2nd Six monthly PhD progress Seminar

on
Reactive Extraction of
Levulinic Acid
Presented By

Anuj Kumar
DT18CME070

Under the Guidance of

Dr. D. Z. Shende
Dr. K. L. Wasewar

Department of Chemical Engineering

 Physical Extraction
Completed Credit
Literature Survey using various
and Audit course
solvents

First 6 Months

2019
Second 6 Months

Reactive extraction
Studies on various
Literature Survey using various
extractants
solvents
December 23, 2019 2
https://www.un.org/en/sections/issues-depth/population/index.html December 23, 2019 3
Why Levulinic Acid

December 23, 2019 4

Importance of
levulinic acid

December 23, 2019 5

 Renewable Resources of
Levulinic Acid

Wheat Straw Rice Straw

Grass Rice Husk

December 23, 2019 6

Bagasse Corn straw
Levulinic acid production on
industrial scale
 Agriculture waste residue at
temperatures nearby 160℃,
the protons of the acidic
medium attack on cellulosic
glycosidic bonds, then,
producing glucose.
 Glucose monomers converted
into 5-hydroxymethylfurfural
(5-HMF).
 5-HMF is rehydrate,
generating levulinic acid with
formic acid.

December 23, 2019 7

 Various methods of separation

Distillation Evaporation Liquid-Liquid

Extraction

Reverse Chromatograp
Adsorption
Osmosis -hic

Reactive Extraction

December 23, 2019 8

 Reactive Extraction

O A reactive extraction system usually consists of a liquid ion

exchanger diluted in solvent. The latter is used to adjust
rheological or physico-chemical properties, since most of the
ion exchangers are highly viscous or even solid.

(4)

December 23, 2019 9

 Objectives

O To study the separation of levulinic acid from aqueous stream.

O To understand the physical and chemical aspects of reactive extraction of

levulinic acid.

O To understand the effects of the following parameters :

a) Distribution coefficient (𝐾𝐷 )

b) Extraction efficiency (E)

c) pH effect

d) Studies of various extractant behaviour at different concentration

December 23, 2019 10

 Materials
Reagent Supplier Essay% Molecula IUPAC Mol. wt. Viscosity Density/g.c
name r name /cP at m-3
formula 25℃
Levulinic SIGMA- 98 C5H8O3 4- 116.12 - 1.14
acid ALDRICH oxopentano
ic acid
Mustard oil Patanjali - - mixture of - - 0.9
Ayurved fatty acid
Ltd. India
Rice bran Cargill - - mixture of - - 0.91
oil India Pvt. fatty acid
Ltd. India
1-Octanol Merck 99 C8H18O Octan-1-ol 130.231 7.36 0.83
specilities
Pvt. Ltd.
1-Decanol Merck 99 C10H22O Decan-1-ol 158.28 12.04 0.8297
specilities
Pvt. Ltd.
Tri-n- Spectroche 99 C12H27O4P Tri-n- 266.32 0.975
butylphosp m Pvt. Ltd. butylphosp
hate (TBP) Mumbai. hate (TBP)
(India)
Trioctylam Spectroche 95 C24H51N Tricapryla 353.68 7.862 0.8
ine (TOA) m Pvt. Ltd. mine
Mumbai.
(India)
Aqueous phase Organic phase
(10 ml) 10 ml Experimental Method

Shaking Centrifuge
Sample Prepare
(5 h @ 25℃) (5 min @ 4000 rpm)

Calculate
𝑲𝑫 𝒂𝒏𝒅 %𝑬

Titration
(0.1 N NaOH) Separate aqueous
Phase
 Result and Discussion

Separation of levulinic acid using various pure solvent

[LA]Cin pH Mustard oil Rice bran oil TBP
(Mol.L-1) (%E) (%E) (%E)
0.1 3.02 0.00 2.50 67.00
0.3 2.74 1.67 4.17 70.00
0.5 2.67 2.50 7.50 69.20
0.7 2.57 4.65 7.86 64.29
1.0 2.50 11.75 8.00 64.80

pH effect on separation

pH vs [LA]Caq
4

3
pH

0
0 0.2 0.4 0.6 0.8 1
[LA]Caq (Mol.L-1)
December 23, 2019 13
 Reactive extraction of levulinic acid with Tri butyl phosphate +
mustard oil:
TBP (%) [LA]in [LA]aq [LA]org KD avg KD %E avg %E

20 0.100 0.086 0.015 0.170 0.279 14.00 21.62

0.300 0.236 0.064 0.270 21.33
0.500 0.389 0.111 0.285 23.57
0.700 0.605 0.095 0.157 24.02
1.000 0.748 0.252 0.336 25.20
40 0.100 0.068 0.033 0.481 0.506 32.00 33.50
0.300 0.191 0.109 0.569 36.33
0.500 0.320 0.181 0.565 36.00
0.700 0.524 0.176 0.335 32.28
1.000 0.691 0.309 0.448 30.90
60 0.100 0.047 0.053 1.116 0.970 53.00 48.90
0.300 0.148 0.152 1.022 54.26
0.500 0.261 0.239 0.916 47.80
0.700 0.428 0.273 0.637 45.24
1.000 0.558 0.442 0.792 44.20
80 0.100 0.038 0.062 1.614 1.485 62.00 59.52
0.300 0.124 0.176 1.424 63.33
0.500 0.199 0.301 1.507 60.20
0.700 0.336 0.364 1.081 57.07
0.100 0.086 0.015 1.222 55.00
December 23, 2019 14
 Separation of levulinic acid using TBP with mustard oil at
298.15 ± K.

Mustard Oil
0.7
0% TBP
0.6 20% TBP

0.5 40% TBP

[LA]Corg(Mol.L-1)

60% TBP
0.4 80% TBP

0.3 100% TBP

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
[LA]Caq(Mol.L-1)

December 23, 2019 15

Reactive extraction of levulinic acid with Tri butyl phosphate + rice
bran oil:

TBP (%) [LA]in [LA]aq [LA]org KD avg KD %E avg %E

20 0.100 0.079 0.021 0.260 0.254 21.00 20.07

0.300 0.240 0.060 0.248 25.16
0.500 0.400 0.100 0.250 22.66
0.700 0.664 0.036 0.054 17.22
1.000 0.857 0.143 0.167 14.30
40 0.100 0.060 0.040 0.658 0.574 40.00 36.13
0.300 0.210 0.090 0.432 42.54
0.500 0.333 0.167 0.500 35.36
0.700 0.526 0.174 0.330 33.26
1.000 0.705 0.295 0.419 29.50
60 0.100 0.054 0.046 0.853 0.849 46.00 45.89
0.300 0.157 0.143 0.909 47.67
0.500 0.264 0.236 0.892 47.20
0.700 0.426 0.274 0.642 44.60
1.000 0.560 0.440 0.787 44.00
80 0.100 0.041 0.059 1.423 1.291 59.00 56.17
0.300 0.124 0.176 1.423 58.67
0.500 0.212 0.288 1.360 57.60
0.700 0.350 0.350 1.000 52.86
0.100 0.417 0.583 1.400 52.71
December 23, 2019 16
 Separation of levulinic acid using TBP with rice bran oil at
298.15 ± K.

Rice bran Oil

0.7
0% TBP
0.6 20% TBP

0.5 40% TBP

[LA]Corg (Mol/L-1)

60% TBP
0.4 80% TBP

0.3 100% TBP

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
[LA]Caq (Mol/L-1)

December 23, 2019 17

Reactive extraction of levulinic acid with TOA, TBA and TBP+ 1-octanol:

Extractant (%) [LA]in [LA]aq [LA]org KD avg KD %E avg %E

TOA 20 0.5 0.134 0.366 2.734 2.24 73.22 60.27

40 0.5 0.100 0.400 4.000 80.00
60 0.5 0.131 0.369 2.819 73.81
80 0.5 0.200 0.300 1.500 60.00
100 0.5 0.429 0.071 0.167 14.29
TBA 20 0.5 0.345 0.155 0.448 0.318 30.96 23.72
40 0.5 0.357 0.143 0.400 28.58
60 0.5 0.383 0.117 0.304 23.34
80 0.5 0.405 0.095 0.235 19.05
100 0.5 0.417 0.083 0.200 16.67
TBP 20 0.5 0.392 0.108 0.277 0.867 21.70 42.37
40 0.5 0.331 0.169 0.511 33.82
60 0.5 0.301 0.199 0.663 39.85
80 0.5 0.238 0.262 1.100 52.39
100 0.5 0.180 0.320 1.784 64.08
December 23, 2019 18
 Separation of levulinic acid using TOA with 1-octanol at
298.15 ± K.

0.450
20% TOA
0.400
40% TOA
0.350
60% TOA
0.300 80% TOA
[LA]org (mol/l)

0.250 100% TOA

0.200

0.150

0.100

0.050

0.000
0.000 0.100 0.200 0.300 0.400 0.500
[LA]aq (mol/l)

December 23, 2019 19

 Separation of levulinic acid using TBA with 1-octanol at
298.15 ± K.

0.180
20% TBA
0.160
40% TBA
0.140 60% TBA
0.120 80% TBA
[LA]org (mol/l)

100% TBA
0.100

0.080

0.060

0.040

0.020

0.000
0.000 0.100 0.200 0.300 0.400 0.500
[LA]aq (mol/l)

December 23, 2019 20

 Separation of levulinic acid using TBP with 1-octanol at
298.15 ± K.

0.350
20% TBP
0.300 40% TBP
60% TBP
0.250
80% TBP
[LA]org (mol/l)

0.200 100% TBP

0.150

0.100

0.050

0.000
0.000 0.100 0.200 0.300 0.400 0.500
[LA]aq (mol/l)

December 23, 2019 21

Reactive extraction of levulinic acid with Aliquate and TOA+ 1-decanol:
Extractant (%) [LA]in [LA]aq [LA]org KD avg KD %E avg %E

Aliquate 20 0.5 0.386 0.114 0.296 0.979 22.81 44.21

40 0.5 0.356 0.144 0.406 28.86
60 0.5 0.274 0.226 0.826 45.23
80 0.5 0.215 0.285 1.330 57.08
100 0.5 0.165 0.335 2.039 67.09
TOA 20 0.1 0.019 0.081 4.376 3.265 81.40 64.66
40 0.1 0.014 0.086 6.168 86.05
60 0.1 0.021 0.079 3.779 79.08
80 0.1 0.035 0.065 1.867 65.13
100 0.1 0.088 0.012 0.132 11.65
TOA 40 0.001 0.0005 0.0005 0.864 4.582 46.35 61.93
40 0.005 0.0007 0.0043 5.882 85.47
40 0.01 0.0012 0.0088 7.333 88
40 0.05 0.0051 0.0449 8.831 89.83

December 23, 2019 22

 Separation of levulinic acid using aliquate with 1-decanol at
298.15 ± K.

0.4
20% Aliquate
0.35 40% Aliquate
60% Aliquate
0.3
80% Aliquate
[LA]org (mol/l)

0.25 100% Aliquate

0.2

0.15

0.1

0.05

0
0 0.1 0.2 0.3 0.4 0.5
[LA]aq (mol/l)

December 23, 2019 23

 Separation of levulinic acid using TOA with 1-decanol at
298.15 ± K.

0.100
20% TOA
0.090
40% TOA
0.080
60% TOA
0.070
80% TOA
[LA]org (mol/l)

0.060 100% TOA

0.050

0.040

0.030

0.020

0.010

0.000
0.000 0.020 0.040 0.060 0.080 0.100
[LA]aq (mol/l)

December 23, 2019 24

 Separation of levulinic acid using 40% TOA with 1-decanol
at 298.15 ± K.

0.0500

0.0450

0.0400

0.0350
[LA]org (mol/l)

0.0300

0.0250

0.0200

0.0150

0.0100

0.0050 40% TOA

0.0000
0 0.001 0.002 0.003 0.004 0.005 0.006
[LA]aq (mol/l)

December 23, 2019 25

 Conclusions

O The edible oils (rice bran oil and mustard) may

be used for the separation of levulinic acid.
O 40% TOA giving higher separation of levulinic
acid at lower concentration compared to TBP
and Aliquate.
O TBP, TOA, TBA and Aliquate can be used in
other solvents for separation of acid.

December 23, 2019 26

 Future Plans

O Separation of levulinic acid using others natural

and chemical solvents.
O Experiment on kinetic study.
O HPLC analysis.
O Experimental study on fermentation process.

December 23, 2019 27

 Conference/Training

O One Week Short Term Training Programme entitled “Current

Environment Challenges & Their Remedies in Science &
Engineering: A Multidisciplinary Approach” (23-28 Sep,
2019) at PIET, Nagpur.
O National Training Programme on “Biogas Technology:
Demonstration and its Implementation” (5th Nov – 8th Nov,
2019) at NIRE Kapurthala (Punjab).
O 2nd International Conference on "Application of Bio
Technology for Industry and Society (ABIS-2016)", 14-16
Nov, 2019 at NIT Jalandhar (Punjab).
O 11th National Conference on Solid State Chemistry and Allied
Areas(NCSCA-2019), 20-21 Dec 2019 at Seth Kesarimal
Porwal College of Arts & Science & Commerce, Kamptee,
Nagpur.
December 23, 2019 28
 Outcomes

O Extractive separation of levulinic acid using natural and

chemical solvents (Submitted 19 Aug 2019)
Manuscript number CDC_2019_312 (Under Review).
O Production of levulinic acid: a promising building block
material for pharmaceutical and food industry: A review
(Submitted in National Conference).
O Production of levulinic acid using agriculture waste
residue: A review (Submitted in International
Conference).
O Reactive Extraction of Levulinic Acid using Tri-n-butyl
phosphate Diluted in Edible Oils (Under writing).
O Separation of levulinic acid affect various extractant;
TOA, TBA, TBP, and Aliquate at different
concentration in aqueous stream (Under writing).
December 23, 2019 29
 References

O Kumaravel, S., Thiripuranthagan, S., Radhakrishnan, R., Erusappan, E., Durai, M.,
Devarajan, A., & Mukannan, A. (2019). Liquid Phase Esterification of Levulinic Acid
into Ethyl Levulinate Over Sulphobenzylated Nanoporous Al-SBA-15 Catalyst. Journal
of nanoscience and nanotechnology, 19(11), 6965-6977.
O United Nations https://www.un.org/en/sections/issues-depth/population/index.htm
O BUSINESS INSIDER https://www.businessinsider.in/excise-duty-in-cigarette-hiked-
tobacco-farmers-in-india-are-struggling-to-make-ends-meet/articleshow/56872791.cms
O Universal Agro Chemical Industries http://universalagri.net/
O Cosmopolitan https://www.cosmopolitan.com/uk/beauty-hair/g14191580/best-skin-care-
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magenta-yellow-black-100-ml-each-bottle-tri-color-combo-pack-
cartridge/p/itmeq8apqzfgxbh7
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O Hardie Polymer https://www.hardiepolymers.com/knowledge/is-solvent-resistance-
predictable/
O Kumar, A., Shende, D. Z., Wasewar, K.L., (2019) Production of levulinic acid using
agriculture waste residue (Unpublished).

December 23, 2019 30

O Morone, A., Apte, M., & Pandey, R. A. (2015). Levulinic acid production from
renewable waste resources: Bottlenecks, potential remedies, advancements and
applications. Renewable and Sustainable Energy Reviews, 51, 548-565.
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Production of Levulinic Acid (LA) from Actual Biomass. Molecules, 24(15),
2760.
O GlobalInfoResearch
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forecast-to-2023_i0166.html (accessed 5 November 2019)
O Uslu, H., İsmail Kırbaşlar, S., & Wasewar, K. L. (2009). Reactive extraction of
levulinic acid by amberlite LA-2 extractant. Journal of Chemical & Engineering
Data, 54(3), 712-718.
O Uslu, H., Bayat, C., Gökmen, S., & Yorulmaz, Y. (2008). Reactive extraction of
formic acid by Amberlite LA-2 extractant. Journal of Chemical & Engineering
Data, 54(1), 48-53.
O Kumar, S., Datta, D. and Babu, B.V., 2011. Differential evolution approach for
reactive extraction of propionic acid using tri-n-butyl phosphate (TBP) in
kerosene and 1-decanol. Materials and Manufacturing Processes, 26(9),
pp.1222-1228.

December 23, 2019 31

O Datta, Dipaloy, Mustafa Esen Marti, Hasan Uslu, and Sushil Kumar. "Extraction
of levulinic acid using tri-n-butyl phosphate and tri-n-octylamine in 1-octanol:
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O Eda, S., Borra, A., Parthasarathy, R., Bankupalli, S., Bhargava, S. and Thella,
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December 23, 2019 32

Thank You
to all

December 23, 2019 33