ZSM zeolite-filled polydimethylsiloxane for 1-butanol/2,3-butanediol separation

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ZSM zeolite-filled polydimethylsiloxane for 1-butanol/2,3-butanediol

separation

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Separation of 1-Butanol/2,3-Butanediol Using

ZSM-5-filled Polydimethylsiloxane Membranes

P. Shao, A. Kumar

24 August 2009

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Introduction

• 2,3-Butanediol, a bio-product

– Hemi-cellulose Glucose 2,3-Butanediol + 2CO

2 + H

2 + 2ATP

• 2,3-Butanediol, an important intermediate

• Industrial solvent:

• Monomers:

R

(MEK)

CH

3

CH

3

H

OH

O

(MEK)

CH

3

CH

3

H

OH

O

CH

3

CH

3

H

OH

(1,3-Butadiene)

(2,3-Butene)

CH

3

CH

3

H

OH

(1,3-Butadiene)

(2,3-Butene)

(4)

Recovery of 2,3-butanediol:

a challenging separation

Challenge analysis in terms of

solubility parameter

• Physicochemical properties

– High affinity for water

– Much bigger molecular size

than water (0.52 nm versus

0.25 nm)

Species

Solubility Parameter (Mpa)

1/2

Water

47.8

0 2,3-Butanediol

33.5

14.3 Challenging

Methanol

29.6

18.2 Challenging

Ethanol

26.5

21.3 Fair

2-Propanol

23.5

24.3 Easy

1-Butanol

23.1

24.7 Easy

• Possible recovery methods

– Distillation

– Vacuum membrane distillation

– Integrated process

(5)

Flowchart of the proposed

integrated process

Fermentator

UF

Extractor

A1

permeate

A2

permeate

1-butanol

reservoir

Permeate with low content of 2, 3-butanediol

A3

permeate

(6)

Solvent selection

criteria

• High partition coefficient

• High selectivity

• Membrane permeability

• Volatility

• Evaporation heat

• Toxicity

• Environmental concerns

• Cost

Candidate solvents

Better Process Economics

Solvents

BP (

o

_C)

Alcohols

1-butanol

117 3-ethyl-3-pentanol

142 2-ethyl-1-butanol

147 1-heptanol

176 2-octanol

180 2-ethyl-1-hexanol

184 1-octanol

195 1-nonanol

213 1-decanol

243 1-dodecanol

259 Esters

dibutyl phthalate

340 tributyl phosphate

289

(7)

Mixed matrix membrane

• Materials

• Polydimethylsiloxane (PDMS)

• ZSM-5 zeolite fillers

n

Si

O

CH

3

CH3

n

Si

O

CH

3

CH3

2. Good interfacial compatibility

1. Dispersion of filler particles

(8)

SEM images

• ZSM-5 loading

– ZSM-5:PDMS= 80w/w%

• Factors contributing

to good dispersion

– Sonicating

– Stronger interactions

– Highly volatile solvent

• Pentane(36

o

_C)

– Increased viscosity of

the dope solution

(9)

Permeability of membranes

with up to 80 % loading

1.0E-08

1.0E-07

1.0E-06

P

erm

ea

bi

li

ty

(c

m

2 /s

)

of t

he

fi

ll

ed

P

D

M

S

2,3-butanediol

1-butanol

1-Butanol in feed: 45 w/w%

(10)

Selectivity versus ZSM-5

loading

3-Dimentional

mass transport

0

5

10

15

20

25

30

40

50

60

70

80

90

100 S

el

ec

ti

vi

ty

of

the

fi

ll

ed

m

em

bra

ne

1-Butanol content (wt. %) in feed

ZSM-5

loading:

80 %

40 %

20 %

(11)

Enhanced product

recovery

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

2 ,3

-B

u

ta

n

ed

io

l

p

u

ri

ty

PDMS with 80% ZSM-5 loading

PDMS

42% 64%

Objective purity

(99.5w/w%)

(12)

Impact of ethanol as a

by-product

Selectivity Permeability

1.0E -09 1.0E -08 1.0E -07 1.0E -06 30 40 50 60 70 80 90 100 M em br an e p er m ea bi lit y (c m 2/ s)

Feed concentration of 1 -butanol (wt.%)

ethanol

1-butanol

2,3-butanediol

1 10 100 0 10 20 30 40 50 60 70 80 90 100

without ethanol

with 0.92 wt.% ethanol

Feed concentration of 1 -butanol (wt.%)

M em br an e s el ec tiv ity fo r 1 -b ut an ol o ve r 2 , 3 -b ut an ed io l

(13)

2,3-Butanediol content

in permeate

0.010

0.100

1.000 M

as

s fra

ct

ion

of 2,3

-but

ane

di

ol

i

n

pe

rm

ea

te

Permeate

(83 w/w%)

3 w/w%

(14)

Permeate recycling

(1-point)

Product: 7.95 kg/h (99.5%)

A

₃

= 35.9 m

2

A

₁

= 49.1 m

2

ΣA=112.6 m

2

A

₂

=27.6 m

2

Feed: 360 kg/h (3.0%)

Recycled permeate: 26.0 kg/h (7.81%)

Permeate: 352.1 kg/h (0.82%)

Feed: 360 kg/h (3.0%)

ΣA=101.1 m

2

Product: 6.60 kg/h (99.5%)

Permeate solvent: 353.4 kg/h (1.20%)

1-point

(15)

Permeate recycling

(3-point)

20.7 kg/h (4.5%)

3.4 kg/h (14.5%)

1.2 kg/h (50.1%)

Permeate: 352.0 kg/h (0.79%)

Product: 8.00 kg/h (99.5%) (3-point)

Feed: 360 kg/h (3.0%)

A

3

=33.4

m

Permeate I

7.95 kg/h (99.5%)

(

1-point

)

(16)

Permeate recycling and

recovery improvement

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 60 70 80 90 100 110

Puri

ty

of

prod

uc

t 2,

3-but

ane

di

ol

With 1-point recycling

Without

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Specific energy demand

of PV and vacuum MD

20

40

60

80

100

120

140

160 pe

ci

fi

c

ene

rgy

de

m

and

for e

nri

chm

ent

(M

J/

kg)

Memebrane distillation

Pervaporation

Drop for 3-point-recycling

Ref: N. Qureshi, M.M. Meagher, R.W. Hutkins,

Recovery of 2,3-butanediol by vacuum

membrane distillation, Sep. Sci. Technol.

29 (1994) 1733-1748.

(18)

Concluding remarks

• ZSM-5 improved the selectivity of the PDMS

membrane. It appears that the optimal ZSM-5

loading is 80 w/w%.

• Permeate recycling enhanced the recovery of

2,3-butanediol, and 1-point recycling is

sufficient.

• The integrated process is more

energy-efficient than the vacuum membrane

distillation.

• Ethanol as an impurity did not significantly

impact on the membrane performance.

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Acknowledgements

• Experimental technicians

– Linda Layton, and Toll Floyd

• SEM technician:

– Dave Kingston

• Financial support

– Agriculture Biomass Innovation Program(ABIP)

Agriculture and Agri-Food Canada (AAFC).

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Future work

• Membrane distillation for enriching butanediol by direct water

removal using more selective distillation membranes.

– Transport mechanism

– Process performance

• Purification of some other bioproducts using ultrafiltration and

nanofiltration membranes.

– Membrane preparation and characterizations

– Membrane/bioproducts interactions

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