FR3138919A1 - METHOD FOR VALORIZING A BIOMASS OIL BY ESTERIFICATION - Google Patents

Abstract

The invention relates to a process for treating a biomass oil with an alcohol to increase the incorporation of compounds from olefins while reducing the content of carboxylic acid compounds. For this purpose, the biomass oil is brought into contact with at least one alcohol and a composition containing olefins in the presence of a homogeneous acid catalyst at a temperature less than or equal to 90 ° C, under a pressure ranging from 200 mbar to atmospheric pressure for 30 minutes to 24 hours to carry out at least one of the following reactions: an esterification of the carboxyl groups, an acetalization of the carbonyl groups, an etherification of the hydroxyl groups, the contacting being carried out by eliminating the water formed by a or more of the above reactions. The biomass oil is first contacted with an excess alcohol and the homogeneous acid catalyst before fractionally adding the olefin-containing composition.

Description

METHOD FOR VALORIZING A BIOMASS OIL BY ESTERIFICATION

The present invention relates to the field of biomass oils, resulting from a pyrolysis of biomass or a hydrothermal treatment of biomass, and more particularly their valorization by esterification, in particular either with a view to their use as is or separated into usable flows for the preparation of fuels and/or for the preparation of lubricants, or with a view to their use in a hydroconversion or cracking process, in particular to manufacture fuels.

Prior art

Biomass oils, also called “bio-oils” can be obtained by pyrolysis or hydrothermal liquefaction of biomass. These bio-oils constitute an interesting alternative for the production of hydrocarbons from renewable resources and reduce greenhouse gas emissions.

Bio-oils, however, are complex liquids, consisting of water and a complex mixture of oxygenated compounds (such as aldehydes, ketones, furans, carboxylic acids, sugar-like compounds, lignin-derived compounds, etc.). Their elemental composition is close to the composition of the starting biomass, in particular with a high oxygen content. Table 1 gives orders of magnitude of several characteristics of pyrolysis and hydrothermal liquefaction bio-oils.

[Table 1] Properties of hydrothermal liquefaction and pyrolysis bio-oils Hydrothermal liquefaction oil Pyrolysis Oil
(Wood, lignocellulosic biomass) Elemental composition (% m) Carbon
Hydrogen
Oxygen
Nitrogen
Sulfur 60-80
5-15
8-20
0-10
<2 10-70
5-10
30-55
0-2
<1 Water content (% m) <15 15-30 Viscosity (mPa.s) (50 °C) from 60 to 1500 or more 10-100 Acid number (mgKOH per gbio-oil) 5-200 50-250

These bio-oils are also chemically and thermally unstable. Chemical instability results in the evolution over time of their physicochemical properties (viscosity, water content, solid content, etc.) which can result in a separation into two phases. Thermal instability results in a very rapid evolution of their properties when heated to temperatures above 80°C.

Due to their particular properties stated above, the use of bio-oils raises numerous problems.

In particular, bio-oils cannot be used as fuel due to their high content of oxygenated molecules, and in particular organic acids. They are also immiscible with fossil hydrocarbons. In addition, they contain many temperature-sensitive molecules, such as sugars.

To be able to be used in refineries for the production of renewable fuels or liquid fuels (or partially renewable if they are mixed with fuels or fuels of fossil origin), bio-oils must therefore be treated to improve their properties and allow their valorization in conventional refining processes and/or to produce fuels. It is thus known to subject bio-oils to hydrocracking or hydrodeoxygenation (HDO) treatment. Due to the high temperatures used, these treatments lead to the formation of char. In addition, HDO requires high hydrogen consumption and is difficult to industrialize due to its high exothermicity.

Studies have also focused on treatments in the presence of an alcohol and an acid catalyst to convert organic acids into esters and aldehydes into acetals and thus improve the properties of the products.

The esterification and acetalization reactions being balanced reactions, the use of excess alcohol and the elimination of water makes it possible to shift the balances. For example, water can be removed using adsorbents or reactive distillation. Since bio-oils are thermally unstable, optimizing the reaction can be difficult when it is necessary to maintain the bio-oils at a temperature lower than a temperature at which they are unstable.

The publication of F.H. Mahfud et al., “Biomass to Fuels: Upgrading of Flash Pyrolysis Oil by Reactive Distillation Using a High Boiling Alcohol and Acid Catalysts”, Process Safety and Environmental Protection, Volume 85, Issue 5, 2007, Pages 466-472 , describes the contacting of a pyrolysis oil with n-butanol in the presence of a solid or liquid acid catalyst, at a temperature of 323-353K under reduced pressure (<10kPa). Operating at reduced pressure eliminates the water present and shifts the balance in favor of esterification. This publication explains that product quality is better in the presence of a solid acid catalyst.

In the presence of a solid catalyst, however, secondary reactions of aging of the oil by polymerization can be observed.

It has also been described to valorize bio-oils by contacting them with olefins and an alcohol. Under acid catalysis conditions, olefins can indeed react with carboxylic acids, water, phenols and alcohols. However, the complex matrices of bio-oils raise numerous problems in terms of phase separation, reaction kinetics and catalyst deactivation.

Thus, the publication Zhang ZJ et al., “Catalytic conversion of bio-oil to oxygen-containing fuels by simultaneous reactions with 1-butanol and 1-octene over solid acids: Model compound studies and reaction pathways.” Bioresour Technol. 2013 Feb;130:789-92, explains that it is possible to valorize a bio-oil by putting it in contact with an olefin/1-butanol mixture in the presence of a solid acid catalyst, at a temperature of 120 °C and atmospheric pressure. Numerous simultaneous reactions are observed (esterification, etherification, hydration of olefins, alkylation of phenols, aldol condensation, dehydration of sugars, etc.). A similar study is presented in the publication Zhang ZJ et al., Catalytic upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalyst”; Green Chem., 2011, 13, 940. The results presented show that in the presence of 1-octene and a solid acid catalyst, at temperatures of 60 to 120 °C, two immiscible phases are formed leading to a low conversion of 1-octene. When the bio-oil is contacted with both 1-octene and 1-butanol, olefin hydrolysis, organic acid esterification, aldehyde and ketone acetalization, and alkylation reactions occur. phenols are observed. Depending on the solid catalyst used, it is possible to avoid phase separation and increase the alcohol and olefin conversion rates depending on the ratio of 1/butanol/1-octene added to the bio- oil.

The amount of olefins that can be added is, however, limited due to the phase separation observed with bio-oil, particularly with the lighter alcohols.

There is thus a need to improve the processes for treating a bio-oil by bringing it into contact with an alcohol and an olefin.

The invention aims to provide a process for treating a biomass oil with an alcohol making it possible to increase the incorporation of compounds from olefins while reducing the content of carboxylic acid compounds.

To this end, an object of the invention relates to a process for treating a biomass oil, comprising:

a) the provision of a biomass oil comprising oxygenated compounds containing at least one hydroxyl group and/or at least one carbonyl group, the biomass oil being chosen from a biomass pyrolysis oil, a hydrothermal liquefaction oil biomass and their mixtures,

b) an optional step of vacuum distillation of the biomass oil supplied by step a) to obtain a distillate and a residue under vacuum (noted RSV),

c) a step of bringing the biomass oil from step a), optionally the vacuum residue from step b), into contact with at least one alcohol and a composition containing olefins in the presence of a catalyst homogeneous acid at a temperature less than or equal to 90°C, under a pressure of 200mbar at atmospheric pressure for 30 minutes to 24 hours to carry out at least one of the following reactions: esterification of the carboxyl groups, acetalization of the carbonyl groups, etherification of the hydroxyl groups, the contacting being carried out by eliminating the water formed by one or more of the aforementioned reactions, and during which:

c(i) the biomass oil, optionally the residue under vacuum, is brought into contact with an excess alcohol and the homogeneous acid catalyst, then

c(ii) a quantity of the composition containing olefins less than or equal to a threshold quantity is added beyond which the reaction medium becomes two-phase,

c(iii) optionally, an alcohol is added in a sufficient quantity to maintain an excess of alcohol in the reaction medium,

c(iv) we repeat step c(ii), and optionally step c(iii), until the end of the reaction,
c(v) the effluent produced containing the biomass oil is recovered, optionally the residue under vacuum, having a reduced content of oxygenated compounds containing at least one hydroxyl and/or carbonyl group,

d) a step of separation of the effluent recovered in step c(v) during which the homogeneous acid catalyst is eliminated by precipitation.

The process according to the invention makes it possible to reduce the strongest acidity resulting from the presence of organic acids present in biomass oil or a biomass oil RSV. These organic acids, particularly the shorter ones (formic, acetic, propionic acid, etc.), are transformed into their respective esters by reaction with an alcohol in the presence of the acid catalyst. The process further makes it possible to stabilize the reactive species present in the biomass oil or biomass oil RSV. Indeed, the -OH and C=O groups present in polyols have several disadvantages. Through their strong polarity, they attract water molecules through hydrogen bonds and make the biomass oil (or a biomass oil RSV) hygroscopic and difficult to dehydrate. These -OH groups also strengthen the polar or hydrogen bonds between the polyols and contribute on the one hand to the high viscosity of biomass oils or their RSV and on the other hand to their instability by thermal polymerization which releases water and makes the matrix more and more viscous and with a high coking rate under high temperature. By reacting alcohols with the polyols, aldehydes and ketones present in the bio-oil, the process produces ethers and acetals which lower the content of OH and C=O groups. Replacing highly polar functions with other, less polar bonds reduces viscosity and improves flow properties at low temperatures. The process also makes it possible to reduce the oxygen and water content, improving the calorific value of the biomass oil (or a biomass oil RSV). Finally, transesterification or trans-etherification reactions can occur and replace long-chain esters and ethers in biomass oil using short-chain alcohols, which is also likely to improve viscosity and reduce the average molar mass of the molecules. Finally, since esters, acetals and ethers are less polar than alcohols or polyols, the process according to the invention makes it possible to improve the miscibility of biomass oils (or RSV of biomass oils) with petroleum fillers.

Advantageously, the biomass oil of step a) can be derived from a biomass chosen from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic waste, alone or as a mixture. .

• chaque alcool ajouté est miscible avec l’huile de biomasse de l’étape a) ou avec le résidu sous vide de l’étape b),
• à chaque mise en œuvre de l’étape c(iii), l’alcool ajouté est identique à l’alcool ajouté à l’étape précédente ou est un alcool présentant un nombre de carbones supérieur au nombre de carbones de l’alcool ajouté à l’étape précédente,
• la composition contenant des oléfines comprend (i) au moins 17 % m d’oléfines, optionnellement de 17 à 100 % m d’oléfines, (ii) de 22 % à 83 % m d’aromatiques lorsqu’elle n’est pas constituée entièrement d’oléfines, et optionnellement (iii) le reste étant constitué de paraffines, et optionnellement de naphtènes,
• l’étape c) est mise en œuvre à une température de 50 °C à 90 °C, optionnellement de 60 à 80 °C ou de 65 °C à 75 °C,
• la quantité de catalyseur acide homogène utilisée représente de 0,5 à 3 % en masse de la quantité d’huile de biomasse, optionnellement de résidu sous vide,
• le catalyseur acide homogène est choisi parmi l’acide sulfurique, l’acide 4-méthylbenzènesulfonique, l’acide benzènesulfonique, l’acide méthylsulfonique, de préférence l’acide sulfurique,
• l’étape c) est réalisée en présence d’un agent de transfert de phase comprenant au moins une fonction amine.

Advantageously, step c) may include one or more of the following characteristics:

• each added alcohol is miscible with the biomass oil from step a) or with the vacuum residue from step b),
• at each implementation of step c(iii), the alcohol added is identical to the alcohol added in the previous step or is an alcohol having a number of carbons greater than the number of carbons of the alcohol added to the previous step,
• the olefin-containing composition comprises (i) at least 17% m olefins, optionally 17 to 100% m olefins, (ii) 22% to 83% m aromatics when not composed entirely of olefins, and optionally (iii) the remainder consisting of paraffins, and optionally of naphthenes,
• step c) is carried out at a temperature of 50°C to 90°C, optionally 60 to 80°C or 65°C to 75°C,
• the quantity of homogeneous acid catalyst used represents 0.5 to 3% by mass of the quantity of biomass oil, optionally vacuum residue,
• the homogeneous acid catalyst is chosen from sulfuric acid, 4-methylbenzenesulfonic acid, benzenesulfonic acid, methylsulfonic acid, preferably sulfuric acid,
• step c) is carried out in the presence of a phase transfer agent comprising at least one amine function.

Separation step d) may advantageously comprise d(i) bringing the effluent from step c) into contact with a basic compound or a weak acid salt to form a precipitate with the homogeneous acid catalyst, d (ii) separation of the precipitate formed from the effluent, d(iii) optionally a washing step with an alcohol.

The process may further comprise a step e) of purification of the effluent from step d) during which the unreacted alcohol(s) are eliminated by distillation.

The effluent from step d) or step e) can also be:

f) treated in a fluidized bed catalytic cracker, and/or

g) treated in a hydrocracker, and/or,

h) treated in a catalytic hydrogenation unit, and/or

i) treated in a hydrotreating unit, and/or

j) used as such or separated into usable streams for the preparation of fuels such as LPG, gasoline, diesel, heavy fuel oil, for the preparation of lubricants and/or for the preparation of special fluids.

The effluent from step d) or step e) can be subjected to treatments f) to j) alone or mixed with a hydrocarbon feedstock of fossil origin.

Definitions

The terms "comprising" and "comprises" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or unlimited and do not exclude additional features, unspecified elements or method steps.

The expressions % by weight and % by mass (also noted % m) have an equivalent meaning and refer to the proportion of the mass of a product compared to 100 g of a composition comprising it.

By “bio-oil” or “biomass oil”, we mean an oil resulting from the pyrolysis of biomass and/or an oil resulting from the hydrothermal liquefaction of biomass.

By “biomass”, we mean an organic material such as wood (hardwood, softwood), straw, energy crops (short rotation coppice (TCR), very short rotation coppice (TTCR), miscanthus, switch grass, sorghum, etc.), forest or agricultural biomass residues such as bark, shavings, sawdust, bagasse, household organic waste, etc.

By “biomass pyrolysis oil” is meant here a crude oil resulting from the pyrolysis of biomass, optionally pretreated, for example by vacuum distillation (to remove water) and/or filtration/adsorption and/or liquid extraction/ liquid. Pyrolysis is a thermochemical decomposition of biomass at high temperature in the absence of oxygen.

The term “pyrolysis” includes different modes of pyrolysis, such as, for example, fast pyrolysis, vacuum pyrolysis, catalytic pyrolysis, hydrogen pyrolysis, and slow pyrolysis or carbonization, etc.

By “hydrothermal liquefaction” (or HTL for “Hydrothermal Liquefaction” in English), we mean a thermochemical conversion process of biomass using water as a solvent, reagent and catalyst for degradation reactions of organic matter, the water typically being in a subcritical or supercritical state.

Atmospheric pressure is the actual pressure measured. It therefore varies around normal atmospheric pressure (1013.25 mbar).

The Conradson carbon content (denoted CCR) is defined by the ASTM D 482 standard and represents for those skilled in the art a well-known evaluation of the quantity of carbon residue produced after pyrolysis under standard conditions of temperature and pressure.

The total acid number (TAN) can be determined according to ASTM D664-18e2 by potentiometric titration.

The carbon, hydrogen and nitrogen content can be measured according to ASTM D5291-21.

Oxygen content can be measured according to ASTM D5622-17.

The water content can be determined according to ASTM D6304-20 by the coulometric Karl Fischer titration method. In particular, vacuum residue samples or esterified oils were prepared at a concentration of 0.01 (g/l) in ethanol.

Olefin content can be measured according to ASTM D1159-07R17.

The contents of carbonyl and carboxyl groups in the oil before and after treatment can be determined by carbon-13 NMR.

Detailed description of the invention

Step a) of supplying a biomass oil containing oxygenated compounds

The biomass oil supplied in step a) may be an oil resulting from the pyrolysis of biomass, an oil resulting from the hydrothermal liquefaction of biomass or a mixture of one or more of these oils.

In one embodiment, the pyrolysis oil can advantageously be a biomass pyrolysis oil or a mixture of biomass pyrolysis oils, in particular from a biomass chosen from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic household waste, alone or in a mixture.

Step (a) of supplying biomass oil can thus comprise the mixture of one or more of the aforementioned oils.

Step (a) may further include:

(a1) a step of liquefying biomass and obtaining a hydrocarbon product comprising a gas phase, a liquid phase and a solid phase,

(a2) a step of separating the liquid phase of said product, said liquid phase forming a biomass oil.

The liquefaction step (a1) may comprise a pyrolysis step, typically carried out at a temperature of 300 to 1000 ° C or 400 to 700 ° C, this pyrolysis being, for example, rapid pyrolysis or flash pyrolysis or a catalytic pyrolysis or hydropyrolysis. In particular, pyrolysis can be rapid pyrolysis consisting of a rapid increase (<2 seconds) of the temperature to 300°C-750°C, leading to depolymerization and fragmentation of the constituent elements of the biomass (holocelluloses (cellulose, hemicellulose ), lignin), followed by rapid quenching of the degradation products.

Alternatively or in combination, the liquefaction step (a1) may comprise a hydrothermal liquefaction step, typically carried out at a temperature of 250 to 500 °C and at pressures of 10 to 25-40 MPa. Reaction times typically vary from a few seconds to several tens of minutes.

The separation step (a2) makes it possible to eliminate the gas phase, essentially the C1-C4 hydrocarbons and the solid phase (typically char) to recover only the liquid organic phase forming a biomass oil.

The biomass treated during step a1) can be defined as an organic plant product, namely a product composed of or derived from agricultural or forestry plant material.

The biomass can be chosen from lignocellulosic biomass, herbaceous biomass (biomass of plants having a non-woody stem), aquifer biomass (plants growing in water or underwater such as algae), paper, cardboard, organic waste, alone or in mixtures.

Biomass can thus include (i) biomass produced by surplus agricultural land, preferably not used for human or animal food: dedicated crops, called energy crops; (ii) biomass produced by deforestation (forest maintenance) or cleaning of agricultural land; (iii) agricultural residues from crops, particularly cereal crops, vines, orchards, olive trees, fruits and vegetables including nuts, agri-food residues, etc.; (iv) forest residues from silviculture and wood processing; (v) agricultural residues from livestock (manure, slurry, litter, droppings, etc.); (vi) organic household waste (paper, cardboard, green waste, etc.); (vii) industrial organic waste (paper, cardboard, wood, putrescible waste, etc.); (viii) algal biomass, namely biomass formed from algae, for example micro-algae (the algal biomass can be a suspension of algae obtained by harvesting algae coming for example from a bioreactor, or an algae residue obtained by dehydration of a suspension of algae) or macro-algae; (ix) herbaceous biomass; (x) vegetable oils contained in certain waste (cashew nut shells or other).

The biomass oil obtained can contain 8 to 55% by mass of oxygen. This oxygen is present in oxygenated compounds containing at least one hydroxyl group (-OH) and/or at least one carbonyl group (>C=O). A biomass oil may in particular contain carboxylic acids, ketones, aldehydes, phenols.

Step b) optional vacuum distillation

The biomass oil supplied in step a) may have a significant water content (up to 30% by mass, for example from 5% to 30% by mass). The presence of water, when it is significant, will increase the total reaction time of step c) to the extent that the water will shift the balance of the esterification and/or acetalization reaction and /or etherification by promoting the reverse reaction, and consequently slowing down these reactions until the water initially present has been eliminated.

Thus, in an advantageous embodiment, the biomass oil supplied in step a) is subjected to vacuum distillation making it possible to separate a distillate and a residue under vacuum, the latter having a low water content, typically lower at 5% by mass, advantageously less than 3% by mass.

Vacuum distillation is advantageously carried out at low temperature in order to avoid decomposition of the biomass oil. Typically, this vacuum distillation is carried out at a temperature of 65 to 75°C under a pressure of 80 to 90 mbar.

Distillation makes it possible to eliminate 80 to 90% by mass of the water initially present, which will shift the balance of the esterification reaction towards the formation of the ester, the balance of the acetalization reaction. towards the acetal and the equilibrium of the etherification reaction towards the formation of an ether during step c). This distillation step can also eliminate some of the most volatile short-chain acids.

When the water content of the biomass oil supplied in step a) is relatively low, for example less than or equal to 5% by mass, step b) can be omitted.

Step c) of esterification / acetalization / etherification

A biomass oil (or its vacuum residue) contains numerous oxygenated compounds containing one or more hydroxyl groups (phenols, polyalcohols) and/or one or more carbonyl groups (carboxylic acids, aldehydes, ketones), which make the oil corrosive, viscous biomass, immiscible with other hydrocarbons and unstable.

Step c) of esterification and/or acetalization and/or etherification of the present invention makes it possible to transform these groups into esters and/or acetals and/or ethers, which has the effect of reducing the viscosity of the oil. biomass (or its vacuum residue), to make it miscible with other hydrocarbons, to reduce its acidity and its instability.

The applicant has implemented at least one innovative process making it possible to treat biomass oil, or a vacuum residue of biomass oil, without decomposition, by esterification and/or acetalization and/or etherification, and incorporation of a maximum quantity of olefins in the matrix.

During this step, the biomass oil provided by step a), preferably the vacuum residue from step b), is thus brought into contact with at least one alcohol and a composition containing olefins in the presence of a homogeneous acid catalyst at a temperature less than or equal to 90°C, under a pressure of 200 mbar at atmospheric pressure for 30 minutes to 24 hours to carry out at least one of the following reactions: esterification of the carboxyl groups, acetalization carbonyl groups, etherification of hydroxyl groups. This contacting is carried out by eliminating (in particular by extraction) the water formed by one or more of the aforementioned reactions. This elimination can be carried out continuously or not over time depending on the water elimination system used. In particular, for industrial implementation, we will prefer to carry out continuous water extraction.

The alcohol used during step c) can be any alcohol advantageously miscible with the biomass oil from step a) or with the vacuum residue from step b). The invention is not limited to a particular alcohol, nor by a carbon chain length of the alcohol. However, we will most often use a C1-C6 or C1-C4 alcohol, preferably of biological origin, in order to promote possible transesterification and/or transetherification reactions with short-chain alcohols.

The composition containing olefins used during step c) may advantageously comprise (i) at least 17% m of olefins, optionally from 17 to 100% m of olefins, (ii) from 22% to 83% m of aromatics when it is not entirely made up of olefins, and optionally (iii) the remainder being made up of paraffins, and optionally of naphthenes.

When the total of constituents (i) and (ii) is not equal to 100% m, the remainder of the composition can thus consist of (iii) paraffins, and optionally naphthenes. Advantageously, each of the constituents (i) and (ii), or even (iii), of the composition is liquid at the implementation temperature of step c).

The olefins can comprise any type of olefins, advantageously liquid at the temperature and pressure conditions of step c). For example, we could use C4-C14 olefins, in particular C5-C10.

Thus, in one embodiment, the composition consists solely of olefins, in particular liquids at the temperature and pressure conditions of step c).

In another embodiment, the composition does not consist solely of olefins and comprises, in particular consists of, (i) at least 17% m of olefins, in particular from 17 to 78% m of olefins, ( ii) from 22% to 83% m aromatics, and optionally (iii) the rest of the composition consists of (iii) paraffins, and optionally naphthenes.

By way of example, the composition may comprise (i) at least 17% by weight of C5-C10 olefins, in particular from 17 to 78% by weight of C5-C10 olefins, (ii) from 22% to 83% m of aromatics, in particular monoaromatics, in C6-C9, and optionally (iii) the remainder consisting of paraffins in C5-C14, and optionally of naphthenes.

For example, the composition containing olefins can be an essence from a fluid catalytic cracking (FCC) process, an essence from a visbreaking process, or even a light cut from a polyolefin pyrolysis oil.

Step c) is also carried out in the presence of a homogeneous acid catalyst in order to promote the reactions involved (esterification, acetalization, reaction of olefins with carbonyl groups, etc.). It is therefore a liquid catalyst.

This catalyst can be chosen from sulfuric acid, 4-methylbenzenesulfonic acid, benzenesulfonic acid, methylsulfonic acid, preferably sulfuric acid.

Typically, the quantity of homogeneous acid catalyst used represents 0.5 to 3% by mass of the quantity of biomass oil from step a), optionally the quantity of vacuum residue from step b).

Step c) can also be carried out in the presence of a phase transfer agent comprising at least one amine function. In particular, it is possible to use aliphatic amines, in particular monoamines, diamines or triamines. Advantageously, the aliphatic chain of the amine used can have a length similar to the length of the olefins present in the composition containing olefins. Possible aliphatic amines thus include aliphatic amines whose aliphatic chain has 4 to 14 carbon atoms, advantageously 5 to 10 carbon atoms. The quantity of phase transfer agent used can be 0.5 to 6% by mass of the quantity of biomass oil, optionally of the quantity of vacuum residue.

Contacting step c) is typically carried out at a temperature of 50°C to 90°C, optionally from 60 to 80°C or from 65°C to 75°C, or in any range defined by two of these limits.

The water formed during step c) can advantageously be eliminated continuously, in particular extracted continuously, typically by distillation, by applying a pressure adapted to shift the balance of the esterification and/or acetalization reactions and/or or etherification towards the formation of esters and/or acetals and/or ethers. This is therefore an elimination by reactive distillation. However, the water can also be removed discontinuously, for example by a reflux device. Reflux makes it possible in particular to carry out light distillation sufficient to extract water or a water-alcohol mixture depending on the conditions, in particular when scanning with an inert gas is carried out.

The pressure at which step c) is carried out is 200 mbar at atmospheric pressure. This pressure will be chosen so as to eliminate the water without exceeding a temperature of 90°C, advantageously a temperature of 80°C, 75°C or 65°C. This pressure could in particular be chosen according to the presence of a possible heteroazeotrope between the water and the alcohol present in the reaction medium in order to first eliminate the water-alcohol heteroazeotrope by distillation. In other words, when a water-alcohol heteroazeotrope is present, we will place ourselves in temperature and pressure conditions such that the temperature is higher than the boiling temperature of the heteroazeotrope but lower than the boiling temperature of the heteroazeotrope. alcohol, the temperature must also be lower than 90 ° C, as previously described.

For example, when the alcohol from step c(i) or c(iii) has a boiling point below 80°C, such as methanol or ethanol, the elimination of the water can be made at atmospheric pressure. When the alcohol from step c(i) or c(iii) has a boiling point above 80°C, step c) can be carried out under a pressure of 200 to 600 mbar. So, for example, a pressure of 200 to 300 mbar can be used when the alcohol is butanol and a pressure of 500 to 600 mbar can be used when the alcohol is propanol.

Advantageously, step c) can be carried out under sweeping of an inert gas, for example under sweeping of nitrogen (N2). Such scanning can be carried out from the start of step c) in order to eliminate oxygen from the air in the installation, then continued to facilitate the entrainment of water vapors and possibly alcohol, and their elimination. For example, a sweep of 2 to 10L/min can be achieved.

According to the invention, step c) is implemented as described below to allow maximum incorporation of olefins into the matrix of the biomass oil (or its residue under vacuum) and thus the improvement of the quality of the treated oil.

Thus, during step c):

c(i) the biomass oil, preferably the vacuum residue of biomass oil, is first brought into contact with an excess alcohol and the homogeneous acid catalyst, then,

c(ii) a quantity of the composition containing olefins less than or equal to a threshold quantity is added beyond which the reaction medium becomes two-phase,

c(iii) optionally an alcohol fraction is added in a quantity sufficient to maintain an excess of alcohol in the reaction medium,

c(iv) we repeat step c(ii), and optionally step c(iii), until the end of the reaction, then,

c(v) the effluent produced containing the biomass oil is recovered, preferably the residue under vacuum, having a reduced content of compounds containing one or more hydroxyl groups (OH) and/or carbonyl groups (C=0).

Each of these steps can be implemented at a temperature and pressure in the previously mentioned ranges with continuous or non-continuous elimination of the water formed.

In one embodiment, step c(i) is carried out at a temperature and a pressure in the previously mentioned ranges for a duration of 15 minutes to 2 hours, advantageously from 15 minutes to 1 hour 30 minutes, or in any defined range by two of these limits.

In one embodiment, the removal of water can be implemented after the start of step c(i), for example 15 to 60 minutes after the start of step c(i) and continued for the remaining duration of implementation of step c(i), for example for at least another 15 to 30 minutes. As long as the elimination of water has not started, the reaction medium can be heated to reflux. Note that when the water is removed by distillation, the temperature and pressure conditions necessary for distillation can be implemented from the start of step c(i): a distillate is then only obtained from from the moment water is formed within the mixture.

During step c(i), alcohol is added in excess. The amount of alcohol added can be determined based on the content of the biomass oil or a biomass oil residue in carbonyl and/or hydroxyl groups so as to add the alcohol with an excess of the order of 50% m. For example, we could use a biomass oil/alcohol mass ratio of 1/0.5 to 1/4.

Advantageously, during step c(i), the catalyst can be added mixed with the alcohol. This can help prevent premature aging of biomass oil or vacuum residue of biomass oil resulting from high acid concentration.

Step c(ii) is then carried out at a temperature and a pressure in the previously mentioned ranges with continuous or non-continuous elimination of the water formed, typically for a period of 15 minutes to 1 hour, advantageously 15 minutes to 30 minutes or in any interval defined by two of these limits.

During this step c(ii), generally at the beginning, a quantity of the composition containing olefins less than or equal to a threshold quantity is added, beyond which the reaction medium becomes two-phase. In a particularly advantageous embodiment, the quantity added is equal to this threshold quantity, in order to maximize the incorporation of olefins into the biomass oil matrix or the biomass oil residue.

The quantity of composition containing olefins added during step c(ii) however remains less than the total quantity capable of reacting with the hydroxyl functions of the carboxylic acids or alcohols present in the biomass oil or in a residue of biomass oil. Also, according to the invention, this step c(ii) will be repeated until the end of the reaction.

The reaction with the olefin-containing composition is considered to be complete when the olefins no longer react with the biomass oil, or the vacuum residue of biomass oil. The end of the reaction can be determined by monitoring the amount of olefins present in the extracted water or in the extracted water-alcohol mixture. As long as the olefins react with the matrix, they are in fact absent from the extracted water or from the extracted water-alcohol mixture. The reaction can thus be considered complete from the moment olefins are detected (present) in the extracted water or in the extracted water-alcohol mixture, for example by means of the ASTM D1159-07R17 standard. Depending on the alcohol used, when a two-phase water-alcohol mixture is extracted, the olefins may be present mainly in the alcohol. The end of the reaction is then determined when olefins are detected in the alcohol. In other cases, this detection is carried out in the extracted water-alcohol mixture.

It should be noted that the esters and ethers formed during the reaction of carboxyl or alcohol groups with alcohols are miscible with olefins. Thus, as they are formed, the threshold quantity of composition beyond which the reaction medium becomes biphasic increases and it is thus possible to increase the maximum quantity of the composition containing olefins added during a step. c(ii).

The water being eliminated (extracted), continuously or not, during step c), depending on the temperature and pressure conditions and the type of alcohol used, part of the alcohol can be carried away with the water eliminated. It may then prove necessary during step c(iii) to regularly add an alcohol in a sufficient quantity to maintain an excess of alcohol in the reaction medium and/or to maintain a constant alcohol concentration in the medium. reaction.

Step c(iii) is carried out at a temperature and a pressure in the ranges previously mentioned with elimination, continuously or not, of the water formed, typically for a period of 15 minutes to 1 hour, advantageously of 15 minutes to 30 minutes.

This step c(iii) can be implemented at the same time, before or after step c(ii). When steps c(ii) and c(iii) are carried out at the same time, and therefore under the same conditions of temperature, pressure and duration, the alcohol can be added mixed with the composition containing olefins, or not.

The alcohol added in step c(iii) may be the same as that added in step c(i) or not. When the alcohol is different, we will then use an alcohol having a number of carbons greater than the number of carbons of the alcohol added in the previous step (namely step c(i) or a previous step c(iii) ). This prevents the presence of an alcohol with a long carbon chain from shifting the balance of reactions carried out in the presence of an alcohol with a shorter carbon chain.

Also, during each step c(i) and c(iii) of step c), only one alcohol is added and not a mixture of alcohols.

When during step c(iii) an alcohol different from that of step c(i) or step c(iii) previously implemented is added, this step c(iii) can be implemented implemented when the shortest alcohol has reacted with the highest possible desired yield. Ideally, the new alcohol is added while there is still alcohol from the previous step in the mixture, the latter being advantageously eliminated by distillation after addition of the new alcohol. This elimination can be easily carried out to the extent that the previous alcohol has a shorter chain and therefore a lower boiling point than the new alcohol. By removing the lighter alcohol after adding the heavier alcohol, it is possible to prevent the biomass oil (or a biomass oil RSV) from being in contact only with the acid catalyst, which could cause premature aging.

The invention thus provides c(iv) to repeat step c(ii), and optionally step c(iii) until the end of the reaction.

The end of the reaction can occur when olefins appear in the eliminated fraction. The end of the reaction can thus be followed by analyzing the quantities of olefins present in the extracted water or in the extracted water-alcohol mixture.

At the end of the reaction, c(v), the effluent produced containing the biomass oil is recovered, optionally the vacuum residue of biomass oil, having a reduced content of oxygenated compounds containing at least one hydroxyl group and/or or carbonyl, and in particular a carboxyl group.

Step d) separation of the effluent

The effluent from step c(v) contains the homogeneous acid catalyst, unreacted alcohol, optionally unreacted olefins, or even the transfer agent.

Separation step d) consists of eliminating the homogeneous acid catalyst by precipitation, in particular by bringing it into contact with a precipitation agent. This precipitating agent is typically a basic compound and/or a weak acid salt.

The quantity of precipitating agent used is sufficient to cause precipitation of all of the catalyst used in step c. This quantity can represent 110 mol% of the acid catalyst used during step c.

This step may comprise d(i) bringing the effluent from step c) into contact with the precipitating agent, in particular a basic compound or a weak acid salt, to form a precipitate with the homogeneous acid catalyst. , then d(ii) separating the effluent from the precipitate formed, optionally from the remaining precipitating agent.

The precipitating agent used during step d(i) to precipitate the homogeneous acid catalyst can advantageously be insoluble in the effluent in order to allow its separation from the effluent at the same time as the precipitate.

For example, calcium carbonate, strontium carbonate, barium carbonate, magnesium carbonate, calcium hydroxide, strontium hydroxide, barium hydroxide, hydroxide can be used as a precipitating agent. magnesium, and salts of these compounds, alone or in mixtures.

Step d(ii) can be carried out by filtration, hydrocyclone, decantation, centrifugation or by two or more of these techniques.

Step d(ii) can be followed by (iii) an optional step of washing the precipitate with an alcohol, preferably with the same alcohol as the alcohol used during step c(i) in the absence of steps c(iii) or that the alcohol used during the last step c(iii) implementation. This makes it possible to recover the effluent adsorbed on the precipitate and thus increase the total quantity of effluent recovered.

Stage e) of purification

The effluent from step d) generally comprises alcohol, and optionally olefins, which have not reacted during step c). Purification step e) makes it possible to eliminate the alcohol present as well as the light fractions. It is typically carried out by distillation, atmospheric or under vacuum.

Distillation is advantageously carried out at low temperature in order to avoid decomposition of the effluent. Typically, this distillation is carried out at a temperature of 65 to 90°C under a pressure ranging from 200 mbar to atmospheric pressure.

Step e) thus makes it possible to recover the biomass oil (or the vacuum residue of biomass oil) treated by esterification and/or acetalization and/or etherification.

Subsequent treatments

The effluent from step d), advantageously the effluent from step e) can then be treated, alone or mixed with a hydrocarbon feed of fossil origin, in one or more refining units such as a cracker fluidized bed catalyst, a hydrocracker, a catalytic hydrogenation unit, a hydrotreatment unit, or even be used as is or separated into streams usable for the preparation of fuels such as LPG, gasoline, diesel, heavy fuel oil , for the preparation of lubricants and/or for the preparation of special fluids.

Examples

In the examples the following notations were used:

HPB: wood pyrolysis oil,

RSV: vacuum residue (from a biomass oil),

RSV-E: esterified vacuum residue, recovered at the end of the reaction after precipitation of the catalyst and after elimination of the excess alcohol present.

Example 1 – Vacuum distillation of a biomass oil

A biomass oil, here an HPB wood pyrolysis oil, was distilled under vacuum using a rotary evaporator. Vacuum distillation was carried out under a pressure of 85 mbar and a temperature of 70 °C. The vacuum residue from this distillation is called “RSV”. After 3 hours of distillation, the RSV represents 76.4% of the initial mass of biomass oil.

The characteristics of the oil and the residue are summarized in Table 2. Note that the dynamic viscosity of RSV cannot be measured at 25 °C (RSV completely frozen), the dynamic viscosity of RSV is 725mPa/s at 80 °C.

Unit HPB RSV Water content by Karl-Fischer ASTM D6304-20 %m 22.72 2.82 TAN ASTM D664-18e2 mg KOH/g 178.86 206.6 Contents (1) Carbon ASTM D5291-21 %m 45.4 57.2 Hydrogen ASTM D5291-21 % m 7.37 6.51 Nitrogen ASTM D5291-21 %m <0.3 0.34 Sulfur ASTM D5291-21 %m <0.5 <0.5 Oxygen ASTM D5622-17 %m 46.43 35.49 Contents (2) Carbon ASTM D5291-21 % m 58.74 58.86 Hydrogen ASTM D5291-21 % m 6.27 6.39 Nitrogen ASTM D5291-21 % m <0.39 0.35 Sulfur ASTM D5291-21 %m <0.65 <0.51 Oxygen ASTM D5622-17 % m 33.9 33.9 CCR ASTM D482 %m 18.5 22.49

(1): Total contents, including oxygen and hydrogen from water

(2): Contents calculated after subtraction of water from the composition

Example 2 – treatment of RSV with butanol and octene

The RSV of Example 1 was treated according to the following procedure in the presence of butanol (BuOH) and 1-octene.

A mixture of butanol and RSV in a mass ratio 1:1.67 is introduced into a 5000 mL three-necked flask equipped with a thermometer, a Soxhlet extractor and a magnetic stirrer. The homogeneous catalyst used is pure sulfuric acid, added in a quantity representing 2% m of the RSV. The catalyst is mixed with the butanol before mixing the latter with the RSV to avoid aging of the RSV by contact with the concentrated acid.

The butanol/RSV mixture is made hot (50°C). Then, 0.16 equivalents of 1-octene (i.e. 16 g of 1-octene per 100 g of RSV) is introduced into the flask and the mixture is heated to 70°C in half an hour.

The mixture is maintained at 70°C for 4.5 hours (TEST 1) or 5 hours (TEST 2) under 300 mbar and nitrogen flow. After an hour, the water is distilled in the form of a heteroazeotrope. After one hour and at regular intervals of 30 minutes, butanol is added to compensate for the evaporated butanol and maintain a 1:1.67 mass ratio of butanol/RSV in the mixture. The quantity of butanol added each time is equivalent to that recovered in the distillate at these intervals.

Over the 4.5 hours of reaction of TEST 1, 35 g of an aqueous phase containing 92.30% m water and 7.70% m BuOH are recovered (which represents 32.30 g of pure water and 2.69 g BuOH) and 180 g of an alcoholic phase containing 79.90% m BuOH and 20.10% water (which represents 143.82 g pure BuOH and 36.18 g H ₂ O). This same total quantity of butanol (143.82 + 2.89 g) is added in portions according to the previous paragraph.

For TEST 2, at the end of the 5 hours of reaction, a total quantity of 103 g of water and 163 g of butanol was recovered.

At the end of the reaction time, 12 g of CaCO ₃ were then added to the reaction mixture in order to neutralize the sulfuric acid by precipitation. The mixture containing the precipitate is then subjected to membrane filtration on a Teflon membrane filter with a porosity of 0.45 μm under a pressure of 6 bar. The separated solid is then washed with butanol to recover all the treated RSV. Then, vacuum distillation was carried out for 7 hours at a temperature of 60°C to 75°C and a pressure of 300 mbar in order to eliminate the alcohol present and obtain the esterified residue denoted RSV-E. For TEST 1, a quantity of 787 g of RSV-E is recovered while 1761 g of RSV-E was recovered during TEST 2. In both cases, the RSV-E is in the form of a monophasic liquid with little viscous brown in color.

The quantities of reagents and products used in TEST 1 and TEST 2 are summarized in Table 3. The mass gain of RSV-E is calculated according to the following formula: ((RSV-E mass-RSV mass)*100/ RSV mass).

Unit Test 1 Test 2 Test 3 Reaction time h 4.5 5 7 Reaction temperature °C 70 70 70 Nitrogen flow dl/min 3-4 3-4 3-4 RSV mass g 484 972.5 500 Catalyst g 9.68 10 10 Alcohol mass g 807.6 1618.01 785 Mass of 1-octene g 80.6 163 335 Total quantity of water extracted g 48.38 103 57 Total amount of alcohol extracted g 66.61 163 210 RSV-E: quantity of esterified RSV g 787.52 1761 893 RSV-E mass gain % m 62.71 81.08 78.60

In summary, the mass balance for TEST 1 is as follows, for an initial RSV mass of 484 g, 80.6 g of 1-octene (corresponding to the added 1-octene) and 223 g of butanol were fixed on butanol, and 609.6 g of BuOH are recovered which can be recycled.

The RSV-E characteristics of the two tests are collected in Table 4.

Unit TEST 1 TEST 2 TEST 3 RSV-E ASTM D664-18e2 TAN mg KOH/g 64.21 61.76 35.33 CCR ASTM D482 % m 20.72 17.87 10.45 Dynamic viscosity at 25°C mPa/s 107.6 86.2 56.3 RSV-E density
ISO 3507:1999 Kg/m3 1028 1009.7 910 Organic elements C ASTM D5291-21 %m 60 63.6 63.8 H ASTM D5291-21 %m 8.6 9.55 11.5 N ASTM D5291-21 % m <0.3 <0.3 <0.3 S ASTM D5291-21 % m 0.55 <0.5 <0.5 Y ASTM D5622-17 % m 25.9 25.1 23.1

Example 3 - treatment of RSV with butanol and octene

The RSV of Example 1 was treated in the presence of butanol and 1-octene. Unlike example 2, the 1-octene was added several times.

The test was carried out as follows. A mixture of butanol and RSV in a mass ratio 1:1.57 is introduced into a 5000 mL three-necked flask equipped with a thermometer, a Soxhlet extractor and a magnetic stirrer. The homogeneous catalyst used is pure sulfuric acid, added in a quantity representing 2% m of the RSV. The catalyst is mixed with the butanol before mixing the latter with the RSV.

The butanol/RSV mixture is produced at 50°C and 0.67 equivalents of 1-octene (i.e. 0.67 g of 1-octene per 100 g of RSV), corresponding to a quantity of 335 g, is introduced into the balloon in 4 times from the beginning with intervals of one hour: the first 3 additions are 83 g each and the fourth addition is 86 g.

The mixture is maintained at 70°C for 7 hours under a pressure of 300 mbar. Throughout the reaction, water is distilled in the form of a heteroazeotrope. A quantity of 57 g of water and 210 g of butanol was recovered.

Then, an amount of 12 g of CaCO ₃ was added to the esterified RSV to neutralize the sulfuric acid. The removal of the homogeneous catalyst is carried out by precipitation as in Example 2, and the treated RSV is recovered. Then, vacuum distillation of the treated RSV was carried out for 7 hours under the same conditions as Example 2 in order to eliminate the excess alcohol and recover the esterified RSV (RSV-E). A quantity of 805 g of RSV-E was recovered in the form of a low-viscosity, brown-colored single-phase liquid.

The quantities of reagents and products used are summarized in Table 3 (see TEST 3). The RSV-E characteristics of this test are summarized in Table 4 (see TEST 3).

Example 4 - treatment of an RSV with methanol

The RSV of Example 1 was treated in the presence of methanol.

The test was carried out as follows. A mixture of methanol and RSV in a mass ratio 1:2.54 is introduced into a 500mL three-necked flask equipped with a thermometer, a soxhlet extractor and a magnetic stirrer. The homogeneous catalyst used is pure sulfuric acid, added in a quantity representing 2% m of the RSV. The catalyst is mixed with the methanol before mixing the latter with the RSV.

The reaction medium remained at room temperature for 5 days. The mixture is then heated to 60°C for 2 hours under atmospheric pressure. Throughout the reaction, a non-azeotropic water-methanol mixture is distilled. A quantity of 161 g of this mixture was recovered at the end of the reaction.

Then, an amount of 3 g of CaCO ₃ was added to the esterified RSV to neutralize the sulfuric acid. The removal of the homogeneous catalyst (2% by weight of sulfuric acid) was carried out by precipitation following the same procedure as that of Example 2 and the treated RSV was recovered. Then, vacuum distillation of the treated RSV was carried out for 2 hours under the same conditions as Example 2 in order to recover the esterified RSV (RSV-E). A quantity of 75 g of RSV-E was recovered in the form of a low-viscosity, brown-colored single-phase liquid.

The quantities of reagents and products used in this TEST 4 are summarized in Table 5.

Unit TEST 4 Reaction time h 2 Reaction temperature °C 60 Nitrogen flow l/min 3-4 RSV mass g 51 Catalyst g 1.02 Alcohol mass g 130 Mass of 1-octene g 0 Total amount of alcohol-water mixture extracted g 161 RSV-E: quantity of esterified RSV g 75 RSV-E mass gain %m 47.06

The RSV-E characteristics of this test (TEST 4) are summarized in Table 6.

Unit TEST 4 TAN of RSV-E Mg KOH/g 129.2 CCR % m 35.03 RSV-E density Kg/m3 1145.4 Organic elements C ASTM D5291-21 %m 57.1 H ASTM D5291-21 %m 7 N ASTM D5762-18a mg/l 622.75 ASTM D5291-21 %m 0.73 Y ASTM D5622-17 %m 31.4

Example 5 - treatment of an RSV with methanol in the presence of FCC gasoline

The RSV of Example 1 was treated according to the following procedure in the presence of methanol (MeOH) and an FCC gasoline.

FCC gasoline includes 17% m C5-C10 olefins, 22% m C6-C9 aromatics, the remainder consisting of C5-C14 paraffins.

We first introduce the RSV, the methanol and the pure H ₂ SO ₄ catalyst (2% m of the RSV) into a three-necked flask of 5000 mL. After 2 hours 10 minutes of slow distillation, 624 g of FCC gasoline are added in three batches (208 g per addition) to achieve a mass ratio (RSV: FCC gasoline: MeOH) of (1: 1.25: 1.57). The esterification was carried out at 60°C for 2h30; the reaction medium also presented a two-phase mixture. In order to improve the miscibility of the system, a quantity of 15 g of octylamine was added (phase transfer agent which corresponds to 0.7% m of RSV), and the reaction was continued for 1h30 at 60°C. In order to improve the miscibility of the system, the reaction medium remained stirred at room temperature for 48 hours, then under reflux for 3 hours at 60-65°C (a slight distillation by evaporation therefore takes place). A reduction in the upper phase was noted. The non-azeotropic methanol-water mixture was distilled, and 337 g of distillate was recovered. Then, a quantity of 12 g of CaCO ₃ was added to the esterified RSV to neutralize the sulfuric acid and recover the treated RSV. The elimination of the homogeneous catalyst was carried out by precipitation according to the same procedure as Example 2. Before proceeding with the distillation of the excess alcohol, the upper phase was isolated which presented a quantity of 152 g probably of FCC gasoline and volatile organic compounds via a separatory funnel under reduced pressure. Then, a vacuum distillation of the treated RSV was carried out for 2h15 under the same conditions as Example 2 in order to eliminate the excess alcohol and recover the esterified RSV (RSV-E). A quantity of 511 g of RSV-E was recovered in the form of a low-viscosity, brown-colored single-phase liquid.

The quantities of reagents and products used in this TEST 5 are summarized in Table 7.

Unit TEST 5 TEST 6 TEST 7 Reaction time h 2+2.5+1.5+3 5+4 8+3+5 Reaction temperature °C 60-65 70 65-70 Nitrogen flow l/min 3-4 3-4 3-4 RSV mass g 500 500 332 Catalyst g 10 12 6.6 Mass of methanol or butanol* g 785 835* 750+585* Mass of 1-octene or gasoline** g 624** 500** 240+312** RSV-E: quantity of esterified RSV g 511*** 890 655 RSV-E mass gain %m - 78.00 97.29

***losses during filtration.

The RSV-E characteristics of this test (TEST 5) are summarized in Table 8.

Unit TEST 5 TEST 6 TEST 7 TAN of RSV-E mg KOH/g 95 47 24 CCR %m 24.8 24.24 6.9 Dynamic viscosity at 25°C mPa/s 153 120 35 DSV-E density Kg/m3 1092.7 1125 904.9 Organic elements C ASTM D5291-21 %m 54.1 64.6 64.5 H ASTM D5291-21 %m 8 8.38 11.5 N [1]: ASTM D5291-21 / [2]: ASTM D5762-18a <0.3%m [1] 603 ppm [2] 81 ppm [2] ASTM D5291-21 %m 0.9 <0.5 <0.5 Y ASTM D5622-17 % m 36.7 25.1 22.69

Example 6 - treatment of an RSV with butanol in the presence of FCC gasoline

The RSV of Example 1 was treated according to the following procedure in the presence of butanol (BuOH) and an FCC gasoline.

The FCC gasoline is identical to that of example 5.

The RSV, butanol, and the pure H ₂ SO ₄ catalyst (2% m of the RSV) are introduced into a three-necked 5000 mL flask. Esterification is carried out at 70°C for 5 hours under a pressure of 300 mbar. After one hour of reaction, the FCC gasoline is added (the mass ratio RSV: BuOH: FCC is 1:1.67:1). After these 5 hours of esterification, the reaction is continued for 4 hours during which the water has been distilled in the form of heteroazeotrope. A quantity of 286 g of butanol and 86 g of water was recovered. Then, a quantity of 12 g of CaCO ₃ was added to the esterified RSV to neutralize the sulfuric acid and recover the RSV treated according to the same procedure as that described in Example 2. Then, vacuum distillation of the treated RSV was carried out for 7 hours under the same conditions as Example 2 in order to eliminate excess alcohol and esterified RSV (RSV-E). A quantity of 655 g of RSV-E was recovered in the form of a low-viscosity, brown-colored single-phase liquid.

The quantities of reagents and products used in this TEST 6 are summarized in Table 7. The characteristics of the RSV-E of this test (TEST 6) are summarized in Table 8.

Example 7 - treatment of an RSV with methanol then butanol in the presence of 1-octene and FCC gasoline

The aim is to demonstrate the possibility of introducing both a mixture of alcohol and olefins. RSV of example 1 was processed according to the following procedure:

RSV and methanol are successively introduced in a mass ratio 1:1.5 into a three-necked 5000 mL flask. Then, the introduction of 2% m of pure H ₂ SO ₄ (relative to the RSV) with 11% by mass of MeOH relative to the RSV is carried out, and the system is maintained under reflux for 8 hours at 65°C (a slight distillation by evaporation therefore takes place). 30% m (relative to RSV) of butanol doped with 0.16 eq of 1-octene (16% m relative to RSV) are then introduced, then the reaction medium is maintained under reflux for 3 h at 65-70 °C with the distillation of the non-azeotropic mixture (MeOH-H ₂ O). During this time, the progressive addition of (3*195 g) of butanol doped with (3*80 g) of octene is carried out in order to achieve a mass ratio RSV: BuOH: octene of 1: 1.67: 0 ,64. A single phase is observed at this stage. Then we try to react more different alkenes by adding 0.94 eq of Naphtha-type FCC gasoline (the same as that in the previous examples). The reaction medium remained under light distillation for 5 h at a temperature of 70° C. under a pressure of 300 mbar to react the alkenes contained in the FCC naphtha gasoline. After neutralization with CaCO ₃ and filtration, the remaining butanol is distilled off. 131 g of a phase composed mainly of hydrocarbons and butanol and 391 g of another heavier and more polar phase (water + traces of methanol) are recovered. A quantity of 655 g of RSV-E is recovered in the form of a low-viscosity, brown-colored single-phase liquid.

The quantities of reagents and products used in this TEST 7 are summarized in Table 7. The characteristics of the products of this test (TEST 7) are summarized in Table 8.

Claims (12)

Process for treating a biomass oil, comprising:
a) the provision of a biomass oil comprising oxygenated compounds containing at least one hydroxyl group and/or at least one carbonyl group, the biomass oil being chosen from a biomass pyrolysis oil, a hydrothermal liquefaction oil biomass and their mixtures,
b) an optional step of vacuum distillation of the biomass oil supplied by step a) to obtain a distillate and a residue under vacuum,
c) a step of bringing the biomass oil from step a), optionally the vacuum residue from step b), into contact with at least one alcohol and a composition containing olefins in the presence of a catalyst homogeneous acid at a temperature less than or equal to 90°C, under a pressure of 200 mbar at atmospheric pressure for 30 minutes to 24 hours to carry out at least one of the following reactions: esterification of the carboxyl groups, acetalization of the carbonyl groups, an etherification of the hydroxyl groups, the contacting being carried out by eliminating the water formed by one or more of the aforementioned reactions, and during which:
c(i) the biomass oil, optionally the residue under vacuum, is brought into contact with an excess alcohol and the homogeneous acid catalyst, then
c(ii) a quantity of the composition containing olefins less than or equal to a threshold quantity is added beyond which the reaction medium becomes two-phase,
c(iii) optionally, an alcohol is added in a sufficient quantity to maintain an excess of alcohol in the reaction medium,
c(iv) we repeat step c(ii), and optionally step c(iii), until the end of the reaction,
c(v) the effluent produced containing the biomass oil is recovered, optionally the residue under vacuum, having a reduced content of oxygenated compounds containing at least one hydroxyl and/or carbonyl group,
d) a step of separating the effluent recovered in step c(v) during which the homogeneous acid catalyst is eliminated by precipitation. Treatment method according to claim 1, wherein each added alcohol is miscible with the biomass oil of step a) or with the vacuum residue of step b). Treatment method according to claim 1 or 2, in which at each implementation of step c(iii), the alcohol added is identical to the alcohol added in the previous step or is an alcohol having a number of carbons greater than the number of carbons of the alcohol added in the previous step. Treatment method according to any one of claims 1 to 3, wherein the olefin-containing composition comprises (i) at least 17% m olefins, optionally from 17 to 100% m olefins, (ii) 22 % to 83% m of aromatics when it is not entirely made up of olefins, and optionally (iii) the remainder being made up of paraffins, and optionally naphthenes. Treatment method according to any one of claims 1 to 4, in which the contacting step c) is carried out at a temperature of 50°C to 90°C, optionally 60 to 80°C or 65°C to 75°C. Treatment process according to any one of the preceding claims, characterized in that the quantity of homogeneous acid catalyst used represents 0.5 to 3% by mass of the quantity of biomass oil, optionally vacuum residue. Treatment process according to any one of the preceding claims, in which the homogeneous acid catalyst is chosen from sulfuric acid, 4-methylbenzenesulfonic acid, benzenesulfonic acid, methylsulfonic acid, preferably sulfuric acid. Treatment method according to any one of the preceding claims, in which step c) is carried out in the presence of a phase transfer agent comprising at least one amine function. Treatment process according to any one of the preceding claims, in which separation step d) comprises d(i) bringing the effluent from step c) into contact with a basic compound or an insoluble salt of weak acid to form a precipitate with the homogeneous acid catalyst, d(ii) the separation of the precipitate formed from the effluent, d(iii) optionally a washing step with an alcohol. Treatment process according to any one of the preceding claims, further comprising a step e) of purifying the effluent from step d) during which the unreacted alcohol(s) are removed by distillation. Treatment method according to any one of the preceding claims, in which the biomass oil of step a) comes from a biomass chosen from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard , organic waste, alone or mixed. Process according to any one of the preceding claims, in which the effluent from step d) or step e) is:
f) treated in a fluidized bed catalytic cracker, and/or
g) treated in a hydrocracker, and/or,
h) treated in a catalytic hydrogenation unit, and/or
i) treated in a hydrotreatment unit, and/or
j) used as such or separated into usable streams for the preparation of fuels such as LPG, gasoline, diesel, heavy fuel oil, for the preparation of lubricants and/or for the preparation of special fluids.