Fatty Acids esterification with ethanol and heavy alcohols ...web.abo.fi/projekt/poke/Saarenmaa/Fatty Acids esterification with... · alcohols using layered zinc carboxylates –

Fatty Acids esterification with ethanol and heavy alcohols using layered zinc carboxylates – Kinetics Modeling and Process Evaluation.

Doctoral Student: Eduardo Paiva Brazilian Advisor: Prof. Fernando Wypych Finnish Advisor: Prof. Tapio Salmi Universidade Federal do Paraná / Åbo Akademy

Introduction

World Energy Matrix (WEM) (MME, 2009)

Feature: Except hydraulics, geothermal and nuclear, all other sources of energy are limitated.

Mundo ainda depende do Petróleo

Carvão Mineral

26%

Gás 21%Biomassa

10%Nuclear

6%

Pertóleo

34%

Outros

Renováveis

1%

Hidráulica

2%

01

Coal Petroleum

Others renewable

Nuclear Hydraulics

Biomass Gas

Introduction

WEM enhancing and fine chemicals obtainment through catalytic esterification of biomass

Advantages: reuse and recovery of catalyst, shortening of process steps and reduction of energy consumption.

Some research in the field:

Zeolites (KARMEE e CHADHA, 2005);

02

Inorganic oxides (MACEDO et. al, 2006; GONÇALVES et. al, 2010 )

Ion exchange resins (NI e MEUNIER, 2007);

Sulfonated carbohydrates (LOU et. al, 2008);

Metallic soaps (CORDEIRO, et. al, 2008, LISBOA, 2012);

Introduction

Metallic Carboxylates

Group results review: Cordeiro (2008) employing Layred Double Hidroxides (LDH) and Lisboa (2012) with different metal carboxylates.

97.4 % methyl esters conversion (molar ratio 4:1 methanol to oil, at 140 ºC, 4% wt. catalyst and 2 h of esterification)

03

Co-product glycerol with assay around 93% (transesterification)

“in situ” transformation layered double hidroxides into zinc laurate (DRX, FTIR)

Catalyst reuse up to 11 cycles without loosing the activity.

20% of equilibrium conversion gain compared to blank experiment (140 ºC, 2h, manganese laurate in the esterification)

Introduction

Precursors – Lamellar compounds (HDLs)

04

Figure 1. Cooper Hydroxide nitrate structure (a) (Cu2(OH)3NO3) and (b) Zinc hydroxide nitrate (Zn5(OH)8(NO3)2.2H2O). i) side view and ii) top view (layer) (ARIZAGA; GUNDAPPA; WYPYCH, 2007)

Introduction

Metallic Carboxylates (Lewis acid catalysts)

05

Figure 2. Zinc octanoate structure (LISBOA et. al, 2012).

06

Introduction

Reaction medium visualized by a pressure cell T150 9bar in the laboratory of high pressure and thermodynamics in Brazil

Objectives

Esterification kinetics evaluation and modeling of main saturated and unsaturated free fatty acids with ethanol and heavier alcohols;

Catalyst recovering and leaching evaluation;

To study the catalyst surfactant influence on the reaction medium;

To provide thermodynamic data concerning the esterification reactions with ethanol and heavy alcohols.

07

The main objective is the enhancement of alkyl esters production using metallic carboxylates and raw materials with high FFA content and water.

Specific Objectives

Development Strategy

Raw Material

08

Lauric acid (C12:0) – Babassu oil (64% C12)

Commercial mix with oleic (92%), linoleic (4.5%), stearic (2.5%) (C18:1, C18:2 and C18:0, respectively)

Anhydrous ethanol (99,8%)

Hydrated ethanol (93 - 95%)

Characterization

Methods

09

The analysis of all components was performed by GC in a suitable column for fatty acids and esters (60 m with polar mobile phase). The calibration was made based on the Internal Standard method proposed by Konstatine Sychev (1998).

Esterification of 4 fatty acids (FA) (90% oleic mix Sigma) was performed in excess of ethanol, n-butanol and n-hexanol (molar ratios of 3,8 and 12 related to FA), 3 temperatures and 2 different amount of catalyst.

A summation of 41 experiments with 7 kinetics points was generated.

MR Reactor Temp. Cat.

alcohol:FA fraction Celsius %

1:3 0.51 135 0.70

1:8 0.48 150 5.00

1:12 0.48 165 -

Table 1. Summary of the conditions employed in the kinetic experiments.

Konstantine Sychev available at: http://www.rasxodniki.ru/jurnal/arhiv/32

Experimental results - Ethanol

Excess of ethanol and catalyst amount influence

10 0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

Ethanolisys Oleic Acid 135 5.0%

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12

0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Ethanolisys Oleic Acid 135 0.7%

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12

OA – Oleic acid (92% of the mix)

EtOH.O – Ethyl oleate

MR [molar ratio acid:ethanol]

135 ̊C



11 0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Ethanolysis Oleic Acid 150 5.0%

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12

0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12




150 ̊C



12 0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12

0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR8

Ac. MR12

EE. MR3

EE. MR8

EE. MR12




165 ̊C


Temperature influence and conversion

13 0 50 100 150 200 250

0

10

20

30

40

50

60

70

80

90

100Ethanolysis Fatty Acids 165 MR8 ZnL5%

Time [min]

Co

nve

rsio

n [%

]

Stearic

Oleic

Linoleic

0 50 100 150 200 250-20

-10

0

10

20

30

40

50

60

70Ethanolysis Fatty Acids 150 MR8 ZnL5%

Time [min]

Co

nve

rsio

n [%

]

Stearic

Oleic

Linoleic


Reproducibility

14

0 200 400 600 800 1000 1200 1400 16000

0.5

1

1.5

2

2.5

3

3.5

4x 10

-3 Ethanolysis Stearic Acid 150 RM12 0.7%ZnL

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

acids

esters

0 200 400 600 800 1000 1200 1400 16000

0.02

0.04

0.06

0.08

0.1

0.12Ethanolysis Oleic Acid 150 RM12 0.7%ZnL

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

acids

esters


15

Zinc Laurate vs Zinc Stearate

0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Ethanolysis Oleic Acid 165 MR8 5%ZnS

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

blank Ac.

EE. ZnS

blank EE.

0 50 100 150 200 250

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Ethanolysis Oleic Acid 165 MR8 5.0%

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

Ac. ZnL

EE. ZnS

EE. ZnL

Experimental results – (n)butanol

16

Excess of butanol and catalyst amount influence

0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Butanolysis Oleic Acid 135 5%ZnS

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR12

EE. MR3

EE. MR12

0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Butanolysis Oleic Acid 135 MR12

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

blank Ac.

EE. ZnS

blank EE.

135 ̊C


17


0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

blank Ac.

EE. ZnS

blank EE.

0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR12

EE. MR3

EE. MR12

150 ̊C


18


0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

blank Ac.

EE. ZnS

blank EE.

0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16


Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. MR3

Ac. MR12

EE. MR3

EE. MR12

165 ̊C


19

Reproducibility butanolysis

0 200 400 600 800 1000 1200 1400 1600

0

10

20

30

40

50

60

70

80

90

100Butanolysis Oleic Acid 165 RM12 5%ZnS

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Oleic

Stearic

Experimental results – (n)hexanol

20

Comparative plots - Hexanolysis

0 200 400 600 800 1000 1200 1400 1600

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

Hexanolysis Oleic Acid 165 MR12

Time [min]

Co

nce

ntr

atio

n [m

ol/L

]

Ac. ZnS

blank Ac.

EE. ZnS

blank EE.

0 50 100 150 200 250

0

10

20

30

40

50

60

70

80

90

100

Oleic Acid 165 5 Zinc cat.

Time [min]

Co

nve

rsio

n [%

]

Oleic Hexanolysis

Oleic Butanolysis

Oleic Ethanolysis

First results

Proposed kinetics – based mechanism

21

Figure 1. Schematic representation of the zinc octanoate structure and the proposed catalytic mechanism involving layered metal laurates (adaptation from Lisboa et. al, 2012).

2)(

2)(

'

2

)(

21)(2

)(ZnLOHRCOORRCOOHZnLZnLRCOOH

DC

B

catA

The overall kinetics can be simplified to the following scheme and step 2 is assumed to be the rate determining step (RDS) of the reaction:

First results

Proposed kinetics

22

where; vi = 1 and rho = bulk catalyst

Vliq can be considered constant.

cati

i mrdt

dn

Based on pseudo-homogeneous catalysis with no diffusion effects.

EWEA

c

WEBA

CCCC

KCC

CCk

r

1

''

cat

AAAAA

c

AAAA

A

CCCCC

KCC

CaCk

dt

dC

0

2

0

2

00

2

1

''

Ethanolysis modeling

23

Based on this first approach:

A

c

WEBA

C

KCC

CCk

r

1

''

0 500 1000 1500 20000

0.05

0.1

0.15

0.2

data set 1

0 500 1000 1500 20000

0.05

0.1

0.15

0.2

data set 2

0 500 1000 1500 20000

0.05

0.1

0.15

0.2

data set 3

datafile(1) = 150C MR 3 5% ZnL datafile(2) = 150C MR8 5% ZnL datafile(3) = 165C MR3 5% ZnL

Oleic Acid – Main compound (92%)


24

datafile(1) = 150C MR 3 5% ZnL datafile(2) = 150C MR8 5% ZnL datafile(3) = 165C MR3 5% ZnL

Others compounds (8%)

0 500 1000 1500 20000

0.005

0.01

data set 1

0 500 1000 1500 20000

2

4

6

8x 10

-3 data set 2

0 500 1000 1500 20000

0.005

0.01

data set 3


25

Statistics first results - Modest

0 200 400 600 800 1000 1200 1400 16000

0.02

0.04

0.06

0.08

0.1

0.12

0.14

data set 1

0 200 400 600 800 1000 1200 1400 16000

1

2

3

4

5

6

7

8x 10

-3 data set 1

Dataset:135C MR3 0.7% ZnL Total SS (corrected for means): 0.8600E-01 Residual SS: 0.2288E-03 Std. Error of estimate:0.1747E-02 Explained (%): 99.73

First results

Next steps

26

As supported by the results its clearly that the catalyst fatty acid matrix (lauric acid) is being exchanged by other types available on the reaction.

Continue experiments with hexanol (next matrix)

Open the catalyst to investigate the acids profile and establish rate exchanging of FA. Seems that stearic is most preferable from a entropic point of view.

Use the blanks reactions to survey thermodynamic data.

Improve model.

Publications:

I. DE PAIVA, EDUARDO JOSE MENDES ; GRAESER, VALERIA ; WYPYCH, FERNANDO ; CORAZZA, MARCOS L. . Kinetics of non-catalytic and ZnL2-catalyzed esterification of lauric acid with ethanol. Fuel (Guildford), v. 117, p. 125-132, 2014.

II. ZATTA, L. ; DE PAIVA, EDUARDO JOSE MENDES ; CORAZZA, MARCOS L. ; WYPYCH, FERNANDO . The use of acid activated montmorillonite as a solid catalyst for the production of fatty acid methyl esters. Energy & Fuels (Online), 2015.

First results

Acknowledgments

27

Thank you for your

attention!

Results

Catalyst Characterization

Figure 3 . X-Ray powder diffraction patterns of the layered zinc laurate.

5 10 15 20 25 30 35 40

0

5000

10000

15000

20000

25000

30000

35000

2 = 18,06°

d = 29,47 A

n = 62 = 6,06°

d = 29,17 A

n = 2

2 = 3,06°

d = 28,87 A

n = 1

Inte

ns

ity

(c

ps

)

2 (Theta)(Grade)

Results

Catalyst Characterization

Figure 4 . FTIR spectra of the layered zinc laurate.

3500 3000 2500 2000 1500 1000 500

30

40

50

60

70

80

90

100

110

120

130Zinc laurate

Fingerprint (all trans)

M

O445

sC

OO

-

1398

s C

H2

1463

2847

2916

Tra

nsm

ita

ncy (

%)

Wave Number (cm-1)

Raw material composition

Raw material characterization

02

Main Comp. code Resp. Area %

Palmitic Acid C16:0 15.30 0.77

Stearic Acid C18:0 45.80 2.30

Oleic Acid C18:1 1835.90 92.08

Linoleic Acid C18:2 86.60 4.34

others 10.20 0.51

1993.90

Table 2. Oleic acid - technical grade (Aldrich) characterization by GC

Recovering of the catalyst after several washings with acetone.

Parallel results

Exp. 14 purged mass(g)

t(min) mass(g) estim. recov.

0 0,028 0,269 0,272

20 0,026

40 0,023

60 0,022

90 0,023

120 0,022

150 0,026

210 0,027

Average 0,025

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Fatty Acids esterification with ethanol and heavy alcohols ...web.abo.fi/projekt/poke/Saarenmaa/Fatty Acids esterification with... · alcohols using layered zinc carboxylates –