UNIVERSIDADE DA MADEIRA

Departamento de Química
Selective alkoxylation of limonene over
Centro de
Química da
Madeira
commercially available clays
Catrinescu, C ª; Castilho, P. C. ª; Fernandes, C a; Breen, C b
ª Centro de Química da Madeira, Chemistry Dept., Madeira University, Campus Universitário da Penteada, 9000-390, Portugal
b Material Research Institute, Sheffield Hallam University, Pond Street, Sheffield S1 1WB, UK

Introduction Tested Parameters Reaction scheme

Terpinyl alkyl ethers are trendy substances in the Clay Nature: 4 clays - characteristics are presented in + ROH2+
perfumery industry, with odours described as Table 1 and results are described in Figure 1.1.
mango-
mango-like (methyl), citrous (ethyl), fresh grass Ion Exchange: Al, Fe, Ni and Na homoionic clays were
(propyl)
propyl) and woody (butyl). Not found in nature in prepared; see Figure 2 for results ROH2+ ROH

amounts worth extracting, terpinyl alkyl ethers are Acid Activation: clays were treated with HCl at 3 different
usually synthesised through the alkoxylation of concentrations; see Figure 4.
4.
monoterpenes; especially limonene and α-pinene are
monoterpenes; Temperature: reactions performed at 25, 40, 60 and 80º 80ºC
Dresden,, Germany

the most used feedstock molecules1,2 – they are Alcohol / limonene ratio: tested at 1:1 and 2:1. OR
renewable menthane-
menthane-like terpenes available in large Clay / limonene ratio: 100, 200, 300 mg / 0.5 ml limonene
quantities from pine turpentine or as by- by-products Nature of Alcohol:
Alcohol: methanol, ethanol, propanol,
propanol, n-butanol
Green--Sustainable Chemistry , September 10 to 15, 2006 , Dresden

from certain industries (e.g. citrines and paper (Figure 3),

3), isopropanol and t-butanol (no reaction) OR

production). Portugal is an important European Reusability of the catalyst.

producer of turpentine, mainly from two pine
species: Pinus pinaster and Pinus pinea. pinea. The (-(-)- Table 1: Clays used as catalysts for alkoxylation of limonene
limonene content reaches levels of 82% in the
turpentine obtained from the later. Sample Mineralogy Origin CEC Other
OR

Alkoxylation of limonene can be carried out only in S(BET) characteristics

the presence of acidic catalysts. Due to corrosion SAz-1 Ca-Montmorillonite Arizona-USA 1.20 Dioctahedral, Mg-
and environmental drawbacks, almost all the tested 40 rich bentonite
SWy-2 Na-Montmorillonite Wyoming-USA 0.87 Dioctahedral, Al-
catalysts are unacceptable for the industry. The
40 rich bentonite
reaction has been shown to proceed with good yields Sap-Ca Ca-Saponite Ballarat, 0.92 Trioctahedral, Mg-
and good selectivity only over β-zeolites.
zeolites. Califórnia-USA 60 rich saponite
For the present study of limonene alkoxylation,
alkoxylation, we SD Na-Montmorillonite Madeira Arch. – 0.81 Dioctahedral, Al-
used 4 clays of different origin as catalysts. These Portugal 132 rich bentonite
Other secondaray products (polymers, p-cymene, etc.)
clays were modified in order to tailor there catalytic CEC: mequiv / g clay S(BET): m2/ g
capacity to the specific reaction.

Figure 1: Product distribution of alkoxylation reaction over 4 clays Figure 2: Selectivity of alkoxylation over 4 homoionic forms of a clay Figure 3: Reactivity with 4 linear chain alcohols

100 70 100 90
1st International IUPAC Conference on Green

90 90 80
60

80 80
70
Conversion/Selectivity
Limonene conversion
Product distribution

70 50 70
conversion / selectivity %

60
60 Isomers 60
40
Mono-ether
Conversion 50
50 Di-ether 50 Conversion
Selectivity
Others Selectivity
30 40
40 Limonene 40

30 30 30
20

20 20
20
10
10 10
10
0 0 0

0
SAz SWy SapCa SD Al-SAz Fe-SAz Ni-SAz Na-SAz MeOH EtOH PrOH BuOH

Reaction conditions: 200 mg clay, 60º

60ºC, 4h, 1 ml MeOH,
MeOH, 0.5 ml Limonene Reaction conditions: 100 mg clay, 80ºC, 2h, 1 ml MeOH, 0.5 ml Limonene 100 mg clay, 80ºC, 2h, 1 ml alcohol, 0.5 ml Limonene

Figure 4: Limonene conversion over 3 acid treated forms of SAz Results discussion
100 The nature of the clay: Limonene reacts readily with dry Nature of the alcohol: Methanol and n-butanol
90 methanol to yield the corresponding methyl terpinyl ether, as gave high limonene conversion and good
80 the main reaction product (good selectivity for all catalysts). selectivity for the mono-
mono-ether. These decreased
Conversio/Selectivity, %

70
Smaller amounts of 1,8,-1,8,-di-
di-methoxy-
methoxy-p-menthanes, isomeric for ethanol and propanol.
propanol. Water contents in the
60
(terpinolene,, α and γ-terpinene,
terpenes (terpinolene terpinene, isoterpinolene),
isoterpinolene), high alcohol, rather than chain length, may be
50
Conversion molecular-
molecular-weight compounds, p- p-cymene and p-menthenes responsible for these findings. t-BuOH failed
Selectivity have also been identified. There is no isomerisation, completely to react with limonene.
40

disproportionation or polymerization in the first stage of

30
reaction. There is a clear correlation between activity and Alcohol/limonene ratio: Doubling the amount of
20
CEC; Al-
Al-SAz-
SAz-1 was not only the most active but also a alcohol did not bring any improvement: small
10
selective catalyst. increase in limonene conversion with a decrease
0
in selectivity for the mono-
mono-ether.
Al-SAz-1 AA1 AA2 AA3 Ion Exchange: Al3+ and Fe3+-exchanged clays have similar
catalytic activity while Ni2+ and Na+ have very little to no Clay / limonene ratio: Conversion increased as
Reaction conditions: 200 mg clay, 40ºC, 20 h, 1 ml MeOH, 0.5 ml Limonene activity at all. The number of acid sites, rather then their more catalyst was used
strength, is the key factor for the reaction progress. Lewis
sites do not promote alkoxylation of limonene. Al- Al-SAz-
SAz-1 is a Temperature: 40 ºC produced the best results
more effective catalyst for the selective production of terpenyll
ethers than sulphuric acid, HPA, ion- ion-exchange resins and Reusability: Al-
Al-SAz-
SAz-1 was used in a series of
Conclusions most zeolites.
zeolites. consecutive reaction runs, separated by filtration
between experiments. The activity decreased after
We demonstrate that some clays, with their
Acid activation: Increasing the severity of the acid treatment each cycle. However, it was almost completely
acidity properly tuned, can be even better decreases the total number of acid sites with a negative restored after washing the spent catalyst with
catalysts than zeolites for the conversion of impact on the process. Harsh acid treatment increases the acetone and thermal activating at 150º
150ºC.
limonene in terpinyl alkyl ethers. external area, mild acid treatment increases the number of
Besides being environmentally acceptable, acid sites.
clays represent a convenient, low cost and
alternative source to the expensive Aknowledgements References
manufactured zeolite catalysts. Financial support from Fundaç
Fundação de Ciência e Tecnologia (Portugal) and [1] Hensen,
Hensen, K., Mahaim C., Hölderich,
lderich, W.F., Appl.
Appl. Catal.
Catal. A: General 149
FEDER (POCTI/CMT/47619/2002) is gratefully acknowledged.
acknowledged. C. (1997) 311-
311-329;
Fernandes is grateful for the financial support provided by the European [2] W.F. Hölderich and D. Heinz Catal.
Catal. 14 (1999) 149 ;
Social Fund under PRODEP Grant Nr. Nr. 05.03/MD/00276.017/03.
05.03/MD/00276.017/03. [3] Stancilescu,
Stancilescu, M., Ikura,
Ikura, M., J. Anal. Appl.
Appl. Pyrolysis 74 (2006) 217-
217-225.