WO2017077090A1 - Method and facility for chemically converting carbonaceous material by means of top gas quenching - Google Patents

Abstract

The present invention relates to a method for chemically converting carbonaceous material comprising at least the steps of: (a) gasifying said carbonaceous material in an entrained-flow or fluidized-bed reactor by means of which a synthesis gas is produced, (b) subjecting said synthesis gas to quenching by adding a quenching fluid thereto, (c) subjecting the quenched effluent to a purification treatment, (d) subjecting the purified effluent to a catalytic synthesis reaction using CO and H2 as reagents by means of which a gaseous effluent and a liquid effluent are obtained, all or a portion of the gaseous effluent obtained in step (d) being used in step (b) as a quenching fluid. The present invention also relates to a facility capable of being implemented during such a method.

Description

 METHOD AND INSTALLATION FOR CHEMICAL CONVERSION

 OF CARBONACEOUS MATERIAL WITH HEATED GAS TEMPERATURE

DESCRIPTION

TECHNICAL AREA

The present invention relates to the general field of recovery of the carbonaceous material and in particular the thermochemical treatment of the carbonaceous material to produce liquid hydrocarbons, (biofuels), petrochemical bases and / or synthetic chemicals.

 More particularly, the present invention relates to a process for the chemical transformation of a carbonaceous material via a gasification and a catalytic synthesis reaction using as reagents carbon monoxide or dihydrogen, said process having a step of quenching the synthesis gas from the gasification of the carbonaceous material using the overhead gas obtained following said catalytic synthesis reaction. The present invention also relates to an installation for implementing such a method.

STATE OF THE PRIOR ART

As a result of the growing demand for energy and the decline in fossil fuels, there has been a particular interest in the energy recovery of biomass and waste such as organic waste.

Thus, the current processes under study or pilot scale, for converting biomass into biofuel by an FT synthesis (for "Fischer Tropsch"), go through a step of gasification of the biomass with steam. water to obtain a synthesis gas consisting essentially of CO and H ₂ . FT synthesis allows from a ratio H ₂ / CO = 2 to obtain chains -CH ₂ - similar to that of the gas oil.

The initial gasification is carried out either in a fluidized bed reactor or in a driven flow reactor. Fluidized bed reactors are less efficient because of the reaction temperature generally between 800 ° C and 1000 ° C, which leads to a lower conversion of biomass to CO + H2 with, for example, the generation of methane (CH ₄ ). They do not require specific preparation of the biomass other than drying and medium grinding, which induce only a small loss of efficiency of the overall process. They can be adapted to the production of synthetic natural gas (or SNG for "Synthetic Natural Gas").

 Driven flow reactors have an excellent efficiency of converting biomass to CO + H2 and are therefore very suitable for the production of fuels or synthetic chemicals from biomass. They therefore serve as a reference in the field of BtL type fuels (for "Biomass to Liquid"). However, they require a thermal pretreatment of the biomass so that it can be finely ground and injected easily, which introduces a loss of mass and / or energy for the process.

 The heat of the process is generally provided by the combustion of a part of the biomass (raw biomass, gas, solid residues, tars, etc.); in this case, the process is called autothermal. Part of the biomass carbon is therefore not converted to biofuel.

 The heat input of the process may be external and, preferably, of nuclear electrical origin without CO2 emission; in this case, the process is said to be allothermal, and the mass yield is higher than that obtained with an autothermal process.

 In processes involving driven flow reactors, a quench ("quench", according to the English terminology) is required at the reactor outlet. It aims to cool down the synthesis gas quickly to stop the ongoing reactions and to cut down some pollutants and particles.

With the exception of the case adapted to the Shell process and described by Martelli et al, 2011 [1] in which the cooling of the gas is done without contact with another flow but with a high temperature exchanger, quenching is typically carried out by adding from a cold flow to the stream of hot synthesis gas at the outlet of the reactor. Thus, there are three major quenching families which use (1) a liquid stream, the most common being water quenching, (2) a solid stream and (3) a gas stream. Various patents, patent applications and publications cover all of these quenching techniques.

 As examples of processes involving quenching with a liquid flow and in particular water, mention may be made of the patent application US 2007/062117 [2]. The method that is the subject of the latter comprises in particular a gasification step, in a driven flow reactor, of a suspension obtained by mixing carbonaceous material to be treated with water or oil and a total quenching step of synthesis gas produced by water injection. In this document, the carbonaceous material to be treated is advantageously bituminous coal, cokes such as oil or bituminous coal or lignite coal. US Patent Application 2007/051044 [3] is another example of a gasification process involving quenching with water.

 Liquid streams other than water are also conceivable. Thus, US Pat. No. 5,433,760 [4] describes a first step of quenching the synthesis gas using a liquid carbon quenching medium associated with a small amount of carrier gas, typically nitrogen, cooled and recycled synthesis gas, water and carbon dioxide. Liquid carbon quenching media include liquid hydrocarbons, asphalt, diesel, residual fuel oils, coal tar, organic waste and amines.

Quenching with a solid flow is in particular envisaged in international application WO 94/26850 [5]. The latter proposes to use pulverulent coal associated with a small amount of nitrogen or carbon dioxide, as carrier gas, in a first step of quenching the synthesis gas. In addition, the CarboV process from Choren relies on quenching with a solid flow while associating it with a recycling process flow. Indeed, the coal resulting from a first stage of biomass transformation (pyrolysis) is reinjected at the outlet of the gasification reactor to perform quenching. This process has been presented several times in international conferences and in particular in 2005 [6]. It should also be noted that US Patent 5,433,760 [4] and International Application WO 94/26850 [5] both provide a second quenching step performed on the synthesis gas having already undergone the first quenching step. In this second quenching step, the quenching stream is gaseous and in particular selected from nitrogen, a cooled and recycled synthesis gas, water and steam. Finally, quenching by gas flow at the reactor outlet and using the recycling of raw synthesis gas was presented in 2012 at the XtL Freiberg conference [7].

 At present, one can consider, as a reference in a fuel synthesis process from biomass involving gasification and FT synthesis, the following sequence of steps:

 preparation of biomass;

 gasification in a driven flow reactor;

 quenching as previously envisaged;

 cleaning of synthesis gas;

 - FT synthesis and

 possible recycling of by-products of synthesis by reforming or high-temperature stage [8].

 Figures 1A to 1E repeat this sequence of steps including the features related to different types of quenching previously mentioned.

 These different types of quenching have a number of disadvantages.

 Thus, in the case of quenching with a liquid flow and in particular with water and in the case of quenching with gas flow and in particular by recycle of synthesis gas, only the sensible heat is used to lower the temperature of the output stream. . In this case, the advantage of using a reaction enthalpy does not exist and the material yield (carbon conversion) is not increased.

In contrast, for solid flow quenching, sensible heat and reaction enthalpy are used to lower the temperature of the output stream. However, in this type of quenching, the solid is only a part of the total incoming solid flow. There is no increase in carbon yield by recycling. The conversion of the solid is generally difficult and incomplete. Furthermore, there are technological difficulties of solid injection and fouling problems at the reactor outlet including soot and inorganic compounds. Equipment wear due to abrasion is generally noted.

 In addition, in the case of quenching with a liquid flow and in particular with water, it is impossible to recover the vaporization energy of the liquids at high temperature. It follows therefore a loss of energy efficiency.

 Finally, all the processes shown diagrammatically in FIGS. 1A to 1E show a conversion reaction from carbon monoxide to steam, also called a "Water Gas Shift" reaction, which results in a loss of carbon and therefore a decrease in material yield. It should be noted, however, that this reaction may not be present for quenching other than liquid flow quenching and especially water quenching.

 The inventors have therefore set themselves the goal of proposing a process for converting biomass and more particularly any carbonaceous material, in which the material and energy yield can be increased when compared to the processes of the prior art.

DISCLOSURE OF THE INVENTION The invention proposes a method and an installation making it possible to overcome all or part of the disadvantages and difficulties encountered in the processes and installations of the prior art.

Indeed, the present invention provides a method and an installation for producing liquid hydrocarbons, (biofuels), petrochemical bases and / or synthetic chemicals from a carbon resource, by implementing a step gasification process in a flow-through reactor and a Fischer-Tropsch type synthesis step with increased material and energy yields compared to the methods of the prior art. The work of the inventors has shown that this object could be achieved by using, during quenching of the synthesis gas resulting from the gasification step, a by-product corresponding to the gaseous effluent resulting from the Fischer-Tropsch synthesis. also known as "overhead gas". In such a system, four advantages are cumulated with:

 (i) recycling a carbon stream i.e. the overhead gas allowing an increase in carbon yield,

 (ii) a use of the reaction enthalpy to lower the temperature of the outgoing flow which leads to an increase in energy efficiency and

 (iii) recovering the sensible energy possible over a wider temperature range by avoiding the stress related to the condensation of water at 100 ° C, also allowing an increase in energy efficiency; and

 (iv) a possible absence of conversion reaction of carbon monoxide to steam i.e. a possible absence of reaction of "Water Gas Shift" also allowing an increase in carbon yield.

 Remarkably, the present invention applies not only to the chemical conversion processes of the carbonaceous feed involving a gasification step and a chemical synthesis step of Fischer-Tropsch type but, more generally, to any chemical conversion process. involving a gasification step and a chemical synthesis step in which the catalytic chemical reaction implemented uses as reagents carbon monoxide (CO) and dihydrogen (hh) and produces a recoverable liquid effluent and a recyclable gaseous effluent.

 Likewise, the present invention applies not only to chemical conversion processes of the carbonaceous feedstock implementing not only a driven flow reactor but also a fluidized bed reactor.

In fact, the present invention proposes a method for combining, in a single step, the quenching of the synthesis gas obtained via the gasification step and the recycling of the gaseous effluent resulting from the subsequent chemical synthesis. Until now, this quenching and recycling corresponded to two independent steps in the processes for converting the carbonaceous material. Thus, the present invention relates to a method of chemical transformation of a carbonaceous material comprising at least the steps of:

 a) gasifying said carbonaceous material in a driven-flow or fluidized-bed reactor whereby synthesis gas is produced;

 b) subjecting the synthesis gas produced in step (a) to quenching by adding to said synthesis gas a quenching fluid;

 c) subjecting the quenched effluent obtained in step (b) to a purification treatment;

d) subjecting the purified effluent obtained after step (c) to a catalytic synthesis reaction using as reagents carbon monoxide (CO) and dihydrogen (H ₂ ) whereby a gaseous effluent and a liquid effluent are obtained ;

 all or part of the gaseous effluent obtained during step (d) being used as quenching fluid during step (b).

By "chemical transformation of a carbonaceous material" is meant a process for producing from a carbonaceous material at least one compound selected from the group consisting of liquid hydrocarbons, (biofuels), petrochemical bases, synthetic chemicals or precursors thereof. By way of illustrative and nonlimiting examples of such compounds, mention may be made of alkanes, alkenes, alcohols such as methanol or ethanol, ethers such as dimethyl ether, synthetic paraffins, gasoline, kerosene, diesel, petrochemical naphtha, lubricating oils or any of their precursors.

 Depending on the carbonaceous material used, the process according to the present invention is similar to a BtL (for "Biomass to Liquid") process, a CtL (for "Coal to Liquid") process or a GtL process (for "Gas to Liquid").

By "carbonaceous material" is meant a material of which at least one of the constituents is an organic, synthetic or natural compound. Any carbonaceous material, solid, liquid or gas, known to those skilled in the art can be used in the context of the present invention. In a particular embodiment, the carbonaceous material is in solid form and is optionally associated with a carbonaceous material, of identical or different nature, in solid, liquid and / or gaseous form.

 Advantageously, the carbonaceous material used in the context of the present invention is chosen from the group consisting of natural gas, shale gas, crude oil, light naphtha, heavy fuel oil, coal, bituminous coal, cokes such as oil or bituminous coal, lignite coal, tar sands, oil shale, organic matter of animal or vegetable origin (also known as "biomass"), an organic matter human activities and any of their mixtures.

 In a particular embodiment, the carbonaceous material is an organic material of animal or vegetable origin or an organic material resulting from human activities. More particularly, the carbonaceous material used in the context of the present invention is chosen from the group consisting of agricultural productions such as dedicated productions called "energetic" such as miscanthus, switchgrass (Panicum virgatum or switchgrass) and coppice with very short rotation such as poplar or willow; crop residues such as cereal straw, corn stover and sugar cane stalks; forest production; forest production residues such as residues from wood processing; agricultural residues from livestock farming such as animal meal, manure and slurry; and organic waste.

Organic waste includes household organic waste, industrial organic waste, hospital waste, sludge from wastewater treatment, sludge from the treatment of industrial liquid effluents, sludge from silo bottoms and their mixtures. Advantageously, the industrial organic waste comprises waste from the agri-food or catering industries; packaging such as pallets, crates and plastic containers; production waste such as sawdust, falling and cutting; used products such as paper, out of service equipment and tires; and materials such as cardboard, textiles and plastics. When the organic waste is in the form of sludge, the latter are typically defined as dried sludge. By "dried mud" is meant a sludge in the form of a solid sludge or sludge and whose dry weight% relative to the total sludge mass is greater than 50%.

 In general, whether the carbonaceous material used in the present invention is solid, liquid or gaseous, the latter advantageously has a moisture content of less than 50%, ie the% by weight of water relative to the total mass of carbonaceous material is less than at 50%.

 In addition, the carbonaceous material used in the present invention may have any ash content. Advantageously, the ash content of this carbonaceous material is between 0.5 and 30% by weight. As a reminder, the ash content of a sample expressed in mass% corresponds to the ratio of the mass of the residue obtained after calcination at a defined temperature and for a given time, to the initial mass of the sample. The ash levels are measured by calcination at 550 ° C according to DIN EN 14775.

Step (a) of the process of the invention is a conventional gasification step carried out in a driven-flow reactor or in a fluidized-bed reactor.

 In the case of a fluidized-bed reactor, step (a) consists in bringing the carbonaceous material optionally pretreated, in the presence of a gasifying agent and optionally an oxidizer, to a temperature greater than or equal to 800 ° C. and in particular between 800 ° C. and 1200 ° C. and this, under an absolute pressure of between 1 bar and 30 bars and in particular between 1 bar and 10 bars, and in particular between 1 bar and 5 bars.

In the case of a driven flow reactor, step (a) consists in bringing the optionally pretreated carbonaceous material, in the presence of a gasifying agent and optionally an oxidizer, to a temperature greater than or equal to 1000 ° C. , especially between 1200 ° C and 1800 ° C and, in particular, between 1300 ° C and 1600 ° C and this, under an absolute pressure of between 1 bar and 80 bars and in particular between 5 bars and 40 bars, and in particular between 25 bars and 35 bars.

 The high temperatures used during this gasification step make it possible to obtain a carbon conversion rate of the carbonaceous material to a high CO gas and thus to reduce the amount of unconverted carbon present in the by-products of the gasification and in particular in the ashes produced during the latter. These high temperatures are obtained by using one or more burner (s) present (s) in the reactor and in particular in the driven flow reactor.

 The gasifying agent or gaseous agent required for the gasification is in particular water vapor, carbon dioxide and / or oxygen. Such a gasifying agent is present in an amount sufficient to allow gasification of the carbonaceous material. Such an amount can be readily determined by those skilled in the art by routine work.

 In addition, during step (a) of the process and / or when the carbonaceous material has insufficient moisture to generate a quantity of water vapor effective to allow the gasification of this carbonaceous material, it may be necessary to inject in the entrained flow reactor or in the fluidized bed reactor, water vapor.

 Finally, during step (a) of the process, it may be necessary to inject, in the driven-flow reactor or in the fluidized-bed reactor, a suitable oxidizer in order to supply the energy for the rise in temperature and for gasification. The oxidant is advantageously a reactive gas comprising oxygen such as air, air enriched with oxygen or pure oxygen.

The gasification of the carbonaceous material during step (a) of the process according to the invention produces a synthesis gas, also known under the name "syngas". The nature and composition of the synthesis gas obtained following step (a) of the process depend in particular on the nature of the carbonaceous material used during the gasification and the oxidizing or reducing conditions used during this step. Advantageously, the synthesis gas produced by the process according to the present invention mainly comprises hydrogen (H ₂ ) and carbon monoxide (CO). By "predominantly" is meant that H ₂ and CO are present in a volume percentage relative to the total volume of synthesis gas greater than 50%, especially greater than 60% and, in particular, greater than 70%.

The synthesis gas also contains, in a minor but significant amount, water (H ₂ O) and carbon dioxide (CO ₂ ) resulting from at least partial combustion of the biomass. These two compounds are not recovered in the rest of the process and can be separated before synthesis. By "minority" is meant that H ₂ 0 and C0 ₂ are present in a volume percentage relative to the total volume of synthesis gas less than 50%, especially less than 40% and, in particular, less than 30%.

In fact, the synthesis gas produced by the process according to the present invention comprises hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), water (H ₂ O). ) and possibly one or more other gaseous element (s), this or these last (s) being advantageously present in the form of traces. The respective proportion of the various elements present in the synthesis gas ie H ₂ and CO depends on the nature of the carbonaceous material treated and the thermal conditions in the entrained flow reactor.

"Trace element" means a gaseous element present in a volume percentage relative to the total volume of the synthesis gas of less than 6%, in particular less than 4%, in particular less than 2%, and more particularly less than 1%. By way of illustrative and non-limiting examples of other gaseous elements present in the synthesis gas produced following step (a) of the process according to the invention and especially present in trace amounts in the synthesis gas produced following step (a) of the process according to the invention, mention may be made of methane (CH ₄ ), acetylene (C ₂ H ₂ ), ethylene (C ₂ H ₄ ), ethane (C ₂ He), inorganic or organic aerosols, inorganic pollutants such as hydrogen sulfide (H ₂ S), ammonia (N H 3), hydrochloric acid (HCI), hydrogen cyanide (HCN) and carbon oxysulfide (COS), organic compounds such as benzene (CeHe), toluene (C7H8) and polycyclic aromatic hydrocarbons such as naphthalene (C10H) as well as solid soot. In the case of a driven flow reactor, the synthesis gas obtained following step (a) of the process according to the present invention is at a temperature greater than or equal to 1000 ° C., in particular between 1200 ° C. and 1800 ° C and, in particular, between 1300 ° C and 1600 ° C. Step (b) of the process according to the present invention consists in lowering the temperature of the synthesis gas to a temperature of less than or equal to 900 ° C., in particular less than or equal to 800 ° C. and, in particular, less than or equal to 700 ° C. ° C and this, by contact with a quenching effluent.

 In the case of a fluidized bed reactor, the synthesis gas obtained following step (a) of the process according to the present invention is at a temperature greater than or equal to 800 ° C. and in particular between 800 ° C. and 1200 ° C. Step (b) of the process according to the present invention consists in lowering the temperature of the synthesis gas to a temperature of less than or equal to 700 ° C. and in particular of less than or equal to 600 ° C., and this, by placing it in contact with an effluent. quenching.

One of the remarkable characteristics of the process according to the invention consists in using as quench effluent a by-product of this process, namely the gas stream obtained following the chemical synthesis step using as starting material H ₂ and CO.

From a technological point of view, step (a) and step (b) of the process according to the present invention can be carried out using a driven flow reactor designed for TGP type water quenching (for "Texaco Gasification Process"), MGP (for "Manufactured Gas Plant"), GSP (for "Gas Turbine Simulation Program") or PDQ. (for "Prenflo with Direct Quench"). The difference between these processes and that of the invention lies in the absence of water recovery from quenching at the bottom of the reactor. It is also possible to use a driven flow reactor designed for SCGP type gas quench (for "Shell Coal Gasification Process"), PSG (for "Prenflo with Steam Generation"), FICFB (for "Fast Internai Circulating Fluidised"). Bed ") or HTW (for" High Temperature Winkler Process "). Step (c) of the process according to the present invention consists of a purification treatment of the quenched effluent, obtained following step (b). By "purification treatment" is meant a treatment for removing compounds such as sulfur compounds, nitrogen compounds, carbon dioxide, tars, halides or alkali metals, present in the quenched effluent, obtained following step (b) and may adversely affect the catalysts used in the subsequent chemical syntheses of step (d) of the process according to the invention. This purification step may possibly make it possible to achieve the ratio H2 / CO adapted to the subsequent chemical synthesis step of step (d) of the process.

 Any method for removing at least one of the aforementioned elements and usually used for the purification of a synthesis gas obtained by gasification can be used in the context of the process according to the present invention.

 Advantageously, the purification step (c) of the process according to the present invention implements at least one step selected from the group consisting of an acid gas removal step, a halogenated compounds elimination step, a step of removal of sulfur compounds, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a step of conversion of carbon monoxide to steam (reaction of "Water Gas Shift" ) and a final purification step on guard bed.

 In a particular embodiment, the purification step (c) of the process according to the present invention does not implement a step of converting carbon monoxide to steam ("Water Gas Shift" reaction).

More particularly, the purification step (c) of the process according to the present invention implements an acid gas removal step combined with at least one other step selected from the group consisting of a halogenated compounds elimination step, a step of removing sulfur compounds, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification step on guard bed. These different treatment steps aimed at purifying the synthesis gas produced by gasification are well known to those skilled in the art. By way of illustrative and nonlimiting examples of such steps, mention may be made of:

 the conversion of carbon monoxide to steam responds to the following overall reaction (I):

CO + H ₂ O -> C0 ₂ + H ₂ (I),

 this conversion uses high temperature catalysts, that is to say implemented at temperatures of 350 ° C, which are typically based on iron and chromium; low temperature catalysts, that is to say used at temperatures of about 200 ° C, which are typically based on copper and zinc or precious metal catalysts, whose operating temperatures are intermediate ;

the elimination of acid gases such as hydrogen sulphide (H ₂ S) or carbon dioxide (CO ₂ ) by use of chemical solvents such as monoethanolamine, diethanolamine, methyldiethanolamine or a mixture thereof and / or or physical solvents such as polyethylene glycol diethyl ether, polyethylene glycol dibutyl ether or methanol;

 the elimination of the halogenated compounds by contacting the synthesis gas with a capture mass with an active phase comprising a zeolite, zinc oxide and / or alumina;

- The elimination of sulfur compounds by implementation of Sulfinol ^® processes Shell, Purisol ^® or Rectisol ^® ;

 catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) carried out in the presence of a catalyst containing a platinum compound, a titanium oxide, a zirconium oxide, an aluminum oxide, a chromium oxide and / or a zinc oxide; and

the final purification to reach the accepted impurity levels as a function of the subsequent catalytic synthesis, implemented on a guard bed based on zinc oxide, zinc oxide and copper and / or activated carbon. As previously explained, the chemical synthesis in step (d) of the process according to the invention may be any chemical synthesis in which the catalytic chemical reaction used uses CO and H ₂ as reagents. Advantageously, this chemical synthesis is selected from the group consisting of catalytic synthesis of Fischer-Tropsch type, catalytic synthesis of methanol, catalytic synthesis of ethanol and catalytic synthesis of dimethyl ether.

 The Fischer-Tropsch type catalytic synthesis responds to the following overall reaction (II):

CO + 2H ₂ -> - (CH ₂ ) - + H ₂ O (II)

 However, this reaction may differ depending on the type of catalysts used. Thus, for iron-based catalysts or for cobalt-based catalysts, the Fischer-Tropsch synthesis reaction corresponds respectively to the following reaction (III) or (IV):

n (CO + 2H ₂ ) -> C _n H _2n + n H ₂ O (III)

n CO + (2n + 1) H ₂ -> CnH _{2n + 2} + n H ₂ O (IV).

Thus, in the context of a catalytic synthesis of Fischer-Tropsch type, the H ₂ / CO ratio is advantageously between 1.5 and 3 and especially between 2 and 2.5.

Catalytic synthesis of methanol using CO and H ₂ as reagents is a reaction known to those skilled in the art. By way of particular example, the latter can be carried out with a catalyst based on copper oxide at a pressure of 50 to 100 bar and at a temperature of between 180 and 270 ° C., depending on the overall reaction (V ) next :

CO + 2H ₂ -> CH ₃ OH (V)

 Thus, in the context of a catalytic synthesis of methanol, the ratio

H ₂ / CO is advantageously between 1 and 3 and in particular between 1.5 and 2.5.

Catalytic synthesis of ethanol using CO and H ₂ as reagents is also a reaction known to those skilled in the art. For exemple in particular, the latter can be carried out with a rhodium-based catalyst as described in [9] according to the following overall reaction (VI):

2 CO + 4H ₂ -> C2H5OH + H2O (VI)

 Thus, in the context of a catalytic synthesis of ethanol, the ratio H2 / CO is advantageously between 1 and 3 and in particular between 1.5 and 2.5.

Finally, any catalytic synthesis reaction of dimethyl ether (DME) using CO and H ₂ as reagents known to those skilled in the art can be used in the context of the present invention. By way of a particular example, the latter may be carried out with a multifunctional catalyst of the copper oxide, zinc oxide or aluminum oxide type, according to the following main reaction (VII):

3 CO + 3H 2 -> CH ₃ OCH ₃ + CO ₂ (VII).

Thus, in the context of a catalytic synthesis of DME, the H ₂ / CO ratio is advantageously between 0.2 and 2 and in particular between 0.5 and 1.5.

It is obvious that the nature of the gaseous effluent and that of the liquid effluent obtained following step (d) of the process according to the present invention will depend on the type of synthesis implemented at this stage. In general, the gaseous effluent at least a portion of which is used as a quench effluent during step (b) comprises at least one element selected from the group consisting of carbon monoxide, carbon dioxide, carbon dioxide and hydrogen and a carbon compound comprising 1 to 20 carbon atoms, said element (s) possibly being combined with water vapor. By way of examples of a carbon compound comprising from 1 to 20 carbon atoms, mention may be made of C 1 to C 20 alkanes, for example pentane and decane, and C 2 to C 20 alkenes, for example propene. and butene. In fact, it is explicitly excluded from the scope of the present invention a gaseous effluent used as quenching gas which would be exclusively composed of water vapor.

Typically, the gaseous effluent used as quenching effluent during step (b) is used directly following step (d): it is not subjected to any treatment such as a purification. In the context of the process according to the present invention, prior to the gasification step (a), the carbonaceous material may be pretreated. Any pretreatment of the organic material to destructure the latter prior to a gasification step is used in the context of the present invention.

 Advantageously, the pretreatment implemented in the context of the present invention comprises at least one step selected from the group consisting of a drying step, a roasting step, a granulation step and a grinding step. These steps are more particularly adapted to a carbonaceous material in solid form or comprising a solid fraction.

 The drying step optionally used in the context of the process according to the invention aims to reduce the moisture content of the organic material to be gasified, in particular to obtain a moisture content of less than 50%. Any technique and any drying device known to those skilled in the art can be used in the context of the invention. Typically, this drying is carried out at a temperature between 40 and 180 ° C, especially between 60 and 160 ° C and, in particular, between 80 and 140 ° C and for a period of between 15 min and 4 h, in particular between 30 minutes and 3 hours, and in particular between 1 and 2 hours. The energy required for this drying can be provided either independently to the process according to the invention, or by combustion of one of the gases produced during the latter. In this case, the energy can be supplied by the combustion of a part of the synthesis gas produced in step (a) and / or by the combustion of a part of the gaseous effluent produced in step ( d).

By "roasting step" is meant a step of subjecting the optionally dried carbonaceous material to a thermochemical treatment at a temperature typically between 200 and 320 ° C, to remove water and modify a portion of the carbonaceous material to make it more friable especially by breaking the fibers (case of the biomass-type carbonaceous material). Roasting the carbonaceous material also produces gases such as water vapor, formic acid, acetic acid, methanol, CO and carbon dioxide. This roasting step is carried out in any roasting oven known to man of career. The energy required for this roasting can be provided either independently to the process according to the invention, or by combustion of a gas produced during the latter. In this case, the energy can be supplied by the combustion of a part of the synthesis gas produced in step (a), by the combustion of a part of the gaseous effluent produced in step (d). and / or by burning a portion of the gases produced during this roasting. Note that these can also be used to provide the energy needed for drying.

 The method according to the present invention may also include granulation pretreatment, also known as pelletizing. This pretreatment consists in pressing the carbonaceous material against a sieve to obtain granules of uniform size and shape, said granules having a bulk density increased relative to the density of the carbonaceous material before granulation. Any technique and any granulation device known to those skilled in the art can be used in the context of the invention.

 When all or part of the carbonaceous material used in the context of the present invention is in solid form, the latter may have to undergo a grinding step to obtain residues having characteristic dimensions, less than 1 mm, especially lower than equal to 500 μιη and, in particular, less than or equal to 300 μιη. Any technique and any grinding device known to those skilled in the art can be used in the context of the invention.

The method according to the present invention may comprise a step of adding H ₂ to at least one of the effluents obtained following step (b) or following step (c) of the process. Advantageously, this addition is carried out on the purified effluent obtained following step (c) and this, prior to the synthesis step (d) of the process according to the invention.

Indeed, to avoid the WGS step, it is possible to use an injection option H ₂ , replacing this step. This addition of H ₂ makes it possible to increase the material yield but can reduce the overall energy efficiency. In addition, a such addition makes it possible to adjust the H2 / CO ratio so as to make it suitable for the subsequent synthesis stage (d), which confers a degree of freedom on the process according to the invention.

The H2 added during this optional additional step can be obtained independently from the process according to the invention or, conversely, be produced during this process. In this case, the H ₂ can come from a reforming step from one or more hydrocarbon (s) produced during the process according to the invention or from one or more hydrocarbon (s) of fossil origin (CH ₄ for example), an alkaline electrolysis step and / or a SOEC type high temperature electrolysis step and this, from H ₂ 0 or an H ₂ mixture 0 / CO produced during the process according to the invention.

The method according to the present invention may also comprise a step consisting in recovering heat energy during the process, in particular in order to increase the energy efficiency of the latter. The heat energy thus recovered can be used in the process according to the present invention or in any other process requiring a supply of heat energy.

 This heat energy can be recovered at any point in the process according to the present invention i.e. following the gasification step and prior to the catalytic synthesis step. Advantageously, the heat energy is recovered following the quenching step (b) and prior to the purification step (c).

 The heat energy thus recovered can, for example, be used to generate steam such as water vapor. Such use is of particular interest in the context of a process according to the invention of the PSG type (for "Process with Steam Generation") which has a heat recovery steam generator (HRSG). .

The present invention also relates to an installation that can be implemented in a method as defined above. The installation according to the invention comprises: a unit for gasification of the carbonaceous material with synthesis gas, said unit comprising at least one driven-flow or fluidized-bed reactor, in particular such as previously defined;

 a quenching unit disposed at the outlet of said gasification unit; a purification unit for the quenched effluent obtained at the outlet of said quenching unit; and

 a catalytic synthesis reaction unit for preparing a gaseous effluent and a liquid effluent from the purified effluent obtained at the outlet of the purification unit; and

 means for recycling the gaseous effluent obtained at the outlet of the reaction unit to the quenching unit.

 The purification unit of the plant according to the invention comprises at least one unit selected from the group consisting of an acid gas removal unit, a halogenated compounds elimination unit, a sulfur compounds elimination unit. , a catalytic hydrolytic unit of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a unit of conversion of carbon monoxide to steam (WGS unit) and a final purification unit on a bed of keep. Advantageously, the purification unit of the plant according to the invention comprises at least one acid gas elimination unit combined with at least one other stage chosen from the group consisting of a unit for eliminating halogenated compounds, a unit removal of sulfur compounds, a catalytic hydrolytic unit of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification unit on guard bed. All that has previously been explained as to the purification steps applies mutatis mutandis to the purification units. Thus, in particular variants, the purification unit of the installation does not include a unit for converting carbon monoxide to steam (WGS unit).

The catalytic synthesis reaction unit of the plant according to the invention comprises at least one unit selected from the group consisting of a Fischer-Tropsch type catalytic synthesis reactor, a catalytic synthesis reactor of methanol, a catalytic synthesis reactor ethanol and a synthesis reactor catalytic dimethyl ether. All that has previously been explained as to catalytic syntheses applies mutatis mutandis to catalytic synthesis reactors.

 The plant according to the invention may further comprise at least one pre-treatment unit for the carbonaceous material. This unit is arranged upstream of the gasification unit. Advantageously, this pretreatment unit comprises at least one unit selected from the group consisting of a drying unit, a roasting unit, a granulation unit and a grinding unit. All that has previously been explained as to the pretreatment steps applies mutatis mutandis to preprocessing units.

The plant according to the present invention may further comprise means for injecting H ₂ to at least one of the effluents obtained at the outlet of the quenching unit or at the outlet of the purification unit. More particularly, these means make it possible to inject H ₂ into the purified effluent obtained at the outlet of the purification unit.

 Finally, the installation according to the present invention may also comprise means for recovering the heat energy of at least one of the effluents circulating in said installation. Advantageously, the heat energy is recovered at the quenched effluent obtained at the outlet of the quenching unit.

Other features and advantages of the present invention will become apparent to those skilled in the art on reading the example below given for illustrative and non-limiting, with reference to Figure 2 attached.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1E show general diagrams of prior art biomass chemical conversion processes using water quenching without recycling (FIG. 1A), water quenching with recycling using steam reforming (FIG. 1B), quenching with a high temperature exchanger (FIG. 1C), quenching with solid recycling (FIG. 1D) and quenching with synthesis gas recirculation (FIG. 1E). Figure 2 shows a block diagram of a particular sequence of a method according to the invention.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS I. Method According to the Invention

The sequence of steps of a process according to the present invention as shown in FIG. 2 is carried out with a driven flow reactor and on a preferably vegetable biomass carbon material of formula C6Hg0 ₄ .

 This biomass is subjected to a first preparation step consisting of a pretreatment as previously defined (Brick I). This pretreatment advantageously comprises one or more steps selected from a drying step, a roasting step, a granulation step and a grinding step.

The biomass thus treated is fed into a driven flow reactor designed especially for a gas quench type PSG (for "Process with Steam Generation"). In this reactor, the biomass undergoes a gasification at a temperature of 1500 ° C., under a pressure of 30 bars, in the presence of H ₂ 0, CO ₂ and / or O ₂ as a gasifier and of O ₂ as oxidant ( Brick 1).

The synthesis gas produced following this gasification step mainly comprises CO and H ₂ in an H ₂ / CO ratio of 0.6. It is then subjected to a quenching step so as to lower its temperature to a value of 800 ° C. (Brick 2). This quenching step consists of contacting the synthesis gas resulting from the gasification with at least a portion of the gaseous effluent or overhead gas, resulting from Fischer-Tropsch catalytic synthesis (Brick 5).

The quenched effluent obtained at the outlet of the quenching unit is subjected to another treatment aimed at recovering the heat energy of this quenched effluent. This treatment uses a heat exchanger and a heat recovery steam generator (HRSG) (Brick 3). At the end of this treatment, the recovered effluent has a temperature of 450 ° C. and an H ₂ / CO ratio of between 1.5 and 2. As previously explained, this sequence and, in general, a process according to the present invention do not have any reactor for converting carbon monoxide to steam (WGS).

The effluent obtained following the heat exchange step (Brick 3) is cleaned so as to remove the impurities it contains up to levels acceptable for the catalytic synthesis of Fischer-Tropsch type subsequently implemented. Brick 4 of Figure 2 thus corresponds to a purification step of the effluent implementing a purification unit. This purification step is more particularly a step of removing acid gases such as hydrogen sulphide (H ₂ S) or carbon dioxide (CO ₂ ) contained in the quenched effluent obtained at the outlet of Brick 3 by use of chemical solvents such as monoethanolamine, diethanolamine, methyldiethanolamine or a mixture thereof and / or physical solvents such as polyethylene glycol diethyl ether, polyethylene glycol dibutyl ether or methanol. Processes using chemical solvents operate at temperatures in the range of 20-30 ° C and atmospheric pressure up to possibly 30 bar. Processes using physical solvents operate at higher pressure and lower temperature. For example, in the case of methanol, the temperatures are from -30 ° C. to -60 ° C. and the pressures from 30 bars to 60 bars.

 Such purification step may be combined with one or more other purification step (s) selected from the group consisting of a halogenated compound removal step, a sulfur compound removal step, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification step implemented on guard bed.

 The purified effluent obtained at the outlet of the cleaning / purification step is subjected to a catalytic synthesis step of Fischer-Tropsch type (Brick 5) using a cobalt or iron-based catalyst and according to the following reaction (III) :

n (CO + 2H ₂ ) -> C _n H _2n + n H ₂ O (III).

However, prior to this synthesis step, the purified effluent obtained at the outlet of the cleaning / purification step is supplemented with H ₂ so as to obtain a H ₂ / CO ratio of 2. The H ₂ used is advantageously obtained via a step of reforming, an alkaline electrolysis step and / or a high temperature electrolysis step typically at 800 ° C and this from water from the process or injected from the outside.

The gaseous effluent obtained after the catalytic Fischer-Tropsch synthesis type predominantly comprises CH _4, C ₂ H _4, C ₂ H6, C3H6, C3H8, C ₄ Hs, C ₄ Hio and small amounts of hydrocarbons with more than 5 carbons, whereas the liquid effluent consists of a mixture of liquid hydrocarbons comprising more than 5 carbons.

II. Improvements obtained by applying the process of the invention. Calculations have been made to compare the performance of the invention with two reference cases which correspond to a standard scheme with water quenching and without recycling (Figure 1A) and with water quenching and recirculation schemes. using steam reforming (Figure 1B).

 The calculations were carried out with the ProsimPlus software, intended to calculate material and energy balances of process sequences.

In the 3 cases, the gasification is carried out in a flux-driven reactor with a biomass mixture, H ₂ 0 and 0 ₂ so as to reach a thermal equilibrium at 1400 ° C. At the outlet of the reactor, the molar ratio H ₂ / CO is 0.54, against about 2 necessary for the synthesis.

 Downstream of gasification, the 3 cases diverge:

- case 1 (prior art, Figure 1A): The quenching is carried out with water to reach a temperature of 800 ° C. The gas is then made to the specifications for the synthesis by undergoing a Water Gas Shift step and a cleaning step (Acid Gas Removal) having among other function to eliminate the C0 ₂ . The proportion of gas treated with WGS is set by the objective of reaching a H ₂ / CO molar ratio of 2. The gas thus obtained is then treated in the synthesis.

- Case 2 (prior art, Figure 1B): The quenching is carried out with water to reach a temperature of 800 ° C. The gas is then made to the specifications for the synthesis by undergoing a Water Gas Shift step and a cleaning step (Acid Gas Removal) having among other function to eliminate the C0 ₂ . The proportion of gas treated the WGS is set by the objective of reaching a molar ratio H2 / CO of 2. The gas thus obtained is then treated in the synthesis. The overhead gas (C1-C4 cut) produced by the synthesis is recycled by means of an isolated steam reforming step. A proportion of the overhead gas is converted to CO + H ₂ and the remainder is burned to provide the energy required for the steam reforming step. Thus, the thermal balance of this step imposes the rate of recycling of the overhead gas. In our calculations, this rate was calculated at 62%, which means that we can expect an industrial recycling rate of between 50% and 70%. This is a strong constraint of this option.

- Case 3 (Invention Figure 2): The quenching is carried out by injection of all or part of the overhead gas (C1-C4 cut) produced by the synthesis and a possible addition of quenching with water. The gas is then made to the specifications for the synthesis by undergoing a Water Gas Shift step and a cleaning step (Acid Gas Removal) having among other function to eliminate the C0 ₂ . The proportion of the gas treated with WGS is set by the objective of reaching a molar ratio of H2 / CO of 2. The gas thus obtained is then treated in the synthesis.

 In this overhead gas quenching configuration, the recycle rate of the overhead gas is free from 0 to 100%, since the rest is provided by quenching with water. 0% corresponds to case 1 presented above. 100% is not conceivable due to the excessive accumulation of inerts in the gas, in particular N2 used for some inertages and partially for the injection of the solid into the RFE. A purge rate, in our case estimated at around 10% is therefore desirable. A recycling rate ranging from 10% to 90% is possible. For the calculations, the inventors worked with the recycling rate range varying between 50% and 90%.

One of the objectives of this quenching being to convert the light hydrocarbons and in particular, the methane, the part of the reactor intended to perform the quenching and the reaction will have to be dimensioned so that a sufficient residence time is left to the gas for the transformation to operate. . In addition, the gas passing from 1400 ° C to 800 ° C, the conversion kinetics can be affected by the temperature conditions encountered by the gas. For these two reasons, the conversion rate of the overhead gas can not be known precisely to date. The inventors have therefore made several calculations with 3 fixed gas conversion rates: 50%, 70% and 90%.

 In each of the three cases, each step was modeled respecting the temperature and pressure levels required in the process. Each reaction step was modeled by an equilibrium equation describing the chemical transformation performed (gasification, water gas shift, steam reforming, synthesis, hydrocracking). This makes sure that material balances are respected. The thermodynamic models included in the software make it possible to calculate the energy balances of each reaction stage, as well as those of the exchangers and compressors.

 The high temperature heat exchanger (HSRG) was not simulated in detail because there is no optimization objective on the energy balance for these calculations (no high energy integration). The cooling of the synthesis gas is still considered in the balance sheet.

 Table 1 below summarizes the results of calculations made in several configurations:

 - the reference process with quenching with water and without recycling (case 1);

the process with water quenching and recycling using steam reforming (case 2): the energy equilibrium of the steam reforming stage imposes a recycling rate of 62%, so there is no need for freedom to set the recycling rate;

- The new process with gas quenched coupling and recycling (case 3): the calculation assumptions include the gas conversion rate, which may depend on the reactor configuration, but the present invention is not the subject. The inventors thus performed the calculations for 3 conversion rates of the overhead gas: 90%, 70% and 50%. As previously explained, gas quenching allows a great deal of latitude in the recycle rate of the overhead gas. The results for 60% recycling, in order to compare with the standard process and recycling with steam reforming and 90% recycling are presented. Case 1 Case 2 Case 3

 Rate of Rate Rate

Ss conversion Gas conversion Gas conversion Gas

Recycled. VapRef of head = 90% of head = 70% of head = 50%

Recycling rate 0% 62% 60% 90% 60% 90% 60% 90%

Gasification C6Hs, 403.6 t / h 100 100 100 100 100 100 100 100

Gasification SynGas t / h 180.4 180.4 180.4 180.4 180.4 180.4 180.4 180.4

Gasification H 2 / CO 0.54 0.54 0.54 0.54 0.54 0.54 0.54 0.54

Table 1 The indicators for comparing the configurations between them are:

 i) the flow rate of water used for quenching which sizes the utilities of the process;

 ii) the flow of syngas leaving the quench, which dimensions the gas cleaning installation;

 iii) the gas flow rate at the output of the FT synthesis and the recycled flow rate that sizes the compression station before recycling;

 iv) the H2 / CO ratio that influences the parameters of the WGS unit; v) the rate of processed syngas in the WGS unit, which is sizing; vi) the CO2 flow rate at the inlet of the gas cleaning unit (AGR) that is sizing;

 vii) the existence of the Vaporeforming step and the associated water and air flow;

 viii) the syngas flow at the input of the FT synthesis, which is sizing;

 ix) the flow rates of N2 and CH4 at the input of the FT synthesis, which are dimensioning as inert;

 x) the material yield of synthetic compounds containing more than 5 carbons (C5 +); and

xi) energy efficiency.

Their evolution is detailed in Table 2 below.

 Table 2

The economic classification, evaluated from the existence of facilities and trends on their size is also a very important criterion, since it aggregates all the previous technical evolutions. The results of the calculations already show trends (increase or decrease in investment and operation). Firstly, the fact of being able to recycle the overhead gas up to 90%, compared with 60% in the case of recycling with steam reforming, is a great advantage, since the process performances are better with a recycling of 90%. % with a 60% recycling.

 The indicators that most favorably influence the process with gas quenching (i.e., the method according to the invention) are:

- The flow rate of H ₂ 0 quenching, which can be reduced to zero, as expected. This is a major gain. There is an economic interest on the utilities, therefore on the investment and the associated operating costs. The reduction is very advantageous compared to recycling with steam reforming which also consumes water and air;

 - the material and energy yields which increases by 60%. The gain is therefore very sensitive with the coupling of quenching and recycling of the FT head gas. Note that at equivalent recycling rate, recycling with steam reforming is penalized by the production of steam and the compression of gases. It loses a little more than 5% of yield;

the elimination of the steam reforming step which has a favorable economic impact and also makes it possible to save 10 t / h of H ₂ 0 vapor and a high air flow rate; and

- the reduction of the C0 ₂ flow rate by 35%, sizing for the gas cleaning unit (AGR), which allows to consider reducing the size of the AGR.

Other indicators favorably influence the process with gas quenching (i.e. the process according to the invention), although with a smaller weight:

 the flow rate of synthesis gas at the quenching outlet drops, due to a smaller flow of water at the inlet. Here too, there is an advantage over recycling with steam reforming in which the gas contains a lot of water;

the H ₂ / CO molar ratio at quenching output increases by 50%, which indicates a decrease in the gas flow rate sent to the Water Gas Shift stage; the flow rate of gas sent to the Water Gas Shift stage decreases by 25%, which makes it possible to envisage a reduction in the size of the unit and therefore the associated investment and operating costs; and

the flow rate of CH ₄ decreases in synthesis input, which is favorable for the dimensions of the unit and for the reaction because the CH ₄ is considered as an inert and therefore a diluent of the gas.

The 4 indicators, which are evolving unfavorably, are all in the direction of increasing the capacity of the synthesis unit by 50 to 80%. This is the flow of syngas at the entry of the synthesis, the flow rate of N ₂ at the entry of the synthesis, the flow of overhead gas (C1-C4) produced and recycled to the quench (associated with a compression unit). Since these indicators are only linked to the FT synthesis unit, their unfavorable impact is counterbalanced by the fact that the investment and operating costs of this unit will be adapted to its production, which increases in the same proportions.

In conclusion

 The calculations show a strong interest in coupling the recycling of the synthesis gases FT overhead gas and quenching at the outlet of the gasification reactor.

 This coupling is more flexible than recycling with steam reforming because the recycling rate can be set from 0 to 100% depending on the objectives sought, whereas, in the case of steam reforming, the recycling rate is imposed by the quantity of FT gas to be burned. to reform the gas (estimated at about 60%).

It should be noted that it is possible to suppress the Water Gas Shift stage and to do this, it is necessary to use an FT with an iron catalyst (which works with H ₂ / CO <2) or an external H ₂ injection if cobalt catalyst or mix with carbonaceous feedstocks richer in C and H such as tires, petroleum cokes or coal.

The recirculation coupling of the synthesis gases FT and quench at the outlet of the gasification reactor makes it possible to significantly reduce the quantity of water consumed by the process, to reduce the size of the installations, with the exception of the unit of FT synthesis, even suppress them (steam reforming) and increase the material and energy yields.

 From the economic point of view, this coupling therefore has a favorable impact on the economics of the process. Compared to a case without recycling, this coupling necessarily imposes a larger investment (management of recycling, compressor and size of FT synthesis), but it allows to significantly increase the fuel production efficiency which is very favorable in term production cost. Compared to recycling with steam reforming, this coupling is much more advantageous economically because it reduces the investment costs (vapor reforming unit removed in particular) and operating, while increasing the production of fuel. In the end, compared to the configuration without recycling, the increase in investment is offset by the increase in yields and the decline in utility costs, which leads to a decrease in the cost of producing fuel.

 Finally, if we compare with cases with exchanger, syngas quenching or solid quenching (see advantages and disadvantages in Table 3 below), we can say that in these 3 cases, recycling can only be done with a steam reforming step, so with the same constraints as the case simulated above (including recycling capped at 60%). These 3 cases and the case of quenching with water do not therefore allow to benefit from all the advantages obtained via the process according to the invention with quenching / recycling coupling.

Table 3 REFERENCES

[1] Martelli et al, 2011, "Coal Coal IGCCS with carbon capture: I nnovative configurations ", Applied Energy, vol. 88, pp. 3978-3989.

 [2] US Patent Application 2007/062117 in the name of Future Energy GmbH and Manfred Schingnitz, published March 22, 2007.

 [3] US Patent Application 2007/051044 to Future Energy GmbH and Manfred Schingnitz, published March 8, 2007.

 [4] US Patent 5,433,760 to Shell Oil Company, published July 18

1995.

 [5] International Application WO 94/26850 in the name of Shell Oil Company, published November 24, 1994.

 [6] Rudioff, 2005, "The Development and Operation of an Optimized Gasifier for Syngas Production from Biomass", International Freiberg Conference on IGCC and XtL Technologies.

 [7] Van Paasen, 2012, Shell Projects & Technology, "TECHNOLOGY DEVELOPM ENT FOR SHELL COAL GASIFICATION", 5th International Freiberg Conference on IGCC and XtL Technologies.

 [8] Patent Application FR 2 861 402 in the name of the Institut Français du

Oil and the Commissioner of Atomic Energy, published April 29, 2005.

 [9] Article by Spivey and Egbebi, 2007, "Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas", Chem. Soc. Rev., vol. 36, pages 1514-1528.

Claims

1) Process for chemical transformation of a carbonaceous material comprising at least the steps of:  a) gasifying said carbonaceous material in a driven-flow or fluidized-bed reactor whereby synthesis gas is produced;  b) subjecting the synthesis gas produced in step (a) to quenching by adding to said synthesis gas a quenching fluid;  c) subjecting the quenched effluent obtained in step (b) to a purification treatment; d) subjecting the purified effluent obtained after step (c) to a catalytic synthesis reaction using as reagents carbon monoxide (CO) and dihydrogen (H ₂ ) whereby a gaseous effluent and a liquid effluent are obtained ;  characterized in that all or part of the gaseous effluent obtained during step (d) is used as quenching fluid during step (b). 2) Process according to claim 1, characterized in that said carbonaceous material is selected from the group consisting of natural gas, shale gas, crude oil, light naphtha, heavy fuel oil, coal, bituminous coal, cokes such as petroleum or bituminous coal, lignite coal, oil sands, oil shale, organic matter of animal or vegetable origin, organic material derived from human activities and any of their mixtures . 3) Process according to claim 1 or 2, characterized in that said carbonaceous material is selected from the group consisting of agricultural productions such as dedicated productions called "energetics"; crop residues such as cereal straw, corn stover and sugar cane stalks; forest production; forest production residues such as residues from the wood processing; agricultural residues from livestock farming such as animal meal, manure and slurry; and organic waste. 4) Process according to any one of claims 1 to 3, characterized in that said step (a) carried out in a driven flow reactor comprises bringing the carbonaceous material optionally pretreated, in the presence of a gasifying agent and optionally an oxidizer, at a temperature greater than or equal to 1000 ° C, in particular between 1200 ° C and 1800 ° C and, in particular, between 1300 ° C and 1600 ° C and under an absolute pressure between 1 bar and 80 bars, especially between 5 bars and 40 bars, and in particular between 25 bars and 35 bars. 5) Process according to any one of claims 1 to 3, characterized in that said step (a) carried out in a fluidized bed reactor comprises bringing the carbonaceous material optionally pretreated in the presence of a gasifying agent and optionally an oxidizer, at a temperature greater than or equal to 800 ° C and in particular between 800 ° C and 1200 ° C and under an absolute pressure between 1 bar and 30 bar and in particular between 1 bar and 10 bar, and in particular, between 1 bar and 5 bar. 6) Process according to any one of claims 1 to 5, characterized in that said purification step (c) implements at least one step selected from the group consisting of an acid gas removal step, a step of elimination of halogenated compounds, a step of removing sulfur compounds, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a step of conversion of carbon monoxide to steam ("Water Gas Shift" reaction) and a final purification step on guard bed. 7) Process according to any one of claims 1 to 6, characterized in that said catalytic synthesis reaction in said step (d) is selected from the group consisting of Fischer-Tropsch type catalytic synthesis, the synthesis methanol catalytic synthesis, catalytic synthesis of ethanol and catalytic synthesis of dimethyl ether. 8) Process according to any one of claims 1 to 7, characterized in that, prior to said gasification step (a), the carbonaceous material is subjected to a pretreatment, the latter advantageously comprising at least one step selected from the group consisting of a drying step, a roasting step, a granulation step and a grinding step. 9) Process according to any one of claims 1 to 8, characterized in that it further comprises a step of adding H ₂ to the purified effluent obtained following said step (c) and this, prior to said synthesis step (d). 10) Process according to any one of claims 1 to 9, characterized in that it further comprises a step of recovering the heat energy of the quenched effluent obtained following said quenching step (b) and prior to said purification step (c). 11) Installation that can be implemented in a method as defined in any one of claims 1 to 10, said installation comprising:  a unit for gasification of the carbonaceous material with synthesis gas, said unit comprising at least one driven-flow or fluidized-bed reactor;  a quenching unit disposed at the outlet of said gasification unit; a purification unit for the quenched effluent obtained at the outlet of said quenching unit; and  a catalytic synthesis reaction unit for preparing a gaseous effluent and a liquid effluent from the purified effluent obtained at the outlet of the purification unit; and means for recycling the gaseous effluent obtained at the outlet of the reaction unit to the quenching unit. 12) Apparatus according to claim 11, characterized in that said purification unit comprises at least one unit selected from the group consisting of an acid gas removal unit, a unit for eliminating halogenated compounds, an elimination unit sulfur compounds, a catalytic hydrolysis unit of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a unit for converting carbon monoxide to steam (WGS unit) and a final purification unit on guard bed. 13) Apparatus according to claim 11, characterized in that said purification unit does not include a unit for converting carbon monoxide to steam (WGS unit). 14) Installation according to any one of claims 11 to 13, characterized in that said catalytic synthesis reaction unit of the plant comprises at least one unit selected from the group consisting of a catalytic synthesis reactor Fischer-Tropsch type, a methanol catalytic synthesis reactor, a catalytic ethanol synthesis reactor and a catalytic synthesis reactor of dimethyl ether. 15) Installation according to any one of claims 11 to 14, characterized in that said installation further comprises  at least one pretreatment unit for the carbonaceous material, advantageously chosen from the group consisting of a drying unit, a roasting unit, a granulation unit and a grinding unit; means for injecting H ₂ into at least one of the effluents obtained at the outlet of the quenching unit or at the outlet of the purification unit; and or  means for recovering the heat energy of at least one of the effluents circulating in said installation.