WO2017013297A1 - Déshydratation de sorbitol en isosorbide en l'absence de dissolvant par catalyse hétérogène à l'aide de résines sulfoniques en tant que catalyseurs - Google Patents

Déshydratation de sorbitol en isosorbide en l'absence de dissolvant par catalyse hétérogène à l'aide de résines sulfoniques en tant que catalyseurs Download PDF

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WO2017013297A1
WO2017013297A1 PCT/ES2016/070550 ES2016070550W WO2017013297A1 WO 2017013297 A1 WO2017013297 A1 WO 2017013297A1 ES 2016070550 W ES2016070550 W ES 2016070550W WO 2017013297 A1 WO2017013297 A1 WO 2017013297A1
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sorbitol
range
catalyst
isosorbide
reaction
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PCT/ES2016/070550
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English (en)
Spanish (es)
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Pedro Jesús Maireles Torres
María José GINÉS MOLINA
José SANTAMARÍA GONZÁLEZ
Ramón Moreno Tost
Josefa María MÉRIDA ROBLES
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Universidad De Málaga
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Publication of WO2017013297A1 publication Critical patent/WO2017013297A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives

Definitions

  • the present invention relates to catalytic processes aimed at the transformation of biomass, in particular lignocellulose, into high value-added chemicals and biofuels. More particularly it refers to the dehydration of sorbitol to isosorbide by heterogeneous catalysis, using as a catalyst a sulfonic resin.
  • biomass processing is carried out. sustainable and integrated way, for conversion into a broad spectrum of chemicals and energy.
  • Two categories of biomass-derived resources are distinguished: those of first generation from high-starch edible plant crops such as sugar cane, beets, sweet sorghum, and vegetable oils, animal fats, etc., and the second generation that use lignocellulosic biomass, Jatropha oil, microalgae, etc.
  • a very important aspect is the use of lignocellulose present in forest, agricultural, agri-food, urban and industrial waste, since it is the main component of biomass.
  • Lignocellulosic biomass is a molecular complex consisting primarily of cellulose, hemicellulose, and lignin. The latter prevents access to sugars Being around the cellulose and hemicellulose present in the biomass, it is necessary to take a slow retratam of it in order for the carbohydrates to be affordable.
  • Iignocellulosic biomass can be treated by two procedures: thermal and hydrolysis,
  • thermochemical route implies a treatment at high temperatures and pressures.
  • the strategies to highlight in this way are gasification, pyrolysis and liquefaction. It is the process commonly used for catalytic conversion or fuel production, as is the case of the Fischer-Tropsch or hydro-oxygenation process.
  • o In the case of performing a hydrolysis or fractionation of the Iignocellulosic biomass, it is possible to isolate lignin and sugars to be treated through biological (enzymatic catalysis) or chemical processes (acid catalysis).
  • hydrolysis can be favored by increasing the system temperature above 225 ° C, combining it with the use of acidic metal catalysts.
  • One of the most attractive routes of cellulose transformation is its conversion to glucose.
  • Glucose is an important precursor to a broad spectrum of chemicals with high added value.
  • sorbitol stands out, one of the polyalcohols obtained by reduction, being a very important product from an industrial point of view.
  • Sorbitol is one of the most important platform products, which is obtained by reducing the glucose present in the lignocellulose composition, in particular in hernicellulose and cellulose.
  • Sorbitol is the hydrogenated form of glucose. It can be easily obtained from cellulose with very low production costs, being an ideal compound for the synthesis of derivatives of great interest in the industry, cellulose hydrolysis and subsequent catalytic hydrogenation of the resulting glucose can also lead to products of degradation of the resulting sorbitol.
  • Isosorbide is a versatile platform chemical, due to its high stability and the two functional hydroxyl groups that allow various chemical modifications, since which can be converted into other functional groups, being able to generate different monomers used for the production of polymeric materials.
  • Isosorbide has excellent physical-chemical properties applicable to different fields of industry, being an extraordinary pharmaceutical intermediate (diuretic, and mainly to treat hydrocephalus and glaucoma), it is used as an additive to improve the resistance and stiffness of polymers such as polyethylene terephthalate (PET), and as a monomer for the production of biodegradable polymers.
  • polymers such as polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • the compounds derived from isosorbide are isosorbide dinitrate and mononitrate, the latter being a compound widely used as a vasodilator for angina pectoris and congestive heart failure.
  • Isosorbide derivatives also find applications such as fuels or fuel additives, due to the high energy content that aiphatic substituents can provide (dimethyl isosorbide (DMI)).
  • DMI dimethyl isosorbide
  • Dehydration of sorbitol to isosorbide takes place through two consecutive stages. It begins with a first cyclization with loss of a water molecule where the chemical intermediates can be formed: 2,5-sorbitan and 1,5-sorbitan, which do not evolve to isosorbide, so they can be considered reaction byproducts, and the 1,4-sorbitan and 3,6-sorbitan, which progress to isosorbide. Subsequently, the second dehydration occurs, with a new cyclization that generates the isosorbide molecule.
  • this reaction is carried out using homogeneous acid catalysis, in the presence of liquid mineral acids, which leads to problems with corrosion of the reactors, neutralization stages and catalyst separation that cannot be reused.
  • solid catalysts represent a more sustainable alternative from an economic and environmental point of view, in addition to allowing in some cases a modulation of selectivity.
  • one of the objectives of Green Chemistry is the substitution of liquid mineral acids used in homogeneous catalytic processes by solid acid catalysts.
  • reaction systems aqueous solutions in gas and liquid phase, use of molten sorbitol have been studied in the presence of a broad spectrum of solid acid catalysts.
  • solid acid catalysts such as zeolites (Andrews et al. WO2001092266 A2, 2001; Liu et al., EP2146998 Al, 2010), tetravalent metal phosphates (Gu et al. ., Catal. Lett. 133 (2009) 214-220), heteropolyacids supported on silica (Sun et al., Korean J. Chem. Eng. 28 (2011) 99-105), sulfated copper oxide (Xia et al. , Catal. Commun. 12 (2011) 544-547), silicotungstic acid (Oltmanns et al., Appl. Catal.
  • sulfonic resins also used as ion exchangers.
  • These ionic exchange resins may have acidic or basic gnipos, in the event that cationic or ammonium exchange is pursued, respectively.
  • cation exchange resins become important, since they have strong acidic sulfonic gnipos (-S03H). They can also be used in a wide pH range.
  • the present invention relates to the development of a heterogeneous catalytic process for the dehydration of sorbitol, obtained from glucose from lignocellulosic biomass, to isosorbide, in a sustainable and efficient way, by proposing the replacement of liquid acid catalysts by solid acid catalysts that subside. the environmental, corrosion and separation problems involved in homogeneous catalysis.
  • styrene-divinylbenzene resins with acidic sulfonic groups whose polymeric structure consists of macroporous polystyrene cross-linked with divinylbenzene, with an acidity of 5.2 eq / kg, with a percentage of residual moisture of the 3%, with a particle size in the range 425-1200 micrometers, a specific area in the range 20-50 m 2 / g, a pore volume in the range 0.2-0.6 ml / g, an average diameter of the pore in the range 23-70 nm, and a thermal stability that extends to a maximum temperature of 180 ° C, as a solid acid catalyst in a heterogeneous catalytic process for the dehydration of sorbitol to isosorbide.
  • the invention relates to the use of styrene-divinylbenzene resins with acidic sulfonic groups whose polymeric structure consists of macroporous polystyrene cross-linked with divinylbenzene, with an acidity of 5.2 eq / kg, with a moisture percentage 3% residual, with a particle size in the range 425-1200 micrometers, a specific area in the range 35-50 m 2 / g, a pore volume in the range 0.2-0.5 ml / g, a average pore diameter in the range 23.1-42.5 nm, and a thermal stability that extends to a maximum temperature of 180 ° C, as a solid acid catalyst in a heterogeneous catalytic process for the dehydration of sorbitol to isosorbide.
  • the invention relates to the use of styrene-divinylbenzene resins with acidic sulfonic groups whose polymeric structure consists of macroporous polystyrene crosslinked with divinylbenzene, with an acidity of 5.2 eq / kg, with a moisture percentage 3% residual, with a particle size in the range 600-850 micrometers, a specific area in the range 20-40 m 2 / g, a pore volume in the range 0.2-0.6 ml / g, a average pore diameter in the range 40-70 nm, and a thermal stability that extends to a maximum temperature of 180 ° C, as a solid acid catalyst in a heterogeneous catalytic process for the dehydration of sorbitol to isosorbide.
  • a second object of the invention relates to a heterogeneous catalytic process for the dehydration of sorbitol to isosorbide which comprises the use of a styrene divinylbenzene resin with acid sulfonic groups as a solid acid catalyst according to the first object of the invention.
  • the process comprises (i) the addition to a reactor of the catalyst and sorbitol in a ratio sorbitol mass: catalyst in the range 10: 1-20: 1, preferably 20: 1; (ii) the reaction of the sorbitol mixture: catalyst under stirring, in the absence of solvent, and at a temperature in the range 140-180 ° C, preferably in the range 140-160 ° C, more preferably at 140 ° C, during a reaction time in the range 90 minutes - 12 hours, preferably in the range 10-12 hours, more preferably for 10 hours; (iii) dilution of the volume of melt resulting from the reaction with distilled water; and (iv) the separation of the catalyst from the sugars by microfiltration of the volume of molten diluted in water.
  • the reaction is carried out at atmospheric pressure without an inert atmosphere.
  • the reaction is carried out at atmospheric pressure but in an inert atmosphere by introducing a stream of an inert gas, for example N 2 .
  • the reaction is carried out under vacuum conditions.
  • the catalytic process comprises, after the step of separating the catalyst from the sugars formed by the dehydration of sorbitol, a step of recovering the catalyst for subsequent reuse, said step comprising washing the catalyst and its drying.
  • the present invention refers to the "S of sulphonic resins, different (among others) from Amberlyst-type resins (which have differences in porosity level, particularly having a smaller average pore diameter than resins whose use is referred to in the present invention), as solid acid catalysts for the dehydration of sorbitol to isosorbide, yields in isosorbide being reached close to 70%, with a total conversion of sorbitol, when molten sorbitol is used at 140 ° C, in the absence of solvent, then 10-hour reaction, when a sorbitolxatalizer mass ratio of 20: 1 is used.
  • the reaction is carried out by melting the sorbitol (mp 95 ° C) at 140 ° C, and conversions close to 100% are achieved after 3 hours of reaction, with yields to isosorbide of 43% which increases to 74.8% at 12 hours.
  • This evolution is justified by the formation of sorbitan, monobit dehydration products of sorbitol, of which 1,4- and 3,6-sorbitan are the only ones that evolve towards isosorbide.
  • catalysts can be reused, being stable in the reaction medium without loss. significant of its catalytic activity.
  • the remaining sorbitol and reaction products are dissolved in water to separate them from the catalyst.
  • the present invention allows the process to be carried out either at atmospheric pressure or under vacuum conditions.
  • the proposed catalysts require lower reaction temperatures to achieve yield values comparable to the data described in the state of the art on dehydration of sorbitol to isosorbide.
  • Figure 4 FTIR spectra of the Purolite CT269DR and CT269DR * (after reaction).
  • Figure 5 Comparison of conversion, selectivity, performance of catalytic resins for 10 hours at 140 ° C.
  • Figure 6 Catalytic activity of Purolite CT269DR as a function of reaction temperature.
  • Figure 7 Kinetic study of sorbitol dehydration at 140 ° C, up to 12 h of reaction time.
  • Figure 8 Kinetic study of sorbitol dehydration at 140 ° C, up to 44 h of reaction time
  • Figure 10 Study of the influence of the size of Purolite CT269DR at 140 ° C, during 90 min with 2 g sorbitol.
  • styrene-divinylbenzene resins with acid sulfonic groups are styrene-divinylbenzene resins with acid sulfonic groups.
  • Three commercial Purolite resins have been used: CT275DR, CT269DR and PD206. These types of resins have large diameter pores, which facilitate access to acid sites and avoid diffusional limitations that could appear with microporous materials. Be It deals with resins with a high concentration of acid centers. Its rnacroporous skeleton is formed by polyvinylbenzenesulfonic groups.
  • This technique allows the determination of the percentage composition of C, N, H and S of the resins studied. It is based on the complete oxidation of the sample by combustion with pure oxygen, in a controlled atmosphere, at a temperature of up to 1100 ° C.
  • the different resulting combustion products, C () 2, i and 2 O. 802 and N2 are subsequently quantified by IR and thermal conductivity sensor.
  • the percentages of carbon range between 35 and 45% with respect to the weight of the sample, while the mass C / S ratios indicate that the degree of sulfonation of these resins is different (Table 3).
  • Table 3 the lowest values are found for reams that have higher specific surfaces, that is, the CT269DR and CT275DR purolites, so it is expected that this suitable combination of high acidity and high surface area results in optimal catalytic behavior.
  • ATD-TG Differential and thermogravimetric thermal analysis
  • FTIR Fourier transform infrared spectroscopy
  • This technique consists in the study of the interaction of infrared radiation with matter. This spectroscopy allows to identify chemical species through the determination of the frequency at which the different functional groups have characteristic absorption bands in the IR spectrum. The concentration of the species is determined from the intensities and areas of the sample bands.
  • Figure 4 shows, as an example, the FTIR spectrum of the CT269DR resin, before and after the reaction. Both spectra are identical, indicating that the resin resists thermally, maintaining its structural integrity after the catalytic process.
  • the vibration modes associated with the sulphonic groups, with symmetric and asymmetric tensions of the S 0 to 620 and 1220 e and the voltage vibration CS at 1050 enr ⁇ , are masked by the intense bands of the organic skeleton of the Purolite resin , formed by divinylbenzene groups.
  • This reaction system consists of a discontinuous hatch reactor immersed in a silicone bath.
  • the reaction is carried out by introducing 2 g of sorbitol and 100 mg of catalyst into the reactor, which in turn is immersed in a liquid bath located on a heating plate, with magnetic stirring at 600 rpm, at 140 ° C for 10 hours, as standard reaction conditions.
  • the reaction time measurement starts once the bath thermometer reaches that temperature, and the reaction is interrupted by cooling the reactor in a cold water bath
  • the melt volume is diluted to 100 ml with distilled water. A fraction is taken from this solution, which is microfiltered and analyzed.
  • ICP-OES inductively coupled plasma emission spectrometry
  • this resin has been screened to obtain particle sizes in the ranges: [0.40-0.50], [0.50-, 71], [0.71-1.00] and [1.00- 1.18] mm.
  • the catalytic data demonstrate an improvement in performance with the use of the catalyst with the smallest particle size, between 0.4-0.5 mm, for which the highest sorbitol conversion is obtained.
  • the study was carried out at 140 ° C with the same sorbitol / catalyst mass ratio, but at 90 minutes of reaction in all cases ( Figure 10).
  • the catalytic activity data obtained in each cycle is shown in the bar chart of Figure 11. A slight decrease in conversion is observed after the first cycle. However, it is possible to maintain an average yield of 27-29% in isosorbide in the first 3 cycles.
  • measures CHNS chemical composition of the catalysts used were made after 2 and 4 or or reaction cycles. The data obtained are shown in Table 6 where no loss of sulfonic groups is observed. The C and H content increases slightly over the 4 cycles, corresponding to the possible carbonaceous residues. This increase in the amount of carbon leads to a continuous increase in the mass C / S ratio, after each cycle or catalytic.
  • Melt reaction system by an inert atmosphere stream
  • a stream of N2 is introduced into a flask with three mouths and an outlet, with the intention of removing the water vapor generated during the dehydration reaction.
  • the temperature is controlled by an external thermometer immersed in the silicone bath at 140 ° C, but in turn a thermometer is introduced through one of the mouths to know the thermal gradient when an inert gas is used.
  • Both the temperature and the reaction time are kept constant, 140 ° C for 10 hours; however, it is necessary to increase the initial sorbitol mass in the system to 4 g to provide a sufficient mass in the reactor, although the sorbitol / catalyst mass ratio of 20: 1 is maintained.
  • the nitrogen injection removes the water formed, but also causes a decrease in the reaction temperature, by removing heat from the medium, observing a difference of up to 30 ° C between the heating bath and the reaction atmosphere, with a negative effect on the evolution of the catalytic dehydration process.
  • CT269DR resin exhibits greater mechanical stability, which ensures its structural integrity in the reaction conditions.
  • reaction temperature was evaluated in the range between 100 and 160 ° C, 140 ° C being the optimum value, sufficiently far from the degradation temperature of the CT269DR resin (180 ° C).
  • the kinetic study showed that a complete conversion of sorbitol is achieved after 3 hours of reaction, but with an isosorbide yield of 43.2%, requiring 10 hours to obtain maximum yield (68.9%).
  • the catalyst is stable under the reaction conditions, as can be inferred from the sulfur analysis of the catalyst used and in the reaction medium.
  • the optimum catalyst loading and particle size have been 100 mg of catalyst panicles with sizes between 0.4 and 0.5 mm.
  • the chemical analysis of the catalysts used confirmed the stability of the catalyst.

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Abstract

L'invention concerne la déshydratation de sorbitol en isosorbide en l'absence de dissolvant par catalyse hétérogène à l'aide de résines sulfoniques en tant que catalyseurs. La présente invention, qui permet de résoudre des problèmes liés à la catalyse homogène et aux besoins associés à d'autres résines sulfoniques et d'autres catalyseurs, concerne l'utilisation de différentes résines de styrène-divinylbenzène, dont la structure polymère comprend du polystyrène macroporeux entrecroisé avec du divinylbenzène, en tant que catalyseurs acides solides dans un procédé catalytique hétérogène pour la déshydratation de sorbitol en isosorbide. L'invention concerne des procédés catalytiques hétérogènes pour la déshydratation de sorbitol en isosorbide en l'absence de dissolvant, dans des conditions de pression atmosphérique et de vide, qui consistent : à ajouter lesdites résines utilisées en tant que catalyseurs selon un rapport de masse sorbitol : catalyseur compris dans la plage 10:1 - 10:2 ; à provoquer une réaction à 140-180 °C pendant 1h30-12 heures ; à procéder à une dilution du volume de fusion ; et à séparer le catalyseur et les sucres par microfiltration.
PCT/ES2016/070550 2015-07-20 2016-07-20 Déshydratation de sorbitol en isosorbide en l'absence de dissolvant par catalyse hétérogène à l'aide de résines sulfoniques en tant que catalyseurs WO2017013297A1 (fr)

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ESP201500549 2015-07-20
ES201500549A ES2548483B2 (es) 2015-07-20 2015-07-20 Deshidratación de sorbitol a isosorbida en ausencia de disolvente mediante catálisis heterogénea usando resinas sulfónicas como catalizadores

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN109261202A (zh) * 2018-09-30 2019-01-25 中国科学院山西煤炭化学研究所 一种用于山梨醇脱水制备异山梨醇的催化剂及其制法和应用

Citations (3)

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WO2002036598A1 (fr) * 2000-11-01 2002-05-10 Archer-Daniels-Midland Company Procédé de production d'alcools de sucre anhydres
WO2009155020A2 (fr) * 2008-05-28 2009-12-23 Archer Daniels Midland Company Production d'esters cycliques de polyols à 5 éléments et à 6 éléments
WO2014070371A1 (fr) * 2012-10-31 2014-05-08 Archer Daniels Midland Company Procédé perfectionné de fabrication de produits de déshydratation interne d'alcools de sucre

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* Cited by examiner, † Cited by third party
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WO2002036598A1 (fr) * 2000-11-01 2002-05-10 Archer-Daniels-Midland Company Procédé de production d'alcools de sucre anhydres
WO2009155020A2 (fr) * 2008-05-28 2009-12-23 Archer Daniels Midland Company Production d'esters cycliques de polyols à 5 éléments et à 6 éléments
WO2014070371A1 (fr) * 2012-10-31 2014-05-08 Archer Daniels Midland Company Procédé perfectionné de fabrication de produits de déshydratation interne d'alcools de sucre

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Title
I. POLAERT ET AL.: "A greener process for isosorbide production: Kinetic study of the catalyticdehydration of pure sorbitol under microwave", CHEMICAL ENGINEERING JOURNAL, vol. 222, 2013, pages 228 - 239, XP055348016 *
M. HART ET AL.: "Acidities and catalytic activities of persulfonated poly(styrene-co-divinylbenzene)ion-exchange resins", CATALYSIS LETTERS, vol. 72, no. 3, 2001, pages 135 - 139, XP055348014 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109261202A (zh) * 2018-09-30 2019-01-25 中国科学院山西煤炭化学研究所 一种用于山梨醇脱水制备异山梨醇的催化剂及其制法和应用

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