FR3059313A1 - PROCESS FOR PRODUCING A SYNTHESIS GAS FROM A LIGHT HYDROCARBON STREAM AND A GAS CHARGE COMPRISING CO2, N2, O2 AND H2O FROM AN INDUSTRIAL UNIT COMPRISING AN OVEN A COMBUSTION - Google Patents

Abstract

Process for producing a synthesis gas containing CO and H 2 from a light hydrocarbon stream and a gaseous feed (70) from an industrial unit comprising a combustion furnace (100) and means for evacuating (200) the gaseous feed, said gaseous feed comprising CO2, N2, O2 and H2O, but not including hydrogen, comprising the following steps: said gaseous feed (101) obtained in said industrial unit upstream of said means for evacuating the gaseous feed; a reaction stream (113) comprising a light hydrocarbon stream (110) comprising methane and said gaseous feed (101) is prepared; said reaction stream (113) is sent to a tri-reforming reactor (1009) to obtain synthesis gas (114).

Description

Holder (s): IFP ENERGIES NOUVELLES Public establishment, HOLCIM TECHNOLOGY LTD.

Extension request (s)

Agent (s): IFP ENERGIES NOUVELLES.

PROCESS FOR THE PRODUCTION OF SYNTHESIS GAS FROM A LIGHT HYDROCARBON FLOW AND A GASEOUS CHARGE COMPRISING CO2, N2, O2 AND H2O FROM AN INDUSTRIAL UNIT COMPRISING AN OVEN COMBUSTION.

FR 3 059 313 - A1 (5 /) Process for producing a synthesis gas containing CO and H ₂ from a stream of light hydrocarbons and a gaseous charge (70) originating from an industrial unit comprising a combustion oven (100) and a means of evacuation (200) of the gaseous charge, said gaseous charge comprising CO ₂ , N ₂ , O ₂ and H ₂ O, but not comprising hydrogen, comprising the following stages:

- said gaseous charge (101) obtained in said industrial unit is taken upstream from said means for discharging the gaseous charge;

- Preparing a reaction stream (113) comprising a stream of light hydrocarbons (110) comprising methane and said gaseous feed (101);

- Said reaction flow (113) is sent to a tri-reforming reactor (1009) to obtain a synthesis gas (114).

200 t L 70 10 100 20 F

Method for producing a synthesis gas from a stream of light hydrocarbons and a gaseous feed comprising CO ₂ , N ₂ , O ₂ and H ₂ O from a industrial unit including a combustion oven

Technical area

The present invention relates to the field of the production of synthesis gas by tri-reforming reaction using a gaseous feed from an industrial unit comprising a combustion furnace. The synthesis gas obtained makes it possible to produce paraffinic or olefinic hydrocarbons, which are bases of high-quality liquid fuels (diesel cut with high cetane number, kerosene, etc.) or petrochemical bases, which can be obtained more particularly at using a FischerTropsch synthesis step.

State of the art

Several processes are known for producing synthesis gas from carbonaceous materials, in particular the partial oxidation reaction and the reforming of methane.

Partial oxidation, or gasification by partial oxidation (known by the acronym POX which comes from the English “partial oxidation” which means partial oxidation), consists of forming by combustion under sub-stoichiometric conditions a mixture at high temperature, generally between 1000 ° C and 1600 ° C, carbonaceous material on the one hand and ar or oxygen on the other hand, to oxidize the carbonaceous material and obtain a synthesis gas. Partial oxidation is compatible with all forms of carbonaceous fillers, including heavy ones. The partial oxidation reaction corresponds to the balance equation (1) below:

_^1/2 O ₂ + CH ₄ CO <=> + 2H ₂ (1)

Reforming methane is a chemical reaction that involves producing hydrogen from methane. There are two types of methane reforming process.

Steam reforming (or steam reforming) known by the acronym SMR which comes from the English “steam methane reforming” which means “methane reforming by steam, consists in reacting the charge, typically a natural gas or light hydrocarbons , on a catalyst in the presence of water vapor to obtain a synthesis gas which mainly contains, apart from water vapor, a mixture of carbon monoxide and hydrogen. Steam reforming is an endothermic reaction whose H ₂ / CO molar ratio is close to 3. Steam reforming meets the following balance equation (2):

CH ₄ + H ₂ O <=> CO + 3H ₂ (2)

Furthermore, dry reforming is a highly endothermic reaction whose H ₂ / CO molar ratio is close to 1. Dry reforming meets the following balance equation (3):

CO ₂ + CH ₄ <=> 2CO + 2H ₂ (3)

However, the H ₂ / CO ratios of the synthesis gas produced during dry reforming or steam reforming are not satisfactory for the production of fuels which require an H ₂ / CO molar ratio of the order of 2. The combination of these two processes makes it possible to obtain rations closer to those desired but the production of carbon (“coke”) which results therefrom on the catalyst is a major drawback.

One solution proposed in the prior art consists in combining three catalytic reactions: dry reforming, steam reforming and the partial oxidation reaction, these three reactions all being carried out in the same reactor. This reaction combination is called catalytic tri-reforming. Catalytic tri-reforming is of interest for the formation of synthesis gas. Indeed, Song et al. (Chemical innovation, 31 (2001) 21-26) describe a process allowing a gas comprising CH ₄ , CO ₂ , O ₂ and H ₂ O to react at high temperature in the presence of a catalyst to produce CO and H ₂ in controlled ratios.

Document US2008 / 0260628 discloses a process for the production of synthesis gas comprising a reaction step of reforming methane by supplying a mixture of carbon dioxide, water vapor and oxygen and using a catalyst based of nickel.

Document US2015 / 0031922 describes a process for the production of synthesis gas by catalytic treadforming using a mixture of hydrocarbons, CO ₂ , H ₂ O and O ₂ . CO ₂ comes from combustion gases from different industrial processes obtained after a separation step, in particular by separation with washing with amines.

Catalytic tri-reforming makes it possible in particular to recover the CO ₂ from combustion fumes (also called here combustion gas or gaseous charge) from power plants (Song et al., Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem., 2004, 49 (1), 128). The synthesis gas thus obtained can then be recovered by the Fischer-Tropsch reaction, in particular for the production of synthetic fuels.

Thus, it is known from the prior art to use a combustion gas from an industrial unit in tri-reforming reactions. However, the combustion gases are taken off the chimneys of the ovens, and therefore have a low temperature,

ie around 150 ° C [cf. Song et al., Prepr. Pap.-Am. Chem. Company, Div. Fuel Chem., 2004, 49 (1), 128]. Consequently, it is necessary to reheat the combustion gases to the temperature of the tri-reforming reaction, ie a temperature typically between 650 and 900 ° C. Furthermore, the relatively low temperature of the combustion gases leaving the chimneys can cause the condensation of water vapor contained in the combustion gases and therefore can significantly modify the H ₂ 0 / Hydrocarbons (HC) ratio which will no longer be optimal. for the catalytic tri-reforming reaction.

The Applicant has developed a new process for producing a synthesis gas obtained from a catalytic tri-reforming reaction using directly, without intermediate CO ₂ separation steps, combustion gases from units industrial facilities including a combustion furnace upstream of the flue gas evacuation chimneys, and more particularly units of the hydrogen production unit type by steam methane reforming, ammonia production unit, lime, glass production unit, or thermal power station supplied with gas, fuel oil or coal. Indeed, the combustion gases (here also called combustion smoke or gaseous feed) from such units have the advantage of having significant concentrations of CO ₂ , this allowing production of synthesis gas with better energy efficiency, a lower greenhouse gas emissions, and higher carbon yield.

Objects of the invention

The present invention relates to a process for producing a synthesis gas containing CO and H ₂ from a stream of light hydrocarbons and a gaseous feed from an industrial unit comprising at least one furnace combustion engine and at least one means of evacuating the gaseous charge to the outside of said industrial unit, said gaseous charge comprising CO ₂ , N ₂ , O ₂ and H ₂ O, optionally CO excluding a gaseous feed from a cement clinker manufacturing unit, but not containing hydrogen, which process comprises the following steps:

a) at least part of said gaseous charge obtained in said industrial unit is taken upstream of said means for evacuating the gaseous charge, said gaseous charge being sampled at a temperature between 180 and 800 ° C;

b) optionally, said gaseous charge obtained in step a) is treated;

c) preparing a reaction stream comprising a stream of light hydrocarbons comprising methane and said gaseous charge obtained in step a) or said treated gaseous charge obtained in step b) and;

d) said reaction flow is sent to a tri-reforming reactor to obtain a synthesis gas, said tri-reforming reactor operating at a temperature between 650 and 900 ° C., a pressure between 0.1 and 10 MPa, and a VVH between 0.1 and

200 Nm / h.kgcatalyst In a particular embodiment according to the invention, the gaseous charge also comprises CO.

Process according to claim 2, characterized in that the reaction flow comprises:

- an O ₂ / HC volume ratio of between 0.02 and 0.3;

- a CO ₂ / HC volume ratio of between 0.10 and 0.5;

- a H ₂ O / HC volume ratio of between 0.2 and 0.9;

- an N ₂ / HC volume ratio of between 0.1 and 3.0.

- a CO / HC volume ratio of between 0.005 and 0.5.

Advantageously, said industrial unit is chosen from a thermal power station supplied with coal or a lime production unit.

Method according to any one of claims 1 to 4, characterized in that a step is carried out between step a) and b) or c) of said process in which the gaseous charge, optionally treated, is filtered.

In another embodiment according to the invention, the gaseous feed does not contain CO, with the exclusion of gaseous feeds from cement clinker manufacturing units. Preferably, the reaction flow comprises:

- an O ₂ / HC volume ratio of between 0.02 and 0.3;

- a CO ₂ / HC volume ratio of between 0.10 and 0.5;

- a H ₂ O / HC volume ratio of between 0.2 and 0.9;

- an N ₂ / HC volume ratio of between 0.1 and 3.0.

Advantageously, the industrial unit is chosen from a hydrogen production unit by steam methane reforming, a glass production unit, or a thermal power station supplied with gas or fuel oil.

Advantageously, said gaseous charge comprises a CO ₂ content of between 5 and 50% by volume.

Preferably, the removal of the gaseous charge in step a) is carried out either directly at the outlet of the combustion oven, or after at least one step of purification of said gaseous charge from the combustion oven, said purification step being carried out by means of an absorber-neutralizer.

In a preferred embodiment, step b) is carried out for treating said gaseous charge obtained in step a), said step b) comprising the following substeps:

i) cooling said gaseous charge taken in step a);

ii) sending said cooled gaseous charge into a first separation flask to obtain a first gaseous effluent and a first liquid effluent;

iii) the first gaseous effluent is sent to a first compressor to obtain a first compressed gaseous effluent;

iv) the first compressed gaseous effluent is cooled to obtain the first cooled compressed gaseous effluent;

v) the first compressed compressed gaseous effluent is sent into a second separation flask to obtain a second gaseous effluent (and a second liquid effluent;

vi) the second gaseous effluent is sent to a second compressor to obtain the second compressed gaseous effluent;

vii) the second compressed gaseous effluent obtained in step vi) is brought into contact with at least part of said second liquid effluent obtained in step v) to form said treated gaseous charge.

Advantageously, said gaseous charge is cooled in step i) to a temperature between 60 and 80 ° C.

Advantageously, said first gaseous effluent is cooled in step iv) to a temperature between 30 and 60 ° C.

Advantageously, the reaction flow is previously heated to a temperature between 500 and 850 ° C.

Advantageously, said stream of light hydrocarbons is a natural gas or a liquefied petroleum gas.

Preferably, an addition of water vapor and / or oxygen is carried out between step a) and d) of said process.

Advantageously, the tri-reforming reactor comprises at least one supported catalyst comprising an active phase comprising at least one metallic element in oxide form or in metallic form chosen from groups VIIIB, IB, IIB, alone or as a mixture.

Description of the figure

FIG. 1 is a simplified schematic representation of an industrial installation comprising a combustion furnace 100 and a device for evacuating combustion fumes 200 from the combustion furnace.

FIG. 2 is a simplified schematic representation of the method according to the invention.

FIG. 3 is a schematic representation of a particular embodiment of the method according to the invention, in which the gaseous charge 70 taken from the industrial unit (step a) is treated (step b) before being brought into contact with a stream of light hydrocarbons 110 (step c) to form the reaction stream 113 of the catalytic tri-reforming reaction (step d).

Detailed description of the invention

Definitions

In the following, groups of chemical elements are given according to CAS Classification (CRC Handbook of Chemistry and Physics, CRC press publisher, editor DR Lide, 81 ^th Edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.

The textural and structural properties of the support and of the catalyst described below are determined by the characterization methods known to those skilled in the art. The total pore volume and the pore distribution are determined in the present invention by nitrogen porosimetry as described in the work "Adsorption by powders and porous solids. Principles, methodology and applications ”written by F. Rouquérol, J. Rouquérol and K. Sing, Academie Press, 1999.

By specific surface is meant the BET specific surface (S _B and in m ² / g) determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the BRUNAUER-EMMETT-TELLER method described in the periodical The Journal of American Society, 1938, 60, 309.

In the context of the present invention, the term “light hydrocarbons” designates hydrocarbon compounds comprising between 1 and 4 carbon atoms (C1-C4).

Description of the process

The present invention relates to a method for producing a synthesis gas containing CO and H ₂ from a stream of light hydrocarbons and a gaseous feed comprising CO ₂ , N ₂ , l 'O ₂ and H ₂ O, and possibly CO, said gaseous charge coming from an industrial unit comprising at least one combustion furnace and at least one means for discharging the gaseous charge towards the outside of said industrial unit. Preferably, the industrial unit is chosen from a hydrogen production unit by steam methane reforming, an ammonia production unit, a lime production unit, a glass production unit, or a power plant. thermal powered by gas, fuel oil or coal.

As with any industrial process, the skilled person is constantly confronted with the problems of increasing the production and productivity of industrial installations. This is why the Applicant has developed a process for producing a synthesis gas containing CO and H ₂ from a stream of light hydrocarbons and a gaseous feed comprising CO ₂ , N ₂ , O ₂ and H ₂ O, and possibly CO, from an industrial unit comprising at least one combustion oven and at least one means of evacuating the gaseous charge towards the outside of said industrial unit.

Referring to FIG. 1, schematically illustrating an industrial unit, combustible material 10 is sent to the combustion furnace 100 (also called here calcination furnace). The product from combustion in the combustion oven 100 is discharged via line 20. The gas charge 70 (also called combustion fumes) from the combustion oven 100 is in turn sent to the outside of the industrial unit by means of a combustion smoke evacuation device 200, such as chimneys.

The combustible material 10 can be any traditional fuel, such as natural gas, fuel oil, coal, or non-conventional fuel, such as biomass or carbonaceous waste (used oils, solvents, tires, sludges from treatment plants , ...).

According to the process for producing synthesis gas according to the invention, the gaseous charge 70 obtained after transformation of the combustible material 10 in the combustion furnace 100 is taken upstream of the means for evacuating the combustion fumes 200 and is then brought into operation. contact with a stream of light hydrocarbons in order to form a reaction stream, the latter being sent to a tri-reforming reactor making it possible to obtain the synthesis gas.

More particularly, with reference to FIG. 2, the process for producing a synthesis gas from a stream of light hydrocarbons and a gaseous feed comprising CO ₂ , N ₂ , O ₂ and H ₂ O, and possibly CO, originating from an industrial unit comprising at least one combustion oven 100 and at least one means of evacuating the gaseous charge 200 towards the outside of said industrial unit, includes the following steps:

a) removing said gaseous charge 70 obtained in said industrial unit upstream of said means for discharging the gaseous charge 200 without carrying out an intermediate separation step, said gaseous charge 70 being sampled at a temperature between 180 and 800 ° C. , preferably between 200 and 500 ° C, and even more preferably between 250 and 500 ° C;

b) optionally, said gaseous charge 70 taken from step a) is treated to obtain a treated gaseous charge 101;

c) preparing a reaction stream 113 comprising a stream of light hydrocarbons 110 comprising methane and said gaseous charge 70 obtained in step a), or optionally said treated gaseous charge 101 obtained in step b) and;

d) said reaction flow 113 is sent to a tri-reforming reactor 1009 to obtain a synthesis gas 114, said tri-reforming reactor 1009 operating at a temperature between 650 and 900 ° C, a pressure between 0.1 and 5 MPa and a VVH of between 0.1 and 200 Nm ³ /h.kg _cata i _yseur.

Steps a) to d) are described in more detail below.

Step a)

In step a), the gaseous charge 70 from the combustion furnace 100 is taken upstream of the means for discharging the gaseous charge 200 towards the outside of the industrial unit without carrying out an intermediate separation step.

All or part of the gaseous charge 70 can be used. The flow rate of the gas charge 70 sampled in step a) is between 10,000 to 2,000,000 Nm ³ / h, preferably from 20,000 to 1,000,000 Nm ³ / h.

In a first embodiment according to the invention, the gas charge 70 sampled in step a) comprises CO ₂ , N ₂ , O ₂ and H ₂ O, CO, but does not comprise no H ₂ . More particularly, the gas charge 70 comprises between 2% to 60% by volume of CO ₂ , preferably between 5% and 50% by volume.

When the industrial unit is a thermal power station supplied with coal, the gas charge 70 comprises between 2% to 30% by volume of CO ₂ , preferably between 5% and 25% by volume, and even more preferably between 5% and 20 % in volume.

When the industrial unit is a lime production unit, the gas feed 70 comprises between 10% to 60% by volume of CO ₂ , preferably between 15% and 50% by volume, and even more preferably between 20% and 50% by volume.

More particularly, the gas charge 70 comprises between 30% to 80% by volume of N ₂ , preferably between 30% and 70% by volume.

When the industrial unit is a thermal power station supplied with coal, the gaseous charge 70 comprises between 50% to 80% by volume of N ₂ , preferably between 55% and 75% by volume, and even more preferably between 65% and 75 % in volume.

When the industrial unit is a lime production unit, the gas charge 70 comprises between 30% to 80% by volume of N ₂ , preferably between 30% and 70% by volume, and even more preferably between 35% and 65% by volume.

More particularly, the gas charge comprises between 0.5% to 20% by volume of O ₂ , preferably between 1% and 15% by volume.

When the industrial unit is a thermal power station supplied with coal, the gas charge 70 comprises between 0.5% to 15% by volume of O ₂ , preferably between 1% and 10% by volume, and even more preferably between 2 % and 10% by volume.

When the industrial unit is a lime production unit, the gaseous charge 70 comprises between 1% to 20% by volume of O ₂ , preferably between 1% and 15% by volume, and even more preferably between 2% and 10% by volume.

More particularly, the gas charge comprises between 0.5% to 30% by volume of CO, preferably between 1% and 30% by volume.

When the industrial unit is a thermal power station supplied with coal, the gas charge 70 comprises between 1% to 30% by volume of CO, preferably between 2% and 30% by volume, and even more preferably between 2% and 25%. in volume.

When the industrial unit is a lime production unit, the gaseous charge 70 comprises between 0.5% to 20% by volume of CO, preferably between 1% and 15% by volume, and even more preferably between 1% and 10% by volume.

More particularly, the gas charge comprises between 2% to 25% by volume of H ₂ O, preferably between 5% and 25% by volume, and even more preferably between 5% and 20% by volume.

In another embodiment according to the invention, the gas charge 70 sampled in step a) comprises CO ₂ , N ₂ , O ₂ and H ₂ O, but does not include H ₂ and does not include CO, excluding gaseous feeds from the manufacture of cement clinker.

More particularly, the gas charge 70 comprises between 7% to 40% by volume of CO ₂ , preferably between 15% and 35% by volume.

When the industrial unit is a hydrogen production unit, the gas charge 70 comprises between 10% to 35% by volume of CO ₂ , preferably between 10% and 30% by volume, and even more preferably between 15% and 25% by volume.

When the industrial unit is a glass production unit, the gas charge 70 comprises between 20% to 60% by volume of CO ₂ , preferably between 25% and 50% by volume, and even more preferably between 30% and 50% by volume.

When the industrial unit is a thermal power station supplied with gas or fuel oil, the gas charge 70 comprises between 2% to 30% by volume of CO ₂ , preferably between 5% and 25% by volume, and even more preferably between 5% and 20% by volume.

More particularly, the gas charge comprises between 20% to 80% by volume of N ₂ , preferably between 25% and 75% by volume.

When the industrial unit is a hydrogen production unit, the gas charge 70 comprises between 40% to 80% by volume of N ₂ , preferably between 45% and 75% by volume, and even more preferably between 50% and 70% by volume.

When the industrial unit is a glass production unit, the gas charge 70 comprises between 20% to 80% by volume of N ₂ , preferably between 25% and 70% by volume, and even more preferably between 30% and 65% by volume.

When the industrial unit is a thermal power station supplied with gas or fuel oil, the gas charge 70 comprises between 50% to 80% by volume of N ₂ , preferably between 55% and 75% by volume, and even more preferably between 65% and 75% by volume.

More particularly, the gas charge comprises between 0.5% to 20% by volume of O ₂ , preferably between 1% and 10% by volume.

When the industrial unit is a hydrogen production unit, the gas charge 70 comprises between 0.5% to 15% by volume of O ₂ , preferably between 0.5% and 10% by volume, and again more preferably between 1% and 5% by volume.

When the industrial unit is a glass production unit, the gaseous charge 70 comprises between 1% to 20% by volume of O ₂ , preferably between 1% and 15% by volume, and even more preferably between 2% and 10% by volume.

When the industrial unit is a thermal power station supplied with gas or fuel oil, the gas charge 70 comprises between 0.5% to 15% by volume of O ₂ , preferably between 1% and 10% by volume, and again more preferably between 1.5% and 5% by volume.

More particularly, the gaseous feed comprises between 2% to 25% by volume of H ₂ O, preferably between 5% and 20% by volume.

When the industrial unit is a hydrogen production unit, the gas charge 70 comprises between 2% to 25% by volume of H ₂ O, preferably between 5% and 25% by volume, and even more preferably between 5 % and 20% by volume.

When the industrial unit is a glass production unit, the gaseous charge 70 comprises between 2% to 25% by volume of H ₂ O, preferably between 5% and 25% by volume, and even more preferably between 5% and 20% by volume.

When the industrial unit is a thermal power station supplied with gas or fuel oil, the gas charge 70 comprises between 5% to 25% by volume of H ₂ O, preferably between 7% and 25% by volume, and even more preferably between 8% and 20% by volume.

The temperature of the gas charge 70 sampled in step a) is between 180 ° C and 800 ° C, preferably between 200 ° C and 500 ° C, customs very preferred between 250 ° C and 500 ° C.

In the particular embodiment according to which the industrial unit is chosen from a lime manufacturing unit or a coal-fired thermal power plant, a step of filtering the combustion fumes 70 sampled in step a) is advantageously carried out in order to reduce the dust content of combustion fumes. For example, the filtration step can be carried out using bag filters or ceramic filters. Preferably, the dust content in the combustion fumes 70 after the filtration step is less than 1000 mg / m ³ , very preferably less than 100 mg / m ³ .

Preferably, the gaseous feedstock 70 sampled in step a) undergoes a desulfurization step in order to reduce the H ₂ S, COS, mercaptans or other sulfur-containing compounds content possibly present in said gaseous feed. This desulfurization step can be carried out by any method known to a person skilled in the art, for example by a step of hydrogenation of the sulfur-containing compounds followed by a step of fixing H ₂ S. During the step of hydrogenation , the sulfur compounds (COS, mercaptans, etc.) are transformed into H ₂ S by reaction with the hydrogen contained in said gaseous charge to be treated. The reaction is carried out at a temperature between approximately 350 to 400 ° C, in the presence of a hydrogenation catalyst. Generally, the hydrogenation catalyst used comprises as active phase at least one metal from group VIB, such as molybdenum, and at least one metal from group VIIIB, preferably chosen from cobalt or nickel. The catalyst further comprises a support comprising a refractory oxide, preferably alumina. Advantageously, the catalyst used is in sulfurized form. The second step for fixing the H ₂ S generally takes place at a temperature of between 200 and 400 ° C. in the presence of a capture mass comprising a compound of the metal, oxide, zeolite, or even carbonate type, and at least one element chosen from the group formed by Ca, Mg, Mn, Fe, Ni, Cu, Zn, Ag, Sn, La, Ce. Preferably, the capture mass comprises Zn in oxide form (ZnO) at a content of between 85% by weight and 100% by weight in oxide form relative to the total weight of the capture mass. Binders can be used such as silica, alumina or an alumina precursor, clays such as bentonite, kaolinite, montmorillonite, alone or as a mixture, in order to impart sufficient mechanical strength to the solid formed . The collection mass can be in the form of preferably cylindrical or multilobed extrudates, spheres or pellets.

Step b) (optional)

In a particular embodiment of the method according to the invention, there is carried out a step b) of processing the gaseous charge 70 sampled in step a). This step allows an adjustment by condensation of the quantity of water necessary for the catalytic trireforming reaction as well as a reduction in the electric power consumed by reduction in the volume flow sucked in.

In step b) of the process according to the invention, the gas charge 70 obtained in step a) is treated to obtain a treated gas charge 101.

Referring to FIG. 3, when step b) of processing the gaseous charge 70 taken in step a) is carried out, step b) comprises the following substeps:

i) the gaseous charge 70 taken in step a) is cooled;

ii) the cooled gaseous charge 102 is sent into a first separation flask 1002 to obtain a first gaseous effluent 103 and a first liquid effluent 118;

iii) the first gaseous effluent 103 is sent to a first compressor 1003;

iv) the first compressed gaseous effluent 104 is cooled;

v) the first cooled compressed gaseous effluent 105 is sent into a second separation flask 1005 to obtain a second gaseous effluent 106 and a second liquid effluent 108;

vi) the second gaseous effluent 106 is sent to a second compressor 1006;

vii) the second compressed gaseous effluent 107 obtained in step vi) is brought into contact with at least part of said second liquid effluent 108 obtained in step v) to form the treated gaseous charge 101.

The temperature of the gas charge 70 sampled in step a) is between 180 ° C and 800 ° C, preferably between 200 ° C and 500 ° C, most preferably between 250 ° C and 500 ° C. The pressure of the gaseous feedstock 70 taken in step a) is of the order of between 0.05 and 0.20 MPa (0.5 and 2.0 bar), preferably between 0.08 and 0.15 MPa (0.8 and 1.5 bar).

In step i), the gas charge 70 is cooled to a temperature between 60 and 80 ° C. by yielding its calories to the flow 113 in a first exchanger 1001. The cooled gas charge 102 is sent to a guard flask 1002 for obtaining a first gaseous effluent 103 and a first liquid effluent 118 (step ii)).

The pressure of the first gaseous effluent 103 is increased between 0.1 and 0.2 MPa (1 and 2 bar) by a first compressor 1003 (step iii) from which comes out a first compressed gaseous effluent 104 which is cooled to a temperature between 30 and 60 ° C by a water exchanger 1004 (step iv).

The first cooled compressed gaseous effluent 105 is sent to a separator flask 1005 to obtain a second gaseous effluent 106 and a second liquid effluent 108 composed essentially of condensed water (step v).

The pressure of the second gaseous effluent 106 coming from the separator 1005 is increased between 0.1 and 0.5 MPa (1 and 5 bar) by a second compressor 1006 from which comes a second compressed gaseous effluent 107 (step vi).

Finally, at least part of the second compressed gaseous effluent 107 obtained in step vi) is brought into contact with at least part of said second liquid effluent 108 obtained in step v) (via line 109) to form the charge. treated gas 101 (step vii). The other part of the second liquid effluent is discharged from the process via line 119, preferably at a flow rate of the order of 15 to 25% by volume relative to the total flow rate of the second liquid effluent 108. Preferably, said at least one part of the second liquid effluent 109 passes through a pump 1007 before being mixed with the second compressed gaseous effluent 107.

Step c)

According to step c) of the process, a reaction stream 113 is prepared comprising a stream of light hydrocarbons 110 comprising methane and the gaseous charge 70 sampled in step a) (cf. FIG. 2) or the treated gaseous charge 101 (cf. figure 3) of step b). The reaction flow 113 is then sent to the tri-reforming reactor 1009.

Preferably the source of hydrocarbon is a natural gas or a liquefied petroleum gas, very preferably the source of hydrocarbon is a natural gas comprising at least 50% by volume of methane, preferably at least 60% by volume of methane, and more preferably at least 70% by volume of methane.

In the particular embodiment in which the method according to the invention comprises a step of processing the combustion fumes collected in step a) (ie when step b) is performed), the reaction flow 113 is obtained by putting in contact the second liquid effluent 108, the second compressed gaseous effluent 107 and the stream of light hydrocarbons. Advantageously, the reaction flow 113 is heated in an exchanger 1001 by the combustion fumes 70 sampled in step a) of the process. The reaction flow from this exchanger 1001 can then be brought to a temperature close to that of the catalytic tri-reforming reaction, to a temperature between 500 to 850 ° C, preferably to a temperature between 750 ° C at 850 ° C, via the heat exchanger 1008. The reaction flow 113 is then sent to the tri-reforming reactor 1009.

Additions of oxygen are carried out in all proportions to obtain a reaction flow 113 with the desired volume ratio between the reagent O ₂ and the source of hydrocarbons (HC). These top-ups can be carried out together or separately, and before or after mixing the gaseous charge with the source of hydrocarbons. In particular, these add-ons can be carried out either by a flow 116 added directly to the gaseous charge 70 sampled in step a), or added by a flow 117 added to the reaction flow 113 before or after passage through the exchanger 1001.

The oxygen source may preferably be atmospheric air or a flow of oxygen originating either from a cryogenic air separation process (ASU, for air separation unit in English terminology), or d 'a pressure inversion adsorption process (PSA, for pressure swing adsorption in English terminology), or a vacuum inversion adsorption process (VSA, for vacuum swing adsorption in English terminology). When a top-up of water vapor is carried out, any source of water vapor or process for generating water vapor may be used.

Preferably, the CO ₂ / HC volume ratio of the reaction flow 113 is between 0.1 and 0.5, very preferably between 0.1 and 0.4.

Preferably, the H ₂ O / HC volume ratio of the reaction flow 113 is between 0.2 and 0.9, very preferably between 0.4 and 0.9.

Preferably, the N ₂ / HC volume ratio of the reaction flow 113 is between 0.1 and 3.0, very preferably between 0.2 and 1.5.

Preferably, the O ₂ / HC volume ratio of the reaction flow 113 is between 0.02 and 0.3, very preferably between 0.05 and 0.2.

When the reaction flow comprises CO, the CO / HC volume ratio of the reaction flow 113 is between 0.005 and 0.5, very preferably the CO / HC volume ratio is between 0.01 and 0.4.

Depending on the composition of the gas charge 70 sampled in step a) or of the treated gas charge 101 obtained in step b), it is possible to add water vapor in all proportions to obtain a reaction flow. 113 with the desired volume ratio between the reagent H ₂ O and the source of hydrocarbons (HC). These top-ups can be carried out together or separately, and before or after mixing the gaseous charge with the source of hydrocarbons. In particular, these top-ups can be carried out either by a flow

116 added directly to the gaseous charge 70 taken in step a), or added by a flow

117 added to reaction flow 113.

Step d)

In step d) the charge containing light hydrocarbons, CO ₂ , N ₂ , O ₂ and H ₂ O, possibly CO, but not comprising H ₂ , is sent to a catalytic reactor 1009 so as to transform said charge and obtain an effluent containing carbon monoxide and hydrogen.

The catalytic tri-reforming reactor 1009 can be any type of reactor suitable for the transformation of the gaseous charge. Preferably, the catalytic reactor will be a fixed bed or fluidized bed reactor. The reaction zone is filled with a heterogeneous catalyst having an active phase in oxide or metallic form composed of at least one element chosen from groups VIII, IB, IIB, alone or as a mixture. The catalyst comprises an active phase content expressed in% weight of elements relative to the total mass of the catalyst of between 0.1% and 60%, preferably between 1% and 30%. Advantageously, the catalyst used comprises a mass content of between 20 ppm and 50%, expressed in% element weight relative to the total mass of the catalyst, preferably between 50 ppm and 30% by weight, and very preferably between 0.01% and 5% by weight of at least one doping element chosen from the groups VIIB, VB, IVB, IIIB, IA (alkaline element), IIA (alkaline earth element), NIA, VIA, alone or as a mixture . The catalyst comprises a support containing a matrix of at least one refractory oxide based on elements such as Mg, Ca, Ce, Zr, Ti, Al, Si, alone or as a mixture. The support on which said active phase is deposited, as well as any dopants, may have a morphology in the form of beads, extrudates (for example of three-lobed or four-lobed form), pellets, cylinders with or without holes, or have a morphology under powder form of variable particle size.

When the active phase of the catalyst is in metallic form, a temperature activation step under reducing gas may be implemented before the injection of the reaction flow 113 into the reactor 1009.

In the reaction zone, the reaction flow is brought to a temperature of 650 ° C to 900 ° C and a pressure of 0.1 and 10.0 MPa (1 bar and 100 bar), preferably between 0.1 and 1, 0 MPa (1 and 10 bar). The hourly volume velocity of the reaction flow is between 0.1 and 200 Nm ^{3 /} h.kgcataiyseur, preferably between 1 and 100 Nm ³ /h.kgcatai _yseurj very preferably between 1 and 50 Nm ³ /h.kg _cata i _yseur. The effluent 114 from reactor 1009 comprising carbon monoxide and hydrogen in a volume ratio H ₂ / CO of between 1 and 3, preferably between 1.5 and 2.7, very preferably between 1, 7 and 2.7. Preferably, this effluent does not comprise more than 50% by volume of N ₂ , very preferably not more than 30% by volume.

Advantageously, the effluent 114 passes through a heat exchanger (heat exchanger 1008 in the embodiment as illustrated in FIG. 3) in order to obtain a cooled effluent 115 between 120 and 250 ° C which can be recovered directly by all the routes known to those skilled in the art. Indeed, the effluent obtained according to the invention has the characteristics of a synthesis gas and can be recovered directly by any means known to those skilled in the art. Preferably, the effluent comprising carbon monoxide is used in Fischer Tropsch synthesis for the production of synthetic fuels. Before recovery of the effluent, it may be advantageous to carry out a purification step, in particular De-Nox and / or De-Sox by any process known to those skilled in the art.

The invention is illustrated by the following examples which are in no way limiting in nature.

Examples

Example 1 Conversion of a combustion effluent from a hydrogen production unit into a gaseous composition comprising carbon monoxide and dihvdroqene (according to the invention)

A gaseous combustion effluent from a hydrogen production unit is removed from the furnace containing 18% volume of CO ₂ , 17% volume of H ₂ O, 1.5% volume of O ₂ and 64% volume of N ₂ . The temperature of this gas flow is 200 ° C. Additions of water vapor and oxygen (from atmospheric air), as well as a flow of natural gas are added to this flow of gas ex-hydrogen production unit in order to obtain the volume ratios following: N ₂ / HC = 1.41; H ₂ O / HC = 0.66; CO ₂ / HC = 0.32; O ₂ / HC = 0.10.

The reaction mixture is brought to 850 ° C. under a position of 0.25 MPa (2.5 bar), in the presence of a nickel-based catalyst (HiFUEL® R110, Johnson Matthey Pic, Alfa Aesar). The schedule of the load space velocity was 8 Nm ³ /h.kg _cata i _yseur.

The effluent obtained contains 23% by volume of CO, 46% by volume of dihydrogen, 1.3% by volume of CO ₂ , 2.8% by volume of H ₂ O, traces of hydrocarbons as well as 27% by volume of N ₂ .

The H ₂ : CO molar ratio is of the order of 2, which is acceptable for use as a feed for a fuel production unit by the Fischer-Tropsch process.

The conversions to CO ₂ and to hydrocarbons are respectively 79% and 96%. The carbon yield of the reaction with respect to the hydrocarbons introduced is calculated at 121%.

Example 2 Conversion of an effluent from a coal-fired power plant furnace into a gaseous composition comprising carbon monoxide and dihydrogen (according to the invention)

A gaseous effluent from a coal-fired power station furnace is removed from the furnace after an electrostatic filtration step containing 15% volume of CO ₂ , 10% volume of H ₂ O, 5% volume of CO, 5% volume of O ₂ and 65% volume of N ₂ . The temperature of this gas flow is 250 ° C. Additions of water vapor and oxygen (by adding atmospheric air), as well as a flow of natural gas are added to this flow of gas ex-thermal power station in order to obtain the following volume ratios: N ₂ / HC = 1.16; H ₂ O / HC = 0.69; CO ₂ / HC = 0.26; CO / HC = 0.09; O ₂ / HC = 0.10.

The reaction mixture is brought to 850 ° C. under a position of 0.25 MPa (2.5 bar), in the presence of a commercial catalyst based on Nickel (HiFUEL® R110, Johnson Matthey Pic, Alfa Aesar). The hourly volume speed of the load is 8 Nm3 / h.kgcatalyst. The effluent obtained contains 24% by volume of CO, 48% by volume of dihydrogen, 1% by volume of hydrocarbons, 1.2% by volume of CO ₂ and 2.7% by volume of H ₂ O as well as 23% by volume of N ₂ .

The H ₂ : CO molar ratio is of the order of 2, which is acceptable for use as a feed for a fuel production unit by the Fischer-Tropsch process.

The conversions to CO ₂ and to hydrocarbons are respectively 76% and 95%. The carbon yield of the reaction with respect to the hydrocarbons introduced is calculated at 123%.

Other synthesis gas production processes with a H ₂ / CO molar ratio close to 2, such as partial oxidation, steam reforming or autothermal reforming, do not make it possible to achieve higher reaction carbon yields 100% compared to the hydrocarbons introduced (part of the CO coming from CO ₂ ). Thus, by the best carbon yields, the method according to the invention allows a less expensive production of a synthesis gas. Indeed, less hydrocarbon is consumed per volume of synthesis gas produced at a given H ₂ / CO molar ratio.

Claims (17)

1. Method for producing a synthesis gas containing CO and H ₂ from a stream of light hydrocarbons and a gaseous feed (70) from an industrial unit comprising at least one furnace combustion (100) and at least one means (200) for evacuating the gaseous charge to the outside of said industrial unit, said gaseous charge comprising CO ₂ , N ₂ , O ₂ and H ₂ O, possibly CO, excluding a gaseous feed from a cement clinker manufacturing unit, but not containing hydrogen, which process comprises the following steps: a) at least part of said gaseous charge (101) obtained in said industrial unit is taken upstream from said means for evacuating the gaseous charge, said gaseous charge being sampled at a temperature between 180 and 800 ° C; b) optionally, said gas charge (101) obtained in step a) is treated; c) preparing a reaction stream (113) comprising a stream of light hydrocarbons (110) comprising methane and said gaseous charge (101) obtained in step a) or said treated gaseous charge obtained in step b) and ; d) said reaction flow (113) is sent to a tri-reforming reactor (1009) to obtain a synthesis gas (114), said tri-reforming reactor (1009) operating at a temperature between 650 and 900 ° C. , a pressure between 0.1 and 10 MPa, and a VVH between 0.1 and 200 Nm ³ /h.kg _cata i _yseur . 2. Method according to claim 1, characterized in that the gaseous charge further comprises CO. 3. Method according to claim 2, characterized in that the reaction flow (113) comprises: - an O ₂ / HC volume ratio of between 0.02 and 0.3; - a CO ₂ / HC volume ratio of between 0.10 and 0.5; - a H ₂ O / HC volume ratio of between 0.2 and 0.9; - an N ₂ / HC volume ratio of between 0.1 and 3.0. - a CO / HC volume ratio of between 0.005 and 0.5. 4. Method according to any one of claims 1 to 3, characterized in that said industrial unit is chosen from a thermal power station supplied with coal or a lime production unit. 5. Method according to any one of claims 1 to 4, characterized in that there is carried out between step a) and b) or c) of said process a step in which the gaseous charge, optionally treated, is filtered. 6. Method according to claim 1, characterized in that the gaseous feed does not contain CO and is not a gaseous feed from a cement clinker manufacturing unit. 7. Method according to claim 6, characterized in that the reaction flow (113) comprises: - an O ₂ / HC volume ratio of between 0.02 and 0.3; - a CO ₂ / HC volume ratio of between 0.10 and 0.5; - a H ₂ O / HC volume ratio of between 0.2 and 0.9; - an N ₂ / HC volume ratio of between 0.1 and 3.0. 8. Method according to claims 6 or 7 characterized in that the industrial unit is chosen from a hydrogen production unit by steam methane reforming, a glass production unit, or a thermal power plant supplied with gas or in fuel oil. 9. Method according to any one of claims 1 to 8, characterized in that said gaseous charge (101) comprises a CO ₂ content of between 5 and 50% by volume. 10. Method according to any one of claims 1 to 9, characterized in that the removal of the gaseous charge (101) in step a) is carried out either directly at the outlet of the combustion oven, or after at least one step for purifying said gaseous charge from the combustion oven, said purification step being carried out by means of an absorber-neutralizer. 11. Method according to any one of claims 1 to 10, in which step b) of carrying out said gaseous charge obtained in step a) is carried out, said step b) comprising the following substeps: i) cooling said gaseous charge (101) taken in step a); ii) sending said cooled gaseous charge (102) in a first separation flask (1002) to obtain a first gaseous effluent (103) and a first liquid effluent (118); iii) the first gaseous effluent (103) is sent to a first compressor (1003) to obtain a first compressed gaseous effluent (104); iv) the first compressed gaseous effluent (104) is cooled to obtain the first cooled compressed gaseous effluent (105); v) the first cooled compressed gaseous effluent (105) is sent into a second separation flask (1005) to obtain a second gaseous effluent (106) and a second liquid effluent (108); vi) the second gaseous effluent (106) is sent to a second compressor (1006) to obtain the second compressed gaseous effluent (107); vii) the second compressed gaseous effluent (107) obtained in step vi) is brought into contact with at least part of said second liquid effluent (108) obtained in step v) to form said treated gaseous charge. 12. The method of claim 11, characterized in that said gaseous charge (101) is cooled in step i) to a temperature between 60 and 80 ° C. 13. Method according to claims 11 or 12, characterized in that said first gaseous effluent (104) is cooled in step iv) to a temperature between 30 and 60 ° C. 14. Method according to any one of claims 1 to 13 characterized in that the reaction flow (113) is previously heated to a temperature between 500 and 850 ° C. 15. Method according to any one of claims 1 to 14, characterized in that said stream of light hydrocarbons (110) is a natural gas or a liquefied petroleum gas. 16. Method according to any one of claims 1 to 15, characterized in that an addition of water vapor and / or oxygen is carried out between step a) and d) of said method. 17. Method according to any one of claims 1 to 16, characterized in that the tri-reforming reactor (1009) comprises at least one supported catalyst comprising an active phase comprising at least one metallic element in oxide form or in metallic form chosen from groups VIIIB, IB, IIB, alone or as a mixture. 1/2 200 J L 70 10 100 20