107 0.0229303 0.013158

4 20 0.2 0.6 57.00976 14534267 350600213 512112 0.0417308 0.023791

8 20 0.2 0.8 56.41951 32205506 370304726 1111393 0.0939954 0.053032

18.5 20 0.2 1 55.19512 88937916 339506565 3057664 0.273114 0.150746

20.5 20 0.2 1.2 54.8 101039858 335138353 3454547 0.313558 0.17183

Time (hrs) Exp. Time (hrs) Water

(g)

10:00am 0.0 0

12:00pm 2.0 0

1:30pm 4.3 0

5:30pm 7.7 1

8:40pm 10.4 1

1:00pm 12.0 2

Time (hrs) Exp. Time (hrs) Water (g)

3:00pm 0 0

4:30pm 1.3 0.6

7:30pm 4.3 0.9

9:00pm 6.0 1.3

11:30pm 8.3 1.8

1:30am 9.3 2.3

2:40am 10.4 2.8

Time (hrs) Exp. Time (hrs) Water (g)

8:30am 0.0 0.0

10:00am 1.3 2.1

11:30am 3.0 3.6

1:00pm 4.3 4.3

2:40pm 6.1 4.9

4:30pm 8.0 7.0

8:30pm 12.0 9.4

Time (hrs) Exp. Time (hrs) Water

(g)

9:00pm 0 0

10:30pm 1.3 1.0

12:00am 3.0 2.0

1:30am 4.3 2.0

11:30am 14.0 4.0

1:00pm 15.3 4.0

Table 5. Water permence at 70oC. PTFE membrane.

memranemembrane.


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