FR3134109A1 - PROCESS FOR OPTIMIZING THE PRODUCTION OF LEVOGLUCOSENONE DURING STEAM CRACKING OF LIGNOCELLULOSIC BIOMASS - Google Patents

Abstract

The present invention relates to the field of valorization of co-products obtained during the production of “black pellets” type fuels with high calorific value from lignocellulosic biomass. More precisely, the invention relates to a process for optimizing and valorizing the production of levoglusenone during a steam cracking process.

Description

PROCESS FOR OPTIMIZING THE PRODUCTION OF LEVOGLUCOSENONE DURING STEAM CRACKING OF LIGNOCELLULOSIC BIOMASS

The present invention relates to the field of valorization of co-products obtained during the production of “black pellets” type fuels with high calorific value from lignocellulosic biomass. More specifically, the invention relates to a process for optimizing the steam cracking parameters making it possible to obtain a greater ratio of levoglusenone during a steam cracking process.

Field of the invention

The transformation of lignocellulosic biomass (wood, agricultural residues, co-products of agriculture and agro-industry) into an energetically dense, transportable and easily storable compound would make it possible to develop and consolidate an industrial stationary energy sector (biofuel used in a fixed point, the home, unlike biofuels) and reduce environmental impacts (fossil CO2 emissions, with biomass without fertilizers or phytosanitary products).

The black pellets are cylinders resistant to degradation by humidity, 1 to 3 cm long, with good mechanical strength allowing storage and handling similar to that of coal. Their combustion generates little ash, with a lower calorific value (LCV) close to 18 to 20 joules/gram of dry matter.

Black pellets are produced from lignocellulosic biomass subjected to steam cracking. This consists of a heat treatment, followed by sudden depressurization to provide a water-proof material during shaping for the production of granules or briquettes. The raw material is actually exploded with steam, which releases finer particles, allowing the material to have strong cohesion during the aggregation or molding phase.

Hydrothermal treatment, also called aqueous fractionation, solvolysis, hydrothermolysis, differs from steam cracking, or, in that it involves using water at high temperature and high pressure to promote the disintegration and separation of the lignocellulosic matrix . This technique is not suitable for the production of black granules since the products obtained are mainly liquid.

Pyrolysis is the chemical decomposition of an organic compound by intense heating in the absence of oxygen. The compounds obtained after pyrolysis differ in their characteristics from those obtained by steam cracking. Steam cracking cannot be compared to a pyrolysis technique in that it uses a steam explosion and is carried out in the presence of oxygen.

It is also necessary to differentiate between roasting processes which are characterized by a thermochemical treatment between 100 and 300°C allowing part of the organic matter to be modified to break the fibers while eliminating water.

The existing steam cracking process makes it possible to produce a lignocellulosic biomass powder, dry, pretreated, without chemical additives, stable and economically viable for commodities such as energy, let alone viable for products with higher added value.

It is known to those skilled in the art that treatment processes, such as steam cracking, make it possible to obtain intermediate products with added value. For example, it is known to those skilled in the art that molecules of interest can be formed under the thermal effect of steam cracking and can be extracted by washing.

Patent application WO2021167511A1, describes a method and system for recovering energy and chemicals from a steam explosion reactor in a biorefinery. In particular, it discloses a process in which the co-produced levoglucosenone is recovered.

The methods known from the prior art provide processes for recovering co-produced molecules of interest. However, there is a need to obtain a process which not only allows the recovery of molecules produced incidentally during the steam cracking process but, conversely , specifically optimizes the production of said molecules of interest while maintaining parameters adapted to obtaining black granules.

The inventors propose a process for producing steam-cracked granules whose parameters are oriented to optimize the production of levoglucosenone through autocatalyzed reactions, such as dehydration. Said autocatalyzed reactions are notably produced and improved thanks to steam cracking in a dry environment.

The proposed process has specific parameters in terms of drasticity (residence time, temperature), access to the substrate (particle size, humidity) or composition of the raw materials (more xylose in hardwoods than in softwoods, more acidity in oak than in other hardwoods) allowing optimization of levoglucosenone production.

The levoglucosenone produced during the steam cracking step can then be recovered from the residual gases by condensation and/or from the powder by steam leaching or by extraction with a solvent.

Thus, the invention therefore consists of a process for producing granules by steam cracking of lignocellulosic biomass optimized to improve the production of an intermediate product such as levoglucosenone comprising the steps of:

• have a lignocellulosic biomass with a humidity level of between 5 and 27%
• treat said biomass by steam cracking at a pressure of between 10 and 25 bars, and preferably between 16 and 19 bars, for 3 to 20 minutes, a temperature of between 203 and 208°C and a severity factor of between 3.5 and 4 .5, and preferably between 4.0 and 4.2 until a powder is obtained
• Recovery of levoglucosenone from residual gases and/or powder by steam leaching or solvent extraction.

Advantages of the invention

The process according to the invention offers a double production in a completely innovative manner: the optimized production of levoglucosenone at the same time as that of biofuel pellets. Thanks to this process, it is possible to reduce production costs by revaluing molecules produced under the thermal effect of steam cracking and extractable by washing, distillation or others.

On the one hand, the process advantageously optimizes the production of levoglucosenone. This molecule is particularly interesting in the field of special polymers, perfumes and pharmaceutical active ingredients. Levoglucosenone is a precursor of a green solvent like the commercial product from the company CIRCA called Cyrène®.

To date, there is no process of industrial size and reality for transforming lignocellulosic biomass into molecules with high added value, having technical reality on a large scale and economic viability, and a good environmental record, without risks. Molecules from biotechnology (enzymes, microorganisms) are almost the only chemical valorization to date on a lignocellulosic basis.

Although the recovery of levoglucosenone during a steam cracking process is known from the prior art, there is no process for specifically optimizing its production and recovery while maintaining the production of good quality granules.

On the other hand, the process has the advantage of producing, simultaneously with the optimized production of levoglucosenone, biofuel pellets, which makes the process economically viable.

Some pellet preparation processes require the use of synthetic chemicals. However, these chemicals are both a source of atmospheric pollution through their production or end of life, but also of toxicity. In addition, the absence of synthetic chemicals in the finished product, namely biofuel pellets, avoids the release of toxic products during its use: no contamination of closed spaces.

Furthermore, the absence of water or its drastic reduction for steam cracking and pressing during the manufacture of biofuel pellets (densification stage) reduces energy costs (less heating) and gaseous or liquid effluents.

The use of steam-cracked biomass (particularly wood), which provides natural cohesive capacities for the preparation of black pellets, makes it possible to reduce environmental impacts (few or no chemicals, pressing processes without water and with less energy) .

A first subject of the invention relates to a steam cracking process from lignocellulosic biomass optimized for the production and recovery of levoglucosenone comprising the steps of:

• have a lignocellulosic biomass with a humidity level of between 5 and 27%
• treat said biomass by steam cracking at a pressure of between 10 and 25 bars, and preferably between 16 and 19 bars, for 3 to 20 minutes, a temperature of between 203 and 208°C and a severity factor of between 3.5 and 4 .5, and preferably between 4.0 and 4.2 until a powder is obtained
• recover levoglucosenone from residual gases by condensation, from powder by leaching, by steam or by extraction with a solvent.

By “lignocellulosic biomass”, we mean plant material whose major constituents are cellulose, hemicellulose and lignin. The proportions of these components vary depending on the plant species. In the context of the invention, the lignocellulosic biomass of interest mainly consists of hardwoods and softwoods rich in glucose.

By “steam cracking in a dry environment”, we mean steam cracking carried out with a lignocellulosic biomass whose humidity level is between 5 and 27% and in which no water or chemical product is added during steam cracking. For the purposes of the invention, the term “chemical product” designates any substance formed by chemical treatment or by the assembly of several different chemical elements in defined proportions.

In one embodiment, the powder obtained at the steam cracking stage is capable of being densified in order to obtain dense granules (“black pellets”) intended to be used as biofuel.

Levoglucosenone is a molecule derived from glucose which is notably produced during steam cracking under specific steam cracking conditions. This molecule is represented by the following formula:

During steam cracking, sugars such as xylose from hemicelluloses and glucose from cellulose, contained in lignocellulosic biomass, can be released or chemically modified to produce intermediate molecules such as levoglucosenone. Thanks to the combination of raw materials rich in accessible glucose and specific steam cracking conditions (temperature, residence time, humidity, particle size to increase the production of these high added value molecules), it is possible to optimize the production and the recovery of this molecule.

The steam cracking process according to the invention allows:

• on the one hand to optimize the production and recovery of an intermediate product such as levoglucosenone produced under the thermal effect of steam cracking and extractable by condensation of residual gases or in the powder by washing, distillation or leaching which, by its added value, constitutes a product of high interest.
• on the other hand to produce a lignocellulosic biomass powder capable of being densified in the form of a granule which has in particular the properties of being: dry, pretreated, without chemical additives, stable and economically viable for commodities such as energy, therefore has even more viable for products with higher added value.

In a particular embodiment, the steam cracking process is carried out as follows:

- obtaining, from wood chips, wood fragments whose size is between 0.5 and 14 mm and having a humidity level of between 5 and 27%;

- continuous introduction of a predetermined volume per minute of said wood fragments into a pressure reactor, said reactor being supplied with substantially saturated water vapor whose pressure is between 16 and 19 bars and the temperature is between 203 and 208°C;

- exposure of the wood fragments introduced into said reactor to said water vapor for a sufficient duration to obtain steam cracking of between 3 and 20 minutes and preferably between 7 and 15 minutes, the value of said exposure duration and the value of the temperature of said substantially saturated steam being selected so that the severity factor is between 3.5 and 4.5, preferably between 4.05 and 4.15;

- continuous extraction from said reactor of the same predetermined volume of wood fragments per minute, through a plurality of orifices opening into a conduit substantially at atmospheric pressure, so as to cause explosive decompression of said extracted wood fragments of said reactor in said conduit;

- separation of said decompressed wood fragments and the residual steam extracted from said reactor, said wood fragments obtained after separation forming a combustible material in powder form.

- Recovery of levoglucosenone in residual gases by condensation

The Treatment Severity Factor is defined by the formula:

FS=Log10(time(min)*exp((T°C-100)/14.75)).

The higher the temperature and the longer the treatment time, the more the severity increases, the more transformation we see in the product, the more carbonaceous matter is lost in the evaporates.

In a first particular embodiment of the invention, the raw material for the steam cracking process is a lignocellulosic biomass rich in glucose. In one embodiment of the invention, the raw material is mainly hardwood and softwood rich in glucose. In a preferred embodiment, the raw material is a mixture of hardwood, eucalyptus and undebarked oak. This raw material is particularly interesting since it allows the recovery of levoglucosenone (high added value molecule), at a concentration of between 3 and 9 mg/L. In a particular embodiment, the steam cracking process makes it possible to obtain a quantity of levoglucosenone of between 1 and 10 mg/L and more particularly between 5 to 10 mg/L.

In an even more advantageous embodiment the raw material is chosen from: a mixture of hardwoods, unbarked oak, softwood sawmill related chips or a mixture of these.

In a particular embodiment, the levoglucosenone is recovered from the powder by leaching or by extraction with a solvent. In an advantageous embodiment, said solvent is a polar solvent. In another embodiment, the solvent in the recovery step is ethanol.

In a particular embodiment, at least part of the powder obtained in the steam cracking step is used in the levoglucosenone recovery step.

In a preferred embodiment, the biomass consists of more than 50% of a biomass rich in glucose. The powder obtained can be used for the recovery of levoglucosenone by leaching and/or by extraction with a solvent such as ethanol.

In another embodiment, the biomass consists of more than 50% of a mixture of hardwoods and softwoods rich in glucose.

In another particular embodiment of the invention, the residence time of said biomass in the steam cracking chamber is between 5 and 10 minutes. In an even more advantageous embodiment, the residence time is 7.5 minutes.

In another particular embodiment of the invention, the temperature in the steam cracking step is between 206°C and 208°C, in an even more advantageous embodiment, the temperature in the steam cracking step is 208°C.

In another particular embodiment of the invention, the severity factor in the steam cracking step is between 4.05 and 4.15

A second object of the invention is the use of the steam-cracked powder or the leaching residue obtained by the process of the invention for the production of steam-cracked granules in order to be used as biofuel.

A third object of the invention is the use of levoglusenone obtained by the process of the invention, as a precursor for the production of green solvent or antiviral molecules.

Indeed, levoglucosenone is used as a precursor for the production of Cyrene, a green solvent used in the chemical industry.

In addition, levoglucosenone constitutes a precursor of antiviral molecules highly sought after in the pharmaceutical industry.

EXAMPLES

EXAMPLE 1: Study of the quantity of THE voglusenone in condensates of different biomass s after e s steam cracking .

1 - Materials and methods

A) Condensate samples.

21 condensate samples were studied. The coding, species, operating conditions and production batch are given for each sample in Table 1.

Sample name Esp e This Severity conditions Production batch 10/01/20 C6 assessment
Oak
3.91 = 203°C; 7.5 mins 1 10/01/20 C8 assessment
Oak 3.96 = 208°C; 6min
1 01/14/20 CNE6 review
Unbarked oak 3.91 = 203°C; 7.5 mins
1 01/16/20 ES6 review
Spicy bark beetle 3.91 = 203°C; 7.5 mins
1 01/16/20 BE6 review
Wood B energy 3.91 = 203°C; 7.5 mins
1 01/17/20 CHA6 review
Charm 3.91 = 203°C; 7.5 mins
1 02/15/20 BBP6 assessment
Wood B panels 3.91 = 203°C; 7.5 mins
1 04/14/20 EUC6 assessment Eucalyptus 3.91 = 203°C; 7.5 mins
1 04/14/20 EUC9 assessment Eucalyptus 4.05 = 208°C; 7.5min 1
04/14/20 EUC3 assessment Eucalyptus 3.67 = 195°C; 7.5min 1 04/15/20 EUC8 assessment
Eucalyptus 3.96 = 208°C; 6min
1
04/15/20 BAP6 assessment
Wood Pallet 3.91 = 203°C; 7.5 mins
1
04/17/20 SHS6 balance sheet pH 3.11 Schilliger softwood sawdust 3.91 = 203°C; 7.5 mins
1 04/17/20 SHP6 balance sheet pH 3.15
Schilliger softwood insert 3.91 = 203°C; 7.5 mins
1 05/13/20 PF6 assessment Forest plaque 3.91 = 203°C; 7.5 mins
1 01/07/20 M2F5 assessment Hardwood Mix 3.81 = 203°C; 6min
1
01/07/20 M2F6 assessment
Hardwood Mix 3.91 = 203°C; 7.5 mins
1
01/07/20 M2F8 assessment
Hardwood Mix 3.96 = 208°C; 6min
1
02/07/20 ES5 review
Bark spruce 3.81 = 203°C; 6min
2
02/07/20 ES6 review
Spicy bark beetle 3.91 = 203°C; 7.5 mins

2
02/07/20 ES8 review Bark spruce 3.96 = 208°C; 6min
2

Table 1: List of condensate samples studied

B) Methods used

B.1 Analysis of sugars and carboxylic acids

The analysis is carried out on an Ultimate 3000 HPLC (Thermo), using an Aminex HPX-87H column (7.8 x 300 mm, 9 μm) heated to 50°C. The samples are filtered through a 0.2 μm RC ³ filter, 20 μL are injected per analysis. The mobile phase consists of 4 mM sulfuric acid, pumped with a flow rate of 0.5 mL/min for 90 minutes. Detection is done in UV at 210 and 280 nm, as well as with an RI ⁴ detector set in positive mode.

The analysis time was increased to 90 min compared to 60 min initially in phase I. This optimization follows the observation of a disturbance of the baseline on the chromatograms of certain samples. This is due to the matrix of the previously injected sample which is very retained on the column used. In order to no longer encounter this type of problem that could affect the quality of the chromatographic peaks, the analysis time was therefore increased.

The analysis of sugars and carboxylic acids was carried out in 4 replicates.

B.2. Analysis of phenolic compounds

The analysis is carried out on an Ultimate 3000 HPLC (Thermo), using an Accucore C18 AQ column (3 x 100 mm, 2.6 μm) heated to 48°C. The samples are filtered through a 0.2 μm RC filter, 1 μL is injected per analysis. The mobile phase consists of a gradient of 0.1% formic acid and acetonitrile.

The proportion of acetonitrile varies from 2 to 30% in 10 minutes with a flow rate of 0.8 mL/min. Detection is done in UV at 320, 210, 280 and 254 nm.

The quantification of levoglucosenone was disrupted at 210 nm by the presence of a co-eluted compound. Following a study carried out on the absorbance of LGO, its maximum absorbance wavelength was determined at 320 nm. This new wavelength was monitored specifically in order to improve the detection limit of the LGO and to overcome co-elution which is no longer visible at 320 nm. The analysis of phenolic compounds was carried out in 3 replicates.

B.3. Using the metered addition method

The metered addition method is a quantitative analysis method, which replaces the calibration method when an effect of the sample matrix is observed. The retention time and/or signal intensity can be modified. This method consists of carrying out a calibration range but from the sample and not in a solvent. The principle is to add to the sample a standard of known and increasing concentration of the molecule that we wish to measure. Here, this method was used to confirm the presence of certain compounds by spiking the samples with the standard. For quantification, external ranges were used.

B. 4. Analysis by mass spectrometry

Mass analysis is carried out on a Q-ToF5 LC (Agilent Infinity 1290/6545), using a Zorbax C18 column (2.1 x 50 mm, 1.8 μm) heated to 40 °C . The samples are filtered through a 0.2 μm RC filter, 1 μL is injected per analysis. The mobile phase consists of a gradient of 0.1% formic acid and acetonitrile. The proportion of acetonitrile varies from 5 to 100% in 18 minutes with a flow rate of 0.45 mL/min. A first detection is done in UV at 220, 250 and 320 nm. A second mass detection is carried out in positive mode, with a scan ranging from 50 to 1000 m/z. The reference masses used to calibrate the analysis are 121.0509 and 922.0098 Da.

B.5. Calculation of relative concentrations

The relative concentrations shown were calculated according to equation 1.

Per sample, and for each compound, the ratio of the concentration (of the compound) to the sum of the concentrations was calculated and reduced to a percentage.

B.6. Statistics

The values presented correspond to averages calculated on the different replicates with their associated standard deviations. The orders of magnitude of the means being very different, in certain cases, the coefficient of variation was calculated. This is a measure of relative dispersion, calculated by taking the ratio of the standard deviation to the mean. It makes it possible to judge the dispersion of values around the average, whatever its order of magnitude. It is often expressed as a percentage.

C) Results

C.1. Average composition obtained with a severity of 203°C and 7.5 min of residence time on different species (in mg/L)

The study of variability was carried out on 13 types of wood extracted according to the severity conditions of 3.91, that is to say at 203°C for 7.5 min. The average concentrations obtained are presented in Table 2.

Esp e This Levoglucosenone (mg/L) Hardwood Mix
8.75 Eucalyptus
3.09 Unbarked oak
5.05 Forest plaque
3.73 Bark spruce 1
2.85 Bark spruce 2
3.31 Charm
2.63 Oak
1.94 Softwood sawmill board
4.58 Wood Pallet
2.11 Wood B panels
0.94 Softwood sawdust from sawmill
4.24 Wood B energy
0.72

Table 2 : Average concentrations obtained with a severity of 3.91 on different species

We observe that the 3 woods which produce the highest concentrations of levoglusenone are: mixture of hardwoods, undebarked oak and sawmill softwood chips; the three weakest are: wood B energy, wood B panels and oak.

C.2. Analysis of the influence of process severity conditions

The influence of the severity conditions of the process was studied on 3 different woods: eucalyptus, mixed hardwoods and bark spruce. Table 3 presents the average concentration of the 3 woods used to study the impact of severity conditions.

Compound Severity Levoglucosenone
Eucalyptus 3.67 (7.5 min; 195°C) 1.6 3.91 (7.5 min; 203°C) 3.1 3.96 (6 min; 208°C) 6.8 4.05 (7.5 min; 208°C) 3.9 Hardwood Mix 3.81 (6 min; 203°C) 6.3 3.91 (7.5 min; 203°C) 8.7 3.96 (6 min; 208°C) 10.1 Spruce Bark beetle 3.81 (6min; 203°C) 2.6 3.91 (7.5 min; 203°C) 3.3 3.96 (6min; 208°C) 4.9

Table 3 : Average concentrations of levoglucosenone (in mg/L) analyzed by LC-UV of 3 species of wood

It appears that the concentration of levoglucosenone increases up to the severity condition 3.96, and that the severity condition 4.05 is too severe and begins to degrade this compound.

Thus, according to this study, severity conditions of 3.91 or 3.96 are optimal for increasing the levoglucosenone concentration.

Conclusion :

The results of the study show that there is variability between the different species of wood studied. The three wood species have generally higher concentrations than other woods. These are hardwood mixtures, eucalyptus and unbarked oak. They actually have a levoglucosenone concentration of between 3 and 9 mg/L. These woods are therefore of interest for the valorization of condensates in the recovery of levoglucosenone.

Claims (9)

Steam cracking process from lignocellulosic biomass optimized for the production and recovery of levoglucosenone comprising the steps of:

• have a lignocellulosic biomass with a humidity level of between 5 and 27%
• treating said biomass by steam cracking at a pressure of between 10 and 25 bars, a temperature of between 203 and 208°C and a severity factor of between 3.5 and 4.5 until a powder is obtained
• Recovery of levoglucosenone from waste gases by condensation into powder by steam leaching or solvent extraction.

Steam cracking process according to claim 1, in which the raw material is mainly hardwoods and softwoods rich in glucose. Steam cracking process according to claim 1 or 2, in which the residence time of said biomass in the steam cracking chamber is between 7 and 15 minutes Steam cracking process according to one of claims 1 to 3, in which the temperature in the steam cracking step is between 206 and 208°C. Steam cracking process according to one of claims 1 to 4 in which the severity factor is between 4.05 and 4.15. Steam cracking process according to one of the preceding claims in which at least part of the powder obtained in the steam cracking step is used for the recovery of levoglucosenone. Steam cracking process according to one of the preceding claims in which a quantity of levoglusenone of between 1 and 10 mg/L is obtained. Use of a steam-cracked powder obtained by the process according to one of claims 1 to 7, for the production of steam-cracked granules suitable for use as biofuel. Use of levoglusenone obtained by the process according to one of claims 1 to 7, as a precursor for the production of green solvent or antiviral molecules.