Patent Application
20220242895
The invention relates to the use of adsorbents based on agglomerated crystals of FAU-type zeolite with an Si/Al atomic ratio greater than 1.5, comprising barium for the liquid-phase separation of “second generation” (2G) C5 and C6 sugars, that is to say comprising respectively 5 or 6 carbon atoms, more particularly glucose and xylose.
The production of “second generation” sugars from lignocellulosic biomass leads to a mixture of C5 and C6 sugars, essentially consisting of xylose (C5 sugar) and glucose (C6 sugar).
The stream of C5 and C6 sugars can be converted by fermentation into biobased molecules, of the alcohol (ethanol, n-propanol used as solvent in pharmacology) or diol type (Sheldon, 2018). For chemical conversion, a step of separating the sugars into C5 and C6 is necessary to enable them to be used in targeted reactions. Glucose (C6) and xylose (C5), being platform molecules, are converted into high value-added bioproducts. Glucose can be converted into sorbitol (used for personal care products), vitamin C, and then into isosorbide, a biodegradable monomer used for the production of polyethylene terephthalate for food use. Another example of the use of glucose is the isomerization thereof to fructose, which is the intermediate molecule for the exploitation of lignocellulosic biomass. Fructose can be dehydrated to hydroxymethylfurfural (5-HMF) which can be converted into biofuel, 2,5-dimethylfuran (DMF), or into acids such as furanodicarboxylic acid (FDCA), which is a precursor of the polymer polyethylene furanoate (PEF), and levulinic acid.
Today crystalline glucose is obtained by crystallization of high-glucose syrup (F. W. Schenck, 2012). Glucose syrup is obtained by enzymatic hydrolysis of starch, a polysaccharide present in first-generation (1G) biomass. However, the greatest use of starch is for the production of high-fructose-corn syrup (HFCS) used mainly in the agro-food industry. Starch-containing plants (wheat, corn, soft wheat) are edible and are in competition with the agro-food industry. Consequently, it is necessary to replace the glucose source with 2G biomass, and there is a need to obtain the purified glucose from the lignocellulosic material.
The prior art relating to the separation of xylose and glucose is quite poor. Two separation techniques are cited:
Despite this low selectivity, the evaluations by Vanneste et al. (Separation and Purification Technology, 2011), show that the separation by chromatographic process on Ca2+ exchanged styrene-DVB resin is economically comparable to separation by nanofiltration.
Zeolites, being crystalline materials, find their application in catalysis, adsorption and separation. Among more than two hundred zeolitic structures (http://www.iza-structure.org/databases) it is the FAU-type zeolite which is the most used in catalytic industrial processes such as the cracking of heavy petroleum cuts or in the separation of hydrocarbons, more particularly for the production of p-xylene from an aromatic feedstock containing C8 isomers. Faujasite, a FAU-type zeolite, exists in two forms: X form with an Si/Al atomic ratio of between 1 and 1.5 (R. M. Milton, 1959) and Y form with an Si/Al ratio of greater than 1.5 (D. W. Breck, 1964). Y-form faujasite-type zeolites, which find the main application in heterogeneous catalysis, can also be used for the separation of sugars (S. Kulprathipanja, 2017), without further clarification regarding their effectiveness for the separation of glucose and xylose.
Surprisingly, it appears that Y type agglomerated zeolitic adsorbents exchanged with barium have both a good adsorption capacity for sugars, which may optionally be improved by a step of zeolitization of the binder, and a favorable glucose/xylose selectivity, and may thus be successfully used in particular when they are produced from small crystals of FAU zeolite, in liquid-phase processes for the separation of glucose and xylose contained in “2nd generation” sugar juices, for example of the simulated countercurrent type.
The invention relates to a process for the liquid-phase separation of glucose from a mixture of C5 and C6 sugars comprising at least xylose and glucose, by adsorption of glucose on a zeolitic adsorbent based on FAU-type zeolite crystals having an Si/Al atomic ratio strictly greater than 1.5 comprising barium, wherein:
Said adsorbent may comprise zeolite crystals having a diameter of less than or equal to 2 μm, preferably less than or equal to 1 μm.
Preferably, the FAU zeolite has an Si/Al atomic ratio greater than or equal to 2.
Very preferably, the FAU zeolite has an Si/Al atomic ratio greater than or equal to 2.3.
Advantageously, the content of barium oxide BaO in said adsorbent is such that the Ba2+ exchange rate is greater than 50%, preferably greater than 60%, and more preferably greater than or equal to 65%.
Advantageously, said adsorbent has a total content of oxides of alkali metal or alkaline-earth metal ions other than barium, potassium and sodium, such that the exchange rate of all of said ions relative to all of the alkali metal or alkaline-earth metal ions, is less than 30%, preferably between 0% and 5%.
Advantageously, the separation by adsorption is carried out in a simulated moving bed: the xylose-enriched liquid phase is removed from contact with the adsorbent thus forming a raffinate stream, and the glucose-enriched phase adsorbed on said adsorbent is desorbed under the action of a desorption solvent, and removed from contact with the adsorbent then forming an extract stream.
Advantageously, the desorption solvent is water.
The separation by adsorption can be carried out in an industrial adsorption unit of simulated countercurrent type with the following operating conditions:
The adsorbent may be in the form of an agglomerate comprising a binder and the number-average diameter of the agglomerates is from 0.4 to 2 mm, preferably between 0.4 and 0.8 mm.
Throughout the description, the expressions “between . . . and . . . ” and “from . . . to . . . ” used in the present description should be understood as including each of the limits mentioned, unless noted otherwise.
The present invention relates to the use of adsorbents based on FAU zeolite having an Si/Al atomic ratio strictly greater than 1.5, comprising barium, for the separation of glucose from a sugar juice containing glucose and xylose, by a simulated countercurrent process.
It has in fact been observed that, surprisingly, a glucose/xylose selectivity of greater than 1.5 could be obtained with adsorbents based on FAU zeolite having an Si/Al atomic ratio strictly greater than 1.5, comprising barium.
The present invention relates to a process for the liquid-phase separation of glucose, preferably of the simulated countercurrent type, from a sugar juice containing glucose and xylose, and using adsorbents based on FAU zeolite having an Si/Al atomic ratio strictly greater than 1.5, comprising barium.
Adsorbents comprising zeolite crystals having a diameter of less than or equal to 2 μm, preferably less than or equal to 1 μm, are preferred. This is because small zeolite crystals generally provide better mass transfer than crystals of the same zeolite with a larger particle size, in particular due to the improved mass transfer. In addition to good selectivity properties with respect to the species to be separated from the reaction mixture, the adsorbent then exhibits good mass transfer properties making it possible to contribute to an efficient separation of the species in the mixture.
The FAU zeolite used is a zeolite comprising barium, having an Si/Al atomic ratio such that Si/Al>1.5, preferably greater than 2, very preferably greater than 2.3, in order to improve the selectivity toward glucose.
The exchange rate of a given cation is defined as the ratio between the number of moles of oxide M2/nO of the cation Mn+ considered and the number of moles of all of the alkali metal and alkaline-earth metal oxides.
The contents of barium and of alkali metal or alkaline-earth metal ions other than barium and sodium, expressed in the form of oxides, are as follows:
The adsorbent used in the process can be prepared according to the following steps:
a) mixing the crystals of desired particle size of FAU zeolite having an Si/Al atomic ratio such that Si/Al>1.5, preferably greater than 2, very preferably greater than 2.3, obtained by any method known to those skilled in the art, described in the literature (D. M. Ginter et al., 1992), in the presence of water with at least one binder based on a clay (kaolin type) or a mixture of clays, and optionally a source of silica;
b) shaping the mixture obtained in a) to produce agglomerates, then drying, optionally followed by a screening and/or cycloning step;
c) calcining the agglomerates obtained in b) at a temperature preferentially ranging from 500° C. to 600° C.;
d) optionally zeolitizing the binder by bringing the calcined agglomerates resulting from step c) into contact with an alkali metal basic aqueous solution, followed by washing;
e) ion exchange of the zeolitic agglomerates obtained in c) or in d) with barium ions, followed by washing and drying of the product thus treated.
The shaping step b) makes it possible to obtain zeolitic agglomerates having sufficient mechanical strength for the use thereof in a process for separating a liquid mixture in a simulated moving bed. However, the presence of binder reduces the proportion of active material in the adsorption sense, said active material being the FAU zeolite having an Si/Al atomic ratio such that Si/Al>1.5.
The optional step d) of zeolitizing the binder thus makes it possible to convert all or part of the binder into active material in the adsorption sense (FAU zeolite having an Si/Al atomic ratio such that Si/Al>1.5) in order to obtain binder-free agglomerates, i.e. no longer comprising a non-zeolitic phase (in an amount typically of less than 2%), or agglomerates with a low binder content, i.e. comprising little (an amount typically of between 2% and 5%) of non-zeolitic phase (generally non-zeolitized residual binder or any other amorphous phase after zeolitization) in the final agglomerate, while maintaining the mechanical strength.
The agglomerates resulting from step c/ or d/, whether they are in the form of beads or extrudates, generally have a number-average diameter ranging from 0.4 to 2 mm, and in particular between 0.4 and 0.8 mm, more preferably between 0.5 and 0.7 mm.
The present invention more particularly relates to a process for the liquid-phase separation of glucose from a sugar juice containing glucose and xylose, taking place by liquid chromatography, advantageously in a simulated moving bed, i.e. simulated countercurrent or simulated cocurrent moving bed, and more particularly simulated countercurrent moving bed.
The desorption solvent is preferably water.
In a liquid-phase adsorption separation process, the adsorbent solid is brought into contact with the liquid feed stream (feedstock) composed of a sugar juice containing xylose and glucose. By using a zeolitic adsorbent based on a zeolite of faujasite Y structure comprising barium, the glucose is then adsorbed in the micropores of the zeolite preferentially with respect to the xylose. The phase adsorbed in the micropores of the zeolite is then enriched in glucose relative to the initial mixture constituting the feed stream. Conversely, the liquid phase is enriched in xylose relative to the initial mixture constituting the feed stream.
When the process takes place in a simulated moving bed, the xylose-enriched liquid phase is then removed from contact with the adsorbent thus forming a raffinate stream, and the glucose-enriched adsorbed phase is desorbed under the action of a desorption stream (or desorption solvent), and removed from contact with the adsorbent then forming an extract stream.
In general, the operation of a simulated moving bed column can be described as follows:
A column comprises at least four zones, each of these zones being made up of a certain number of successive beds, and each zone being defined by its position between a feed point and a withdrawal point. Typically, a simulated moving bed unit for the separation of sugars is fed with at least one feedstock F to be fractionated (sugar juice) and one desorbent D, sometimes referred to as a desorption solvent or eluent (generally water), and at least one raffinate R containing the least selectively adsorbed feedstock products and desorbent and an extract E containing the most adsorbed feedstock product and desorbent are withdrawn from said unit.
Conventionally, 4 different chromatographic zones are defined in a column operating in simulated countercurrent mode.
The operating conditions of an industrial adsorption unit of simulated countercurrent type are advantageously the following:
One of the techniques of choice for characterizing the adsorption of molecules in the liquid phase on a porous solid is to carry out a breakthrough. In his book “Principles of Adsorption and Adsorption Processes”, Ruthven defines the technique of breakthrough curves as the study of the injection of a range of adsorbable constituents.
Several types of adsorbents are prepared: zeolitic adsorbents based on Y zeolite (A to D), ion-exchange resin (E).
The characteristics of the adsorbents are as follows:
A breakthrough test (frontal chromatography) is performed with the adsorbents A to E to evaluate their efficiency.
The procedure for obtaining the breakthrough curves is as follows:
The injection of the feedstock is maintained for a sufficient time for the composition of the effluent to correspond to the composition of the feedstock.
The pressure is sufficient for the feedstock to remain in liquid phase at the adsorption temperature (30° C.), i.e. 0.12 MPa.
The composition of the feedstock used for the tests is as follows:
The selectivity of the glucose (G) relative to the xylose (X) is calculated from the adsorbed mass quantities qG and qX of the two compounds (the latter being determined by material balance from the analysis of the breakthrough effluent) and of the composition of the feedstock (feedstock in which the mass fraction of the compounds is yG and yX):
The breakthrough results are given in Table 1 below
Example 1 shows that the zeolitic adsorbent in accordance with the invention has improved properties of selectivity of glucose relative to xylose compared to the adsorbents or resins known from the prior art in the separation of sugars.
The breakthrough tests (frontal chromatography) are performed with the adsorbent A at several temperatures to evaluate their efficiency.
The procedure for obtaining the breakthrough curves is as follows:
The injection of the feedstock is maintained for a sufficient time for the composition of the effluent to correspond to the composition of the feedstock.
The pressure is sufficient for the feedstock to remain in liquid phase at the adsorption temperature (30° C., 40° C., 50° C., 60° C.), i.e. 0.12 MPa.
The composition of the feedstock used for the tests is as follows:
The breakthrough results are given in Table 2 below
The example shows that a zeolitic adsorbent in accordance with the invention has properties of selectivity of glucose relative to xylose which are favorable to the separation of glucose over the entire temperature range tested.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR1907089 | Jun 2019 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/066154 | 6/11/2020 | WO | 00 |
