guerbet reaction - anr

Evaluation and Fine-Tuning of the Acid-Base Properties of Heterogeneous Catalysts for

Guerbet Alcohols Synthesis Franck Dumeignil

Unité de Catalyse et de Chimie du Solide - UMR CNRS 8181 Université Lille Nord de France 59655 Villeneuve d’Ascq Cedex – France http://uccs.univ-lille1.fr

ANR SUSTAINABLE CHEMISTRY CONFERENCE

2012

2

Snapshot of the project

Coordinator: UCCS Partners: • Research Laboratories:

– LCS – IRCELYON

• Industry: – ARKEMA

Project labelled by the International cluster: AXELERA

Start date: 01/11/2009 End date: 31/10/2012

Extended to 31/12/2012

ANR Sustainable Chemistry Conference, Lyon 18-19 September 2012

3

Outline

INTRODUCTION

SELECTED CATALYTIC SYSTEMS

STRATEGY

PROBING REACTIONS

GUERBET REACTION, SOME FINDINGS

CONCLUSION


4 ANR Sustainable Chemistry Conference, Lyon 18-19 September 2012

INTRODUCTION SELECTED CATALYTIC SYSTEMS STRATEGY PROBING REACTIONS GUERBET REACTION, SOME FINDINGS CONCLUSION

Basic sites

Pathway of the Guerbet reaction

Redox sites / Dehydrogenation sites (Basic sites)

Hydrogenation sites

Acid sites

GENERAL PRINCIPLE OF THE GUERBET REACTION


Producing long chain alcohols from short chain alcohols

Two target products: n-propanol and iso-butanol

1 ethanol + 1 methanol / 1 n-propanol + 1 methanol

6

Main objectives & challenges


• Synthesis of n-propanol and isobutanol from ethanol and methanol (Design of multifunctional catalysts with acid, base & redox properties, screening of numerous formulations);

• Elaboration of a parallel testing equipment for low cost catalysts screening with a competitive market price compared to existing solutions (Mobilisation of competencies in chemical engineering, electronics, informatics, catalysis…);

• Fine characterization of acid and base properties of catalytic systems, as well as of their redox capabilities (correlation of spectroscopic observations & microcalorimetry results with reactivity of the catalysts).

7

Structure of the project: Workflow


8

Main achievements


• 2 Formulations selected for upscaling (Patent application?)

• Parallel testing equipment for low cost catalysts screening designed and validated (Patent application under progress; Startup creation envisioned)

• New route identified to produce longer chain alcohols [Patent(s) application(s) under consideration]

• New methodologies/technologies developed for fine characterization of acid-base properties

EQUIPEX

10

Catalysts selection: Two strategies


Repositioning Development of Hydrotalcites

Pre-selection of 171 acid and/or basic catalysts extracted

from the Arkema’s catalysts library

Concerted selection with partners of 8 representative catalysts

from Zirconia, Titanium oxide, and Cu-based families

Additional supply of catalysts during the course of the project

(Hydroxyapatite family)

Variation of the Mg/Al ratio

Effect of metal nature (Cu, Co, Ni, Fe, Mn

Introduction of various amounts of Cu

Mg5,5Y0,5Al2CO3(OH)12.4H2O

Mg6-xCuxAl2CO3(OH)12.4H2O

[M2+1-xM3+

x(OH)2][An-x/nH2O]z

Mg6Al2(OH)16CO3.4H2O

Calcination MgO, MgAl2O4, Al2O3

(CuO, CuAl2O4)

12

Progressive integration of results

Advanced IR Spectroscopy


Jigsaw pieces pre-fitting (Punctual correlations)

Puzzle completion (Full integration)

NEXT STEP

Glycerol conversion

Micro-Calorimetry

Advanced IR Spectroscopy

GUERBET REACTION

Characterizations: BET, XRD, NMR…

Isopropanol reaction

Test reactions

Advanced Charact.

ETC…

14

Two reactions to probe catalysts properties

Isopropanol reaction


Glycerol conversion

- Development of a refined methodology based on DoE - Still under interpretation to correlate with Guerbet reaction

Probing functionalities / Finding a discriminating criterion?

Determining the Acid/Base ratio using the Acrolein/Acetol ratio?

Glycerol reactivity vs. Microcalorimetry (1)

15

Confrontation of the microcalorimetry results with glycerol reaction tests (recently, integration of IR spectroscopy results)


• Line made up of 2 parts :

Calorimeter Heat quantity

Volumetric line Adsorbed gas quantity

C80

Volumetric

line

Ammonia (pKa = 9.24)

Glycerol reactivity vs. Microcalorimetry (2) Probing of 2 different series of ‘on-shelves’ industrial catalysts (from Arkema’s library)

Probing & titration of acid sites

Probes (experiments performed at 423 K)

Probing & titration of basic sites

Sulfur dioxide (pKa = 1.89)

1. ZrO2-based catalysts

TiO2-based catalysts

CuZn, CuCr

2. Hydroxyapatite-based


Ca10(PO4)6(OH)2

17

Sample name Vtotala

(μmol SO2/m2)

Virrevb

(μmol SO2/m2)

Vtotala

(μmol NH3/m2)

Virrevb

(μmol NH3/m2)

ZrO2 (C740) 3.93 3.59 1.99 1.05

ZrO2 + 10%WO3 (CO)

0.37 0.26 2.52 1.54

ZrO2 + 10%WO3 + 4% HPW

0.13 0.09 2.73 1.41

ZrO2 + 25.75% CeO2 (C700)

4.19 3.78 1.66 0.72

ZrO2 + 30.13% La2O3 (C660)

3.53 3.22 1.05 0.43

TiO2 anatase (C4000)

0.69 0.43 3.26 2.03

TiO2 rutile (C4001)

1.89 1.73 7.59 4.37

HPW TiO2 (C139)

0.20 0.15 2.61 1.85

Cu-Zn (C702) 4.6 4.3 Reaction with NH3 at 423 K

Reaction with NH3 at 423 K

Cu-Zr (C701) 3.5 3.4 Reaction with NH3 at 423 K

Reaction with NH3 at 423 K

Notes: a Amount of probe molecule adsorbed under an equilibrium pressure of 0.2 torr (27 Pa). b Amount of irreversibly chemisorbed probe molecule under an equilibrium pressure of 0.2 torr (27 Pa).

Virr and Vtotal calculated from adsorption isotherms of NH3 and SO2 on different materials.

Differential heats of adsorption as a function of surface coverage for adsorption of NH3 and SO2 at 423 K.

The profiles of differential heats vs. uptake of the gas probe are multi-indicative; they provide data concerning the amount, strength, and strength distribution of the active sites.



Results on series 1

0

10

20

30

40

50

60

70

80

0 1 2 3 4

ZrO2 (C740)ZrO2 WO3 (CO)ZrO2 WO3 HPW (JB-09)ZrO2 CeO2 (C700)ZrO2 La2O3(C660)TiO2 anatase (C4000)TiO2 rutile(C4001)TiO2 HPW (C139)Cu-Cr (C701)Cu-Zn (C702)

Sel

ecti

vity

Acr

ole

in (

%)

Vtotal (μmol SO2/m2)18



Correlations observed on series 1 (1)

Number of basic sites vs. Acrolein selectivity

19




V (μmolNH3/m2)/V (μmolSO2/m2) ratio vs. Acrolein selectivity

0

10

20

30

40

50

60

70

80

90

0 5 10 15 20 25

ZrO2 (C740)ZrO2 WO3 (C0)ZrO2 WO3 HPW (JB-09)ZrO2 CeO2 (C700)ZrO2 La2O3 (C660)TiO2 anatase (C4000)TiO2 rutile (C4001)HPW TiO2 (C139)

Vtotal (μmolNH3/m2)/Vtotal (μmolSO2/m2)

Sele

ctiv

ity A

crol

ein

(%)

20



Results on series 2 (1)

Differential heats of adsorption as a function of surface coverage for adsorption of NH3 and SO2 at 423 K.

Sample name Vtotala

(μmol SO2/m2)

Virrevb

(μmol SO2/m2)

Vtotala

(μmol NH3/m2)

Virrevb

(μmol NH3/m2)

1.5 HAP (C705)

0.2 0.1 1.4 0.6

1.66 HAP (C704)

4.6 3.9 3.2 0.6

Ca/HAP (JB-90)

1.1 0.9 1.0 0.3

P/HAP (JB-89)

0.5 0.3 1.8 0.5

W/HAP (JB-91)

1.4 1.1 1.8 0.6

Virr and Vtotal calculated from adsorption isotherms of NH3 and SO2 on different materials.

Notes: a Amount of probe molecule adsorbed under an equilibrium pressure of 0.2 torr (27 Pa). b Amount of irreversibly chemisorbed probe molecule under an equilibrium pressure of 0.2 torr (27 Pa).

SO2 NH3

21




Number of basic sites vs. Acrolein or Acetol selectivity

Vtotal (μmolSO2/m2) Vtotal (μmolSO2/m2)

Acro

lein

sel

ectiv

ity (%

)

Acet

ol s

elec

tivity

(%)

22




V (μmolNH3/m2)/V (μmolSO2/m2) ratio vs. Acrolein or Acetol selectivity

Vtotal (μmolNH3/m2)/Vtotal (μmolSO2/m2) Vtotal (μmolNH3/m2)/Vtotal (μmolSO2/m2)

Acro

lein

sel

ectiv

ity (%

)

Acet

ol s

elec

tivity

(%)

23



Conclusions

Series 1:

The number of basic sites directly affects the selectivity to acrolein. Direct correlations between surface acid-base properties and selectivity to acetol not observed.

Series 2:

The number of basic sites directly affects the selectivity to acrolein and acetol. Increasing the proportion of acid sites gives an increase in acrolein selectivity and a decrease in acetol selectivity.

Difficult to find an ‘Universal’ discriminating criterion... Now integrating the IR spectroscopy results to get further insights

(e.g., by also taking into account the nature of the sites)

24

Glycerol reactivity: Nature of the sites by IR


Development of a new methodology for basic sites based on CO2 adsorption

2D coupling of IR spectra with gravimetric measurement: Quantitative distribution of sites (Lewis and Brønsted type)

Coupling of a microbalance with an IR cell


Acet

ol y

ield

s

Amount of basic sites


Basic sites and acetol yield

Complex relationship between acetol yields and global basicity (amount and strength of carbonate species)

25



Acid sites(pyridine adsorption) and acrolein yield

26

Brønsted

Lewis Acro

lein

yie

lds

Average acid strength

Acro

lein

yie

lds

Lewis acid sites

Highest acrolein selectivities (>70%) systematically found when Brønsted acidity is present (e.g., W-based catalysts)

In the absence of Brønsted acidity, acrolein yield correlates with the number of Lewis acid sites.

28

Catalysts and test conditions


In the followings, we report the results on the series based on Mg6Al2(OH)16CO3.4H2O, varying the Mg/Al ratio

Test conditions

200 mg catalyst + 200 mg SiC (80-100 µm)

10 % C2H5OH, 10 % CH3OH, 79.6 % He, 0.4 % Kr

50 mL/min (GHSV ~ 2500 h-1)

In-house specifically designed parallel test rig

Coupling with pseudo-2D ultra-fast GC-MS

29

Mg/Al=x: Ethanol conversion


200

250

300350

400

0

5

10

15

20

25

Mg/Al=2 Mg/Al=3Mg/Al=4

Mg/Al=5Mg/Al=6

Mg/Al=7

200 250 300 350 400

Ethanol conversion as a function of temperature for the Mg/Al=x series

30

Mg/Al=x: Methanol conversion


200

250

300350

400

0

5

10

15

20

25

Mg/Al=2 Mg/Al=3Mg/Al=4

Mg/Al=5Mg/Al=6

Mg/Al=7

200 250 300 350 400C

onve

rsio

n d

e m

étha

nol(

%)

Methanol conversion as a function of temperature for the Mg/Al=x series

Trend observed for basic sites


Basic sites quantity: Same trend as that of conversion

Reaction over medium strength basic sites

Tota

l num

ber o

f bas

ic s

ites

(μmol/g)

Total number of basic sites on the Mg/Al=x series (microcalorimetry)

Medium strength (100 < Q < 150 kJ.mol-1)

Increase in the number of stronger sites

Presence of intense infra-red bands Atmospheric CO2 strongly adsorbed

Selectivity (1)


Selectivity at iso-ethanol conversion (12 %; 10 % for methanol)

Presence of a lot of ‘other’

products (between 40 and 80 %)

Formation of Guerbet alcohols

on catalysts exhibiting both

dehydrogenation products

(acetaldehyde formation; basic

sites) and intermolecular

dehydration products (acid

sites)

Formation of 1-butanol and 1-

propanol (no isobutanol)

Selectivity (2)


Nature of ‘other’ products

Before Catalytic Test EtOH+MeOH

After Catalytic Test

Selectivity (3)

34

Selectivity at 400°C

For Mg/Al= 2 and 3, almost no

‘other products’ but not strong

coupling of dehydrogenation

and acid functions

More Guerbet alcohols for

Mg/Al= 2 and 3

Mg/Al=3 selected for Cu-doping


35

Insights in the reaction mechanism


Development of a dedicated IR Operando bench (ethanol)

• Working conditions:

– T 100 – 400°C – PEtOH = 0 – 0.2 bar – WHSV = 0 – 10-4 s-1

• IR analysis of the surface

• IR, GC & MS analysis of the products

• Poisoning experiments

36

Insights in the reaction mechanism


Typical Operando results (ZrO2 / Ethanol)

0 2 4 6 8 10 120

5

10

15

20

EtOH convesrion

EtO

H Co

nver

sion

(%)

Time (h)

5% EtOH 5% EtOH, preads. CO2 5% EtOH + 5% CO2

0 2 4 6 8 10 120

1

2

3

4

5

6 5% EtOH 5% EtOH, preads. CO2 5% EtOH, +5% EtOH CO2

Acet

alde

hyde

yie

ld (%

)

Time (h)

0 2 4 6 8 10 120,0

0,1

0,21-Butanol

5% EtOH 5% EtOH, preads. CO2 5% EtOH, +5% EtOH CO2

1-Bu

tano

l yie

ld (%

)

Time (h)

Acetaldehyde

1700 1600 1500 1400 1300 1200 1100 1000

1545

104710951143

142614421534

45 min - 7 h

5 - 15 min

Wavenumber (cm-1)

1 s - 3 min

Tim

e on

stre

am

C=O

C-O

Continuous deactivation: Surface transformation of ethoxy groups to carboxylates

Interpretation of results over other catalytic systems is ongoing…

ANR Sustainable Chemistry Conference, Lyon 18-19 September 2012 38

Conclusion

A complex reaction with many products Difficult to ‘stop’ the reaction; progression of cascade reactions (multi-

iterations of the Guerbet reaction and ‘parasite’ reactions (over multifunctional catalysts)

New methodologies developed to characterize the acid-base versatility

of catalysts Development of a new parallel testing equipment Some efficient catalysts were identified: patents under

consideration/writing (but cannot be disclosed at this stage) Now necessary to integrate the complete set of results from all the

different & complementary techniques (on-going brainstorming)

39

Acknowledgements (1) Thanks to all the project’s participants!


UCCS Prof. Carole LAMONIER Prof. Jean François LAMONIER Prof. Rose-Noëlle VANNIER Prof. Sébastien PAUL Dr. Mickaël CAPRON Dr. Caroline PIROVANO Dr. Alain RIVES Dr. Jérémy Faye Mrs. Fadime HOSOGLU Mr. Jeremy MATON

LCS

Dr. Arnaud TRAVERT Dr. Françoise MAUGÉ Dr. Pawel STELMACHOVSKI Dr. Sergey SIROTIN Mr. Philippe BAZIN Mrs. Valérie RUAUX

IRCELYON

Dr. Aline AUROUX Dr. Simona BENNICI Mr. Dusan STOSIC

ARKEMA

Dr. Jean-Luc DUBOIS Dr. Jean-Luc COUTURIER Dr. Christophe CALAIS Dr. Markus BRANDHORST

40

Acknowledgements (2)

This work is entrusted by the Agence Nationale de la Recherche through a

subvention within the contract ANR-09-CP2D-19

THANK YOU VERY MUCH FOR YOUR KIND ATTENTION !


ANNEXES



A.K. Kinage et al., Catal. Commun., 11 (2010) 620-623

Glycerol reactivity over acid and basic sites

OHHO

OH OH

+ OHHO

OH2 O

+

OHHO

-H3O

OH

-H2OOHO

-H2O

O

acrolein

Bronsted-siteglycerol

a

b

OHHO

OH+

Lewis-siteglycerol

MO

M

MO

M

OH

OHHO

HOH

OH+

M M

OH OH

HO

acetolLewis-site

MO

M

-H2O

O

pseudo-

Bronsted-site

Bronsted-site

A. Alhanash et al., Appl. Catal. A, 378 (2010) 11–18


Glycerol reactivity over Lewis and Bronsted acid sites

44

Calorimeter

Calibration volume

Vacuum measurement

Measure cell

Reference cell

Trap

Trap

Turbo pump

Oven


Adsorption calorimetry line

45 ANR Sustainable Chemistry Conference, Lyon 18-19 September 2012 45

Calorimetry principle (1)

t

Sign

al

P

Q

t

Sign

al

P

Q

Recorded data for each dose of probe molecule:

pressure

Differential heat As a function of time

46 ANR Sustainable Chemistry Conference, Lyon 18-19 September 2012 46

NH3 irreversibly chemisorbed – desorption under vacuum at 423 K

(at P~0.2 torr) – second NH3 adsorption at 423 K

{ Active site

Calorimetry principle (2)

47

1,3-butadiène formation (1)



1,3-butadiène formation (2)

- H2OH

O

OH

H

O

+H2 H

OHH

- H2O

H

H

B-


Carbon footprint Carbon footprint (from cradle to gate) estimated with Bilan Carbone® method

Products Current “oxo”

technology

Alternative bio-based

technology

n-butanol + 2.2 eqCO2/kg Guerbet

- 0.1 eqCO2/kg

isobutanol + 2.2 eqCO2/kg Corn fermentation + 0.4 eqCO2/kg

Even if the assessment has to be refined taking into account the final results of the project (yields in particular), Guerbet technology appears as an efficient route from an environmental point of view compared to the petrochemical-based “oxo” process

Process data extracted from "Biobutanol: The Next Big Biofuel", Topical Report Nexant, Chem Systems, Feb. 2008


Glycerol test conditions

Equipment & conditions Gas phase – Fixed bed - T=280°C-350°C (oven temperature) Catalyst=4 ml – Particle sizes=300-500 µm Feed : glycerol 6.3% / water 75% / nitrogen 18.7% (% vol) GHSV = 4400 h-1 (total gas feed in NL/h / catalyst app. vol.) Sampling time=1h30

350°C

20°C

280°C

Gly H2O O2

sampling

90’ 75’ 90’ 60’ 180’

H2O


Surface reactions involved in EtOH conversion

guerbet reaction - anr

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