Furfuryl alcohol production by liquid phase catalytic transfer hydrogenation of furfural on alumina as Lewis acid catalyst

Jiménez-Gómez, Carmen Pilar; Cecilia-Buenestado, Juan Antonio; Moreno-Tost, Ramón; Santamaría-González, José; Maireles-Torres, Pedro Jesús

Abstract

Currently, much attention is being paid to the development of efficient and environmentally friendly technologies for the sustainable production of energy, fuels and chemicals [1]. In this context, lignocellulosic biomass appears as a renewable alternative feedstock to fossil resources. Thus, dehydration of C5 carbohydrates leads to furfural (FUR), a versatile platform molecule for the synthesis of a large spectrum of chemicals. Among them, the most important is furfuryl alcohol (FOL), accounting for 65% of FUR production, which finds application in the preparation of resins used as high-quality cores and molds for metal casting, reactive solvent for phenolic resins in the refractory industry, chemical building block for the synthesis of tetrahydrofurfuryl alcohol and pharmaceuticals and manufacture of fragrances [2,3]. FOL is prepared industrially by the catalytic hydrogenation of furfural, which can be carried out in vapor or liquid-phases, being the former in the presence of copper chromite the preferred industrial route. However, other products such as 2-methylfuran, tetrahydrofurfuryl alcohol and 2-methyl tetrahydrofuran can result from furfural hydrogenation, besides furan and THF, different pentanediols, 2-pentanone and 2-pentanol, cyclopentanone and cyclopentanol. The selectivity pattern depends strongly on reaction conditions and on the nature of the catalyst used. Nevertheless, a synthetic approach based on the catalytic transfer hydrogenation (CTH), based on the Meerwein-Ponndorf-Verley (MPV) reduction of an aldehyde (or ketone) coupled to the oxidation of a secondary alcohol, has been also proposed, which does not require supply of external hydrogen and the alcohol can be chosen in order to produce an aldehyde or ketone with industrial applications [4,5]. The present contribution deals with the production of FOL from furfural by CTH, using different commercial aluminas as catalysts and a secondary alcohol as hydrogen donor, in liquid phase. The results have demonstrated that the formation of other by-products is minimized and FOL is produced in high yield, at temperatures ranging between 90 and 150ºC, by using 2-propanol. Thus, full conversion of furfural and a FOL selectivity higher than 90 mol% are attained after only 2 h, at 150ºC, a FUR concentration of 0.25 M in 2-propanol and a catalyst/FUR weight ratio of 1:1 (Fig. 1). A reaction mechanism, involving Lewis acid sites present on the alumina surface in the activation of FUR and 2-propanol, has been put forward. Different experimental parameters (FUR concentration, reaction temperature, catalyst loading, type of alumina and nature of alcohol) have been optimized in order to achieve suitable FOL yields. Moreover, reutilization has been evaluated to support the advantage of the heterogeneous catalytic process which allows the reuse of the solid catalyst. Finally, and considering that dehydration of xylose to furfural is accomplished in the presence of solid acid catalysts, the one-pot synthesis of FOL from xylose has been undertaken by tuning selected experimental variables.

Furfuryl alcohol production by liquid phase catalytic transfer hydrogenation of furfural on alumina as Lewis acid catalyst

Author: Jiménez-Gómez, Carmen Pilar,Cecilia-Buenestado, Juan Antonio,Moreno-Tost, Ramón,Santamaría-González, José,Maireles-Torres, Pedro Jesús

Year: 2017

Source: https://riuma.uma.es/xmlui/bitstream/10630/13724/3/ISGC2017_Mairelesetal.pdf

Fu u yl alcohol p oduc ion by liquid phase ca aly ic ans e hyd ogena ion o
u u al on alumina as Lewis acid ca alys
C.P. Jiménez-Gómez, J.A. Cecilia, R. Mo eno-Tos , J. San ama ía-González,
P.
Mai eles-To es
Uni e sidad de Málaga, Depa amen o de Química Ino gánica, C is alog a ía y
Mine alogía (Unidad Asociada al ICP-CSIC), Facul ad de Ciencias, Campus de
Tea inos, 29071 Málaga, Spain
Keywo ds: biomass; lignocellulose; ca aly ic ans e hyd ogena ion; u u al; u u yl
alcohol; alumina
Cu en ly, much a en ion is being paid o he de elopmen o e icien and
en i onmen ally iendly echnologies o he sus ainable p oduc ion o ene gy, uels
and chemicals [1]. In his con ex , lignocellulosic biomass appea s as a enewable
al e na i e eeds ock o ossil esou ces. Thus, dehyd a ion o C5 ca bohyd a es leads o
u u al (FUR), a e sa ile pla o m molecule o he syn hesis o a la ge spec um o
chemicals. Among hem, he mos impo an is u u yl alcohol (FOL), accoun ing o
65% o FUR p oduc ion, which inds applica ion in he p epa a ion o esins used as
high-quali y co es and molds o me al cas ing, eac i e sol en o phenolic esins in
he e ac o y indus y, chemical building block o he syn hesis o e ahyd o u u yl
alcohol and pha maceu icals and manu ac u e o ag ances [2,3]. FOL is p epa ed
indus ially by he ca aly ic hyd ogena ion o u u al, which can be ca ied ou in apo
o liquid-phases, being he o me in he p esence o coppe ch omi e he p e e ed
indus ial ou e. Howe e , o he p oduc s such as 2-me hyl u an, e ahyd o u u yl
alcohol and 2-me hyl e ahyd o u an can esul om u u al hyd ogena ion, besides
u an and THF, di e en pen anediols, 2-pen anone and 2-pen anol, cyclopen anone and
cyclopen anol. The selec i i y pa e n depends s ongly on eac ion condi ions and on
he na u e o he ca alys used. Ne e heless, a syn he ic app oach based on he ca aly ic
ans e hyd ogena ion (CTH), based on he Mee wein-Ponndo -Ve ley (MPV)
educ ion o an aldehyde (o ke one) coupled o he oxida ion o a seconda y alcohol,
has been also p oposed, which does no equi e supply o ex e nal hyd ogen and he
alcohol can be chosen in o de o p oduce an aldehyde o ke one wi h indus ial
applica ions [4,5].
The p esen con ibu ion deals wi h he p oduc ion o FOL om u u al by CTH, using
di e en comme cial aluminas as ca alys s and a seconda y alcohol as hyd ogen dono ,
in liquid phase. The esul s ha e demons a ed ha he o ma ion o o he by-p oduc s is
minimized and FOL is p oduced in high yield, a empe a u es anging be ween 90 and
150ºC, by using 2-p opanol. Thus, ull con e sion o u u al and a FOL selec i i y
highe han 90 mol% a e a ained a e only 2 h, a 150ºC, a FUR concen a ion o 0.25
M in 2-p opanol and a ca alys /FUR weigh a io o 1:1 (Fig. 1). A eac ion mechanism,
in ol ing Lewis acid si es p esen on he alumina su ace in he ac i a ion o FUR and
2-p opanol, has been pu o wa d. Di e en expe imen al pa ame e s (FUR
concen a ion, eac ion empe a u e, ca alys loading, ype o alumina and na u e o
alcohol) ha e been op imized in o de o achie e sui able FOL yields. Mo eo e ,
eu iliza ion has been e alua ed o suppo he ad an age o he he e ogeneous ca aly ic
p ocess which allows he euse o he solid ca alys . Finally, and conside ing ha
dehyd a ion o xylose o u u al is accomplished in he p esence o solid acid ca alys s,
he one-po syn hesis o FOL om xylose has been unde aken by uning selec ed
expe imen al a iables.
Figu e 1. Kine ic o ca aly ic ans e hyd ogena ion o u u al in he p esence o alumina as a
unc ion o he eac ion empe a u e (Expe imen al condi ions: 0.25 M FUR in 2-p opanol;
ca :FUR weigh a io= 1:1, 100 mg ca alys ) Closed symbols: FUR con e sion, Open symbols:
FOL yield
The au ho s a e g a e ul o inancial suppo om he Spanish Minis y o Economy and
Compe i i eness (CTQ2015-64226-C3-3- R p ojec ), Jun a de Andalucía (P12-RNM-1565), and
FEDER (Eu opean Union) unds.
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