METHOD AND REACTOR FOR PRODUCING SYNTHESIS GAS FROM A CARBON AND HYDROGEN SOURCE IN THE PRESENCE OF AN OXY FLAME
20230249969 · 2023-08-10
Inventors
- Raynald LABRECQUE (Shawinigan (QB), CA)
- Robert SCHULZ (Sainte-Julie (QB), CA)
- Michel VIENNEAU (Saint-Hubert (QB), CA)
- Germain LAROCQUE (Beloeil (QB), CA)
Cpc classification
C10K3/026
CHEMISTRY; METALLURGY
C01B2203/0238
CHEMISTRY; METALLURGY
B01J2219/00155
PERFORMING OPERATIONS; TRANSPORTING
C01B3/02
CHEMISTRY; METALLURGY
C01B3/36
CHEMISTRY; METALLURGY
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01B3/12
CHEMISTRY; METALLURGY
B01J2219/00159
PERFORMING OPERATIONS; TRANSPORTING
C10G47/22
CHEMISTRY; METALLURGY
B01J19/0006
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/0255
CHEMISTRY; METALLURGY
Y02P20/141
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J19/0013
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/0283
CHEMISTRY; METALLURGY
International classification
C01B3/36
CHEMISTRY; METALLURGY
C01B3/12
CHEMISTRY; METALLURGY
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The technology relates to a method of producing synthesis gas comprising carbon monoxide (CO) and hydrogen (H.sub.2), wherein the synthesis gas is produced by a reduction reaction of a first flow comprising a carbon source and an excess of hydrogen in contact with an Oxy-flame. The hydrogen comes from a reducing stream, a first portion of which ends up in the first flow, and a second part of which is used to generate the Oxy-flame by combustion of the hydrogen in the presence of a second flow comprising oxygen (O.sub.2), the second flow coming from an oxidizing stream. The first flow and the second flow are at a distance from each other such that the Oxy-flame supports the reaction between the carbon source and the hydrogen. A reactor, which can have different configurations, is also proposed for implementing the method.
Claims
1. A method of producing synthesis gas comprising carbon monoxide (CO) and hydrogen (H2), wherein the synthesis gas is produced by a reduction reaction of a first flow comprising a carbon source and an excess of hydrogen in contact with an Oxy-flame, and wherein: the hydrogen comes from a reducing stream, a first part of which ends up in the first flow and a second part is used to generate the Oxy-flame by combustion of hydrogen in the presence of a second flow comprising oxygen (O.sub.2), the second flow coming from an oxidizing stream, the first flow and the second flow are at a distance from each other such that the Oxy-flame supports the reaction between the carbon source and the hydrogen.
2. The method according to claim 1, wherein the reduction reaction is carried out in the absence of solid catalyst.
3. The method according to claim 1, wherein the Oxy-flame generates ionic species and free radicals which promote the conversion of the carbon source to CO.
4. The method according to claim 1, wherein the carbon source comprises: CO.sub.2; or at least one type of oxygenated molecules of formula C.sub.αH.sub.βO.sub.γ wherein α is between 1 and 5, β is between 2 and 10 and γ is between 1 and 4; or one or more hydrocarbons; or a mixture of at least two of these carbon sources.
5. The method according to claim 1, wherein the carbon source comprises CO.sub.2 and the reduction reaction comprises a reverse reaction of gas to water or “Reverse Water Gas Shift”.
6. The method according to claim 1, wherein the reducing stream is hydrogen.
7. The method according to claim 1, wherein the reducing stream comprises hydrogen and the carbon source.
8. The method according to claim 1, wherein the reducing stream comprises hydrogen and CO.sub.2.
9. The method according to claim 1, wherein the reducing stream comprises hydrogen, CO.sub.2 and at least one type of oxygenated molecules of formula C.sub.αH.sub.βO.sub.γ where α is between 1 and 5, β is between 2 and 10 and γ is between 1 and 4.
10. The method according to claim 1, wherein the oxidizing stream is oxygen.
11. The method according to claim 1, wherein the oxidizing stream comprises oxygen and CO.sub.2.
12. The method according to any one of claims 1 to 6 claim 1, wherein the reducing stream comprises only hydrogen, the oxidizing stream comprises only oxygen and the carbon source is supplied by an independent stream.
13. The method according to claim 12, wherein the independent stream comprises CO.sub.2 or the independent stream comprises CO.sub.2 and methane.
14. (canceled)
15. The method according to claim 1, wherein the oxygen comes from a water electrolysis reaction and/or the hydrogen comes from a water electrolysis reaction and/or the carbon source comes from a gas mixture resulting from a biomass gasification or pyrolysis process.
16. (canceled)
17. (canceled)
18. The method according to claim 1, wherein the reduction reaction is carried out at an average temperature of at least 600° C.
19. (canceled)
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21. The method according to claim 1, wherein the first flow and the second flow are at a distance from each other of between 0.1 mm and 100 mm, or at a distance from each other of between 0.3 mm and 50 mm, or at a distance from each other of between 0.6 mm and 30 mm.
22. (canceled)
23. (canceled)
24. The method according to claim 1, wherein the carbon source comprises CO.sub.2 and the reduction reaction is carried out using an H.sub.2/CO.sub.2 molar ratio of between 2 and 7.
25. The method according to claim 1, wherein the carbon source comprises CO.sub.2 and the reduction reaction is carried out using an O.sub.2/CO.sub.2 molar ratio of between 0.35 and 0.9.
26. The method according to claim 1, wherein the reduction reaction is carried out using an O.sub.2/H.sub.2 molar ratio of between 0.1 and 0.3.
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37. A reactor for producing a synthesis gas comprising carbon monoxide (CO) and hydrogen (H.sub.2), said reactor comprising: a reaction chamber wherein the synthesis gas is produced by a reduction reaction of a first flow comprising a carbon source and an excess of hydrogen in contact with an Oxy-flame, at least one first means for supplying the reaction chamber with a reducing stream comprising hydrogen, a first part of the reducing stream ending up in the first flow and a second part being used to generate the Oxy-flame in the reaction chamber, by combustion of hydrogen in the presence of a second flow comprising oxygen (O.sub.2), at least one second means for supplying the reaction chamber with an oxidizing stream forming the second flow, the first flow and the second flow being at a distance from each other such that the Oxy-flame supports the reaction between the carbon source and the hydrogen.
38. (canceled)
39. The reactor according to claim 37, wherein the Oxy-flame generates ionic species and free radicals which promote the conversion of the carbon source to CO.
40. The reactor according to claim 37, wherein the carbon source comprises: CO.sub.2; or at least one type of oxygenated molecules of formula C.sub.αH.sub.βO.sub.γ wherein α is between 1 and 5, β is between 2 and 10 and γ is between 1 and 4; or one or more hydrocarbons; or a mixture of at least two of these carbon sources.
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Description
BRIEF DESCRIPTION OF THE FIGURES
[0078]
[0079]
[0080]
[0081]
[0082]
[0083]
[0084]
[0085]
DETAILED DESCRIPTION
[0086] All technical and scientific terms and expressions used herein have the same meanings as those generally understood by the person skilled in the art of the present technology. The definition of certain terms and expressions used are nevertheless provided below.
[0087] The term “about” as used in the present document means approximately, in the region of, and around. When the term “about” is used in connection with a numerical value, it modifies it, for example, above and below by a variation of 10% compared to the nominal value. This term can also take into account, for instance, the experimental error of a measuring device or the rounding of a value.
[0088] When an interval of values is mentioned in the present application, the lower and upper limits of the interval are, unless otherwise indicated, always included in the definition.
[0089] The chemical structures described here are drawn according to the conventions of the field. Also, when an atom, such as a carbon atom, as drawn appears to include an incomplete valence, then the valence will be assumed to be satisfied by one or more hydrogen atoms even if they are not explicitly drawn.
[0090] In the present description, the terms “synthesis gas” and “syngas” are used interchangeably to identify a gas mixture comprising at least carbon monoxide (CO) and hydrogen (H.sub.2). In some embodiments, the syngas or syngas can comprise CO.sub.2. According to one embodiment, the H.sub.2/CO molar ratio in the synthesis gas is greater than or equal to 1. In other embodiments, the synthesis gas can have an H.sub.2/CO molar ratio of at least 1.8, for example between 1.8 and 5.0. According to another embodiment, the H.sub.2/CO molar ratio in the synthesis gas is greater than or equal to 2. Thus, the H.sub.2/CO molar ratio in the synthesis gas can be 1.8 or 1.9 or 2.0 or 2.1 or 2.2 or 2.3 or 2.4 or 2.5 or 2.6 or 2.7 or 2.8 or 2.9 or 3.0 or 3.1 or 3.2 or 3.3 or 3.4 or 3.5 or 3.6 or 3.7 or 3.8 or 3.9 or 4.0 or 4.1 or 4.2 or 4.3 or 4.4 or 4.5 or 4.6 or 4.7 or 4.8 or 4.9 or 5.0. However, synthesis gases with different and various H.sub.2/CO molar ratios can be obtained.
[0091] The term “stream” is used to describe the different gas streams which feed the reaction chamber in which the formation of the synthesis gas is carried out. As will be described in more detail below, the method uses at least one stream containing hydrogen (H.sub.2) and at least one stream containing oxygen (O.sub.2). The carbon source used in the method, depending on its nature, can be fed either by an independent stream, or by the O.sub.2 containing stream, or by the H.sub.2 containing stream. The streams entering the reaction chamber are in gaseous state. If necessary, reagents in the liquid state can be vaporized so that they arrive in the reaction chamber in gaseous form.
[0092] The term “flow” is used to describe the various gas flows that are involved in carrying out the synthesis gas production reaction, inside the reaction chamber. As will be described in more detail below, the reaction involves a reducing flow containing hydrogen (H.sub.2) and the carbon source which are going to react with each other to form synthesis gas, and an oxidizing flow containing oxygen (O.sub.2) which is going to react with hydrogen (H.sub.2) to form an Oxy-flame.
[0093] The term “carbon source” describes the chemical compound(s) that are used to provide the carbon that ends up in the synthesis gas produced. Thus, the carbon source provides at least the carbon that ends up in the carbon monoxide (CO) being produced. Different chemical compounds can be used as a carbon source. According to one embodiment, the carbon source can comprise CO.sub.2. According to another embodiment, the carbon source can comprise one or more types of oxygenated carbon-based molecules of formula C.sub.αH.sub.βO.sub.γ where α is between 1 and 5, β is between 2 and 10 and γ is between 1 and 4. The carbon source can also comprise one or more hydrocarbons such as, for example, alkanes, alkenes and/or aromatics. It is also possible for the carbon source used to produce the synthesis gas to be a combination of two or more of the different sources described above. Thus, according to certain embodiments, the carbon source can comprise CO.sub.2 and one or more oxygenated molecules of the C.sub.αH.sub.βO.sub.γ type. According to other embodiments, the carbon source can comprise CO.sub.2 and one or more hydrocarbons, for example CO.sub.2 and methane. In the case where the carbon source only contains hydrocarbons, an intake of oxygen atoms will be required. This oxygen can be provided by CO.sub.2, but it can also be supplied in the form of water vapor. According to some embodiments, the carbon source can comprise one or more hydrocarbons, CO.sub.2 and water vapor. The water vapor, when required, can come from the reaction which generates the Oxy-flame (see reaction (G) below) and/or can be fed into the reaction chamber.
[0094] The present document therefore presents an innovative method for the production of synthesis gas from a carbon source. As stated previously, the carbon source can vary. In some embodiments, the carbon source comprises CO.sub.2 which can generally derive two major categories of sources: anthropogenic sources, linked to human activities and natural sources, so-called biogenic. The present method can use CO.sub.2 originating from both these types of sources and can also use pure CO.sub.2. According to another embodiment, a gas mixture comprising CO.sub.2 and one or more types of oxygenated molecules of formula C.sub.αH.sub.βO.sub.γ where α is between 1 and 5, β is between 2 and 10 and γ is between 1 and 4 can be used. Alternatively, the carbon source can simply comprise one or more types of C.sub.αH.sub.βO.sub.γ molecules.
[0095] According to another embodiment, a gas mixture comprising CO.sub.2 and hydrocarbons, such as alkanes (e.g., methane), alkenes and/or aromatic molecules, can also be used. However, it is also possible to use only hydrocarbons as carbon source. According to some embodiments, the carbon source can comprise CO.sub.2, one or more types of C.sub.αH.sub.βO.sub.γ molecules and one or more types of hydrocarbons. A wide range of organic molecules, including products from fossil sources, which can optionally contain sulfur, can be present in the gas mixture providing the carbon source.
[0096] More specifically, the method of producing syngas is carried out by reacting the carbon source with an excess of hydrogen on contact with an Oxy-flame. According to the present technology, an “Oxy-flame” means a flame produced by the combustion of hydrogen in the presence of an oxidant such as oxygen (O.sub.2) according to the following reaction (F):
H.sub.2+½O.sub.2.fwdarw.H.sub.2O (vapor)+Heat (F)
[0097] This flame is bright and radiant and provides the heat required to support the reaction that produces the synthesis gas from the carbon source. This flame can generate ionic species and free radicals which can catalyze the conversion of the carbon source to CO. According to certain embodiments, the Oxy-flame can make it possible to reach an average temperature, in the reaction chamber, of at least about 600° C. According to other embodiments, the average temperature reached in the reaction chamber is at least about 1200° C. The temperature reached in the reaction chamber can be up to about 2200° C. Thus, the reaction of producing the synthesis gas in the reaction chamber can be carried out at an average temperature of at least 600° C. up to about 2200° C. The Oxy-flame can be qualified as a “reducing oxy-flame” because the combustion reaction between hydrogen and oxygen takes place in the presence of an excess of hydrogen. In one embodiment, the oxidant which is used to produce the Oxy-flame can be an oxygen (O.sub.2)-based mixture, preferably pure oxygen. By “pure” oxygen, it is understood that this does not necessarily mean a purity of 100%, but that the oxygen-based mixture substantially comprises O.sub.2 and may be accompanied by certain impurities such as N.sub.2, H.sub.2O for example.
[0098] As mentioned above, the reaction to form the synthesis gas is carried out in the presence of excess of hydrogen. By “excess of hydrogen”, it will be understood that the quantity of hydrogen (H.sub.2) must be sufficient on the one hand to allow the combustion reaction (F) to produce the Oxy-flame and on the other hand to be able to carry out the conversion reaction of the carbon source into synthesis gas. The amount of hydrogen required can be determined depending on the carbon source used and considering the stoichiometry of the reactions involved.
[0099] According to another embodiment which will be explained in more detail below, the hydrogen required in the present method as well as the oxygen used to produce the Oxy-flame, can, at least in part, result from a water electrolysis reaction. This can be even more advantageous if the water electrolysis system is powered by renewable electricity. The combustion which produces the Oxy-flame can be initiated using an ignition device, such as an electric arc, an incandescent wire, or any other known source of energy.
[0100] According to certain embodiments, the present method can produce a syngas essentially containing H.sub.2 and CO in an H.sub.2/CO molar ratio close to 2. According to a particular embodiment, the present method is suitable for the production of syngas whose composition meets the conditions shown by equations (D) and (E) reported above. This is made possible by varying the proportions of the different gas streams producing the oxidizing flow and the reducing flow.
[0101]
[0102] In the reaction chamber (10), there are therefore two distinct flows: a first which comes from an oxidizing gas with pure oxygen called oxidizing flow, and another flow, called reducing flow, resulting from a hydrogen-based reducing gas mixture and containing the carbon source. These two flows are close to each other. According to one embodiment, the two flows can be separated by a distance “d” from each other such that 0.1 mm≤d≤100 mm. According to another embodiment, the distance d separating the two flows may be such that 0.3 mm≤d≤50 mm. This distance can preferably be such that 0.6 mm≤d≤30 mm. Thus, the distance d separating the two streams can be 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm, 100 mm, or any distance between these values. It should be noted that the reducing and oxidizing flows which end up in the reaction chamber can come from various streams. As a matter of fact, the reducing flow comes from a reducing stream comprising at least H.sub.2 and the oxidizing flow originates from an oxidizing stream comprising at least oxygen. However, the carbon source which ends up in the reducing flow in the reaction chamber, can be supplied either by the reducing stream, or by an independent stream, or by the oxidizing stream if this carbon source comprises CO.sub.2 only.
[0103] A first embodiment of the syngas production method is shown in
[0104] The second part (8b) of the hydrogen flow is used as the reagent ingredient for the RWGS reaction (A). The heat required for this reaction comes from the Oxy-flame (9).
[0105] Reactions (F) and (A) take place inside the reaction chamber (10) to form a gas mixture (12) composed of hydrogen, carbon monoxide, carbon dioxide and water vapor. The gas mixture (12) is also called wet syngas. This gas mixture (12) is discharged through the opening (13) of the reactor.
[0106] The reactor used for this embodiment comprises a wall (14) which can be filled with refractory and insulating materials (11). The volume of the reaction chamber (10) is determined by the cylindrical space defined by the length L and the diameter D. In the reactor, combustion can be initiated using a conventional ignition device such as for example an electric arc, an incandescent wire (not shown in the figure). According to one embodiment, the reactor can be equipped with a device allowing to measure the temperature inside the reaction chamber. Such a device can for example be a thermocouple (not shown in the figure). The injection tube (4) of the oxidizing stream (3) can be fixed by means of a device (15). According to some embodiments, the fixing device (15) can be used both as a guide for the injection tube (4) and as a sealing system. The fixing device (15) can for example comprise clamps with cable gland.
[0107] According to some embodiments, the length L of the reaction chamber can be between 1 cm and 300 cm, preferably between 10 cm and 100 cm. The diameter D of the reaction chamber can for example be between 0.3 cm and 100 cm, preferably between 1 cm and 50 cm. According to some embodiments, these values of length and diameter of the reaction chamber can also be applied to the reactors shown in
[0108] According to certain embodiments, the different gas flows can be characterized by certain parameters which will be defined below. Some of these parameters depend on different distances which are shown for example in
[0109] The oxidizing flow (6) can be characterized by a velocity parameter v1 according to the following equation (G):
v1=V1((π/4).circle-solid.D.sub.1^2) (G)
where V1 corresponds to the volumetric flow rate of the oxidizing stream (3) at the temperature and pressure conditions in the reaction chamber, and D.sub.1 is the inside diameter of the inlet tube (4) of the oxidizing stream (3). In the equations, the symbol “.circle-solid.” means “multiplied” and the symbol “^2” means “squared”.
[0110] The diameter D.sub.1 is such that the velocity v1 characterizing the oxidizing flow (6) is at least 1 m/s, based on the volumetric flow rate V1. According to another embodiment, the diameter D.sub.1 is such that the velocity v1 is between 5 m/s and 150 m/s, preferably between 5 and 100 m/s. The velocity v1 can therefore be for example between 5 m/s and 90 m/s, between 5 m/s and 80 m/s, between 5 m/s and 70 m/s, between 5 m/s and 60 m/s, between 5 m/s and 50 m/s, between 5 m/s and 40 m/s, between 5 m/s and 30 m/s, between 5 m/s and 20 m/s, or between 5 m/s and 10 m/s.
[0111] The flow of the reducing flow (8a, 8b) is characterized by a velocity parameter v2 according to the following equation (H):
v2=V2/((π/4).circle-solid.(D^2−D′.sub.1^2)) (H)
where V2 is the volumetric flow rate of the reducing flow (8a, 8b) at the temperature and pressure conditions in the reaction chamber, D is the internal diameter of the reactor and D′.sub.1 is the external diameter of the inlet tube (4) of the oxidizing current (3).
[0112] The opening (7) characterized by (D/2−D′.sub.1/2) can be such that the velocity v2 of the reducing stream flowing in the annular space defined between the outer wall of the tube (4) and the circumference of the opening (7), will be at least 1 m/s based on the volumetric flow rate V2. According to another embodiment, the opening (7) (D/2−D′.sub.1/2) is such that the velocity v2 is between 5 m/s and 150 m/s, preferably between 10 and 100 m/s. The velocity v2 can therefore be for example between 10 m/s and 90 m/s, between 10 m/s and 80 m/s, between 10 m/s and 70 m/s, between 10 m/s and 60 m/s, between 10 m/s and 50 m/s, or between 10 m/s and 40 m/s.
[0113] According to some embodiments, it is possible to define a parameter to characterize the proximity level between the reducing flow (8a, 8b) and the flow producing the Oxy-flame (9). This parameter can be defined by the distance d according to the following equation (I):
d=(D−D′1)/4 (I)
[0114] As previously indicated, the distance d can be between 0.1 mm and 100 mm, preferably between 0.3 mm and 50 mm, and preferably between 0.6 mm and 30 mm. The distance d can also be any distance within these value ranges.
[0115] According to one embodiment, the volume of the reaction chamber (10) of the reactor allows a certain residence time for all the reactants inside the reaction chamber (10) of at least 0.01 second. This residence time can be defined according to the following equation (J):
t=((π/4).circle-solid.D^2.Math..circle-solid.L)/(V1+V2) (J)
where L is the length of the chamber of reaction (10), i.e., the length of the interior volume of the reactor as shown for example on
[0116] According to certain embodiments, V1 can be between 2 L/min (3.33E−5 m.sup.3/s) and 100000 L/min (1.67 m.sup.3/s), preferably between 5 L/min (8.33E−05 m.sup.3/s) and 50000 L/min (0.84 m.sup.3/s). According to some embodiments, V2 can be between 10 L/min (1.67E−04 m.sup.3/s) et 300000 L/min (5 m.sup.3/s), preferably between 25 L/min (4.17E−04 m.sup.3/s) and 200000 L/min (3.33 m.sup.3/s).
[0117] According to certain embodiments, the method for producing the syngas can be carried out using an H.sub.2/CO.sub.2 molar ratio of between 2 and 7. The O.sub.2/CO.sub.2 molar ratio can for example be between 0.35 and 0.9. The production of syngas can be carried out using, for instance, an O.sub.2/H.sub.2 molar ratio of between 0.1 and 0.3.
[0118] According to certain embodiments, the method for producing the syngas can be carried out using the following molar proportions of the different reagents: [0119] H.sub.2/CO.sub.2 molar ratio between 2 and 7; and [0120] O.sub.2/CO.sub.2 molar ratio between 0.35 and 0.9; and [0121] O.sub.2/H.sub.2 molar ratio between 0.1 and 0.3.
[0122] The temperature reached inside the reaction chamber during the syngas production can be at least 600° C. This temperature can be at most 2200° C. It will be understood that the temperature can therefore vary between a value of 600° C. and 2200° C., and can therefore be for example 1000° C., 1100° C., 1200° C., 1300° C., 1400° C., 1500° C., 1600° C., 1700° C., 1800° C., 1900° C., 2000° C., 2100° C. and 2200° C. or any temperature between these values. It is understood that inside the reaction chamber, a temperature profile is established during the reaction. Thus, the temperature is not necessarily the same at a particular spot relative to another spot inside the reaction chamber. In other words, there are warmer and cooler areas inside the reaction chamber. When we talk about the temperature reached in the reaction chamber, we are therefore talking about a representative average temperature.
[0123] The temperature can vary depending on the pressure in the reaction chamber during the syngas production reaction. The pressure to carry out the syngas production reaction can be at least 0.5 atm. According to some embodiments, the production of syngas can be carried out at a pressure of not more than 3 atm. According to some embodiments, the pressure can therefore be 0.5 atm, 1 atm, 1.5 atm, 2 atm, 2.5 atm or 3 atm, or even any pressure between these values. For instance, the pressure can be between 1 atm and 3 atm.
[0124] In some embodiments, for a given flow rate of CO.sub.2 and H.sub.2, the O.sub.2 feed rate can be adjusted so as to obtain a desired level of temperature and heat inside the reactor to operate the RWGS reaction. Furthermore, the flow rate of H.sub.2 can be adjusted so as to obtain the H.sub.2/CO ratio or the R2 ratio defined by equation (E) that we wish to have for the gas mixture (12) discharged by the opening (13).
[0125]
[0126] According to one embodiment, the carbon source forming the stream (2) can essentially comprise CO.sub.2 and the reaction which takes place in the reaction chamber is the RWGS reaction (A).
[0127] According to another embodiment, the carbon source forming the stream (2) can comprise organic molecules of chemical formula C.sub.αH.sub.βO.sub.γ where α can vary between 1 and 5, β can vary between 2 and 10 and γ can vary between 1 and 4. Other types of organic molecules can also form the stream (2), such as hydrocarbons such as alkanes (e.g., methane), alkenes, aromatics. These organic molecules can optionally be mixed with CO.sub.2 in the stream (2).
[0128] When the carbon source comprises organic molecules of the C.sub.αH.sub.βO.sub.γ type, the following reactions can occur in the reaction chamber: [0129] Syngas formation according to equation (K):
C.sub.αH.sub.βO.sub.γ+a′H.sub.2+Q.fwdarw.cH.sub.2+dCO+e′H.sub.2O+fCO.sub.2 (K) [0130] Hydrogen combustion according to equation (L):
a″H.sub.2+bO.sub.2.fwdarw.e″H.sub.2O+Q (L) [0131] where a′, a″, b, c, d, e′, e″ and f are stoichiometric coefficients whose values depend on the molecules involved and the operating conditions considered to achieve the production of synthesis gas, and Q is the heat involved in the process.
[0132] With a=a′+a″ and e=e′+e″, the sum of equations (K) and (L) therefore gives the following stoichiometric equation (M):
C.sub.αH.sub.βO.sub.γ+aH.sub.2+bO.sub.2.fwdarw.cH.sub.2+dCO+eH.sub.2O+fCO.sub.2 (M)
[0133] The stoichiometric coefficients can be determined starting from the chemical formula of the organic compound used as the carbon source.
[0134] For example, for a=1, the coefficients can have the following values: [0135] a between 1 and 5 [0136] a″ between 0.5 and 2 [0137] b between 0.25 and 1 [0138] c between 2 and 3 [0139] d between 0.5 and 1 [0140] e between 0.5 and 2.5 [0141] e″ between 0.5 and 2 [0142] f between 0.15 and 0.75.
[0143] As mentioned above, stream (2) can comprise a mixture of CO.sub.2 and organic molecules of formula C.sub.αH.sub.βO.sub.γ. In this case, both reactions (A) and (M) can occur in the reaction chamber to form the syngas.
[0144] When the carbon source comprises a hydrocarbon, production of syngas can take place in the reaction chamber in the presence of an oxidant to allow oxidation of the hydrocarbon. Such an oxidant can comprise water vapor and/or CO.sub.2. The water vapor can be generated by the H.sub.2 combustion reaction (F) during the formation of the Oxy-flame and/or can be fed independently into the reaction chamber.
[0145] If the carbon source comprises methane as a hydrocarbon, the following reactions can occur in the reaction chamber, depending on the oxidant involved (water vapor, CO.sub.2):
CH.sub.4+H.sub.2O.fwdarw.CO+3H.sub.2 (N)
CH.sub.4+CO.sub.2.fwdarw.2CO+2H.sub.2 (O)
[0146] If the carbon source comprises a hydrocarbon of the formula C.sub.nH.sub.m, the following reaction can occur in the reaction chamber:
C.sub.nH.sub.m+nH.sub.2O.fwdarw.NCO+(n+½m)H.sub.2 (P)
[0147] Thus, the present method of producing syngas offers the possibility of using various carbon sources. For example, the carbon source can be a gas mixture produced by industrial processes such as biomass gasification or pyrolysis processes.
[0148] It should be noted that the various reaction parameters mentioned above in relation to
[0149]
[0150] As can be seen in
[0151] In the embodiment illustrated in
[0152] It should be noted that the various reaction parameters mentioned above in relation to
[0153]
[0154] According to this embodiment, several Oxy-flames can form in the reaction chamber. The distance parameter between the reducing flow and the oxidizing flow (Oxy-flame) for this embodiment can be defined as follows:
d=(r.sub.1−r.sub.2)/2 (Q)
[0155] As for all embodiments, the distance d can preferably be between 0.1 mm and 100 mm. According to another embodiment, the distance d separating the two flows can be between 0.3 mm and 50 mm, or even preferably between 0.6 mm and 30 mm. The distance d can also be any distance within these ranges of values.
[0156] As mentioned above, according to some embodiments, the hydrogen which is needed in the reducing stream and which is used to obtain the syngas, can be produced from renewable resources. Notably, the hydrogen can be produced from a water electrolysis system powered by electricity from renewable sources. The stream comprising the carbon source (e.g., CO.sub.2) which is also needed as a reagent, can itself be a gas mixture resulting from biomass gasification or pyrolysis techniques, as mentioned above. Thus, overall, it is possible to produce syngas from a captured carbon source, water and electricity from renewable sources.
[0157] This embodiment of the method of producing syngas from renewable resources is shown on part of
[0162] Specifically, as can be seen in
[0163] The gas (G1) resulting from the production of syngas (30) is then rapidly cooled (40) in order to limit/prevent the reverse reaction of reaction (A) from occurring. Cooling can be carried out using a conventional method. According to a preferred embodiment, the cooling (40) can be carried out by means of a direct contact cooler with a stream of water (H.sub.2O-b). According to one embodiment, the gas (G1) is cooled to a temperature above the dew point of the hot gas and not exceeding 250° C. According to some embodiments, the dew point of the hot gas (G1) is less than 90° C. at atmospheric pressure. For example, the dew point of hot gas (G1) is between 60° C. and 90° C. at atmospheric pressure. According to some embodiments, the gas (G1) can be cooled to a temperature between 90° C. and 250° C.
[0164] The cooled gas (G2) obtained after the cooling (40) is a wet gas. This gas (G2) can then undergo a second cooling which can be carried out by condensation (50). According to some embodiments, this condensation can be carried out using a cooler-condenser. According to a preferred embodiment, the condensation step (50) can be carried out such that the gas (G2) is cooled to a temperature of 35° C. and below. At the outlet of the cooler-condenser, one obtains on the one hand syngas (G3) and on the other hand condensed water (H.sub.2O-c). Part of the condensed water (H.sub.2O-c) can be recycled (H.sub.2O-b flow) to the cooling stage (40) while the other part of the condensed water can be discharged (H.sub.2O-d flow). According to some embodiments, the H.sub.2O-d flow can be used, at least in part, to supply water to the electrolysis system (20).
[0165] As mentioned previously, the syngas production method described in the present document can allow producing CO and H.sub.2 based gas mixtures based (syngas) which are balanced, i.e., with appropriate proportions of CO and H.sub.2, to then allow the production of a variety of products by conventional chemical syntheses. Thus, it is possible, by controlling the nature and the quantity of reagents used (e.g., the flow rate of the gas streams), to produce a syngas where the proportion of CO and H.sub.2 is adapted such that the mixture is directly usable in a subsequent chemical synthesis. It is also possible to play on the proportion of CO and H.sub.2 in the syngas, by controlling the temperature, the pressure and the O.sub.2 feed rate in the reaction chamber. In addition, the temperature in the reactor can be controlled by the flow rate of oxygen supplied. According to one embodiment, the syngas produced contains H.sub.2 and CO in a molar ratio H.sub.2/CO≥2. The syngas produced by the described method can also contain CO.sub.2. In this case, the molar ratios of H.sub.2, CO and CO.sub.2 in the syngas can be such that (H.sub.2—CO.sub.2)/(CO+CO.sub.2)≥2.
[0166] By respecting these molar ratios, the syngas produced by the present method can be used to produce a large number of commodity chemicals. Amongst these products, we can particularly find methanol and hydrocarbons such as those found in motor gasoline, diesel, kerosene, to name a few examples.
[0167] The syngas production method described above and the reactor that can be used to perform this method therefore have several advantages. The reagents are easily accessible and can be derived from renewable sources. It is not necessary to resort to the use of solid catalysts. The conversion rate of the reactants can also be greater than the conversion rate observed in the case of a RWGS reaction carried out in a conventional manner in the presence of a catalyst. Finally, the present method is characterized by its robustness, in that it is versatile and simple to implement. These advantages therefore make it possible to reduce production costs in addition to the beneficial environmental effect of recycling carbon sources such as CO.sub.2 for example.
EXAMPLES
Example 1
[0168] This example is based on a small reactor as shown schematically in
[0172] An ignition system used to ignite a pulsoreactor, i.e., a spark plug with ignition at 20 kV, was inserted inside the reactor, very close to the upper end of the inner and median tubes. A perforation was made to allow the spark plug to be inserted (not shown in the figure for clarity). The change in the temperature level in the reactor is monitored using thermocouples. The temperature is measured in a lower part and also in an upper part of the reaction zone inside the mini reactor. That is, one temperature reading near the base of the reaction zone (where gases are injected) specifically 13 mm higher than the line at the start of the reaction zone (see
[0173] The experimental set-up includes the following: the reactor itself, a tube and jacket heat exchanger allowing rapid cooling of the gases leaving the reactor, a condensate recovery tank, a gas relative humidity (RH) analysis system, and finally, an analysis system (CO.sub.2/CO/C.sub.xH.sub.y/O.sub.2) to allow measuring the contents in CO, CO.sub.2, hydrocarbons (C.sub.xH.sub.y) as well as the oxygen content of the gas produced, at the outlet of the gas cooling system.
[0174] A system of mass flow meters with automated control valves is also set up. The system is provided with a software for programming changes in the composition of the gas mixture introduced into the reactor. Finally, manual valves are used to direct each of the gases into the desired reactor tube.
[0175] To avoid flashbacks on ignition, ignition is carried out in stages (lasting approximately 1 second). The main stages of the ignition sequence comprise: 1) start the H.sub.2 injection, 2) after a few seconds, inject the oxygen in successive stages until the desired flow rate, each stage lasting a few seconds, 3) start the CO.sub.2 injection.
[0176] Once ignition occurs, one can proceed to the analysis steps as such. Each of these stages has a duration of 60 seconds. After this period of time, the various measurements are carried out. The input flow rates (standard liters (SL) at 25° C., 1 atm per min) are as follows: [0177] CO.sub.2: 1.3 SL/min [0178] O.sub.2: 0.93 SL/min [0179] H.sub.2: 6.1 SL/min
[0180] The CO.sub.2 and O.sub.2 flows are premixed. The operating pressure is nearly 1 atm.
[0181] The following results were obtained: [0182] CO molar concentration in the gas: 22.2% [0183] CO.sub.2 molar concentration in the gas: 8.1% [0184] Hydrocarbon molar concentration: trace [0185] CO/CO.sub.2 molar ratio in the produced gas: 2.74 [0186] CO.sub.2 to CO conversion rate: 73% [0187] Average temperature in the reaction chamber: 686° C. [0188] Velocity of the O.sub.2/CO.sub.2 mixture at the inlet (at average temperature, 1 atm): 16.4 m/s [0189] Velocity of H.sub.2 at the inlet (at average temperature): 21.1 m/s [0190] Residence time in the reactor (s): <0.06 s [0191] Ratio R2=(H.sub.2—CO.sub.2)/(CO+CO.sub.2): 2.26
[0192] For the calculation of the R2 ratio, the concentration of H.sub.2 is calculated from an atomic balance. The atomic balance is itself carried out taking into account all the inputs (CO.sub.2, H.sub.2, O.sub.2) and taking into account the composition of the outgoing gas (CO and CO.sub.2 content, hydrocarbon content expressed in CH.sub.4 equivalent, gas humidity, residual oxygen content). The atomic balance on the hydrogen atoms makes it possible to calculate the hydrogen composition of the gas at the outlet of the reactor.
Example 2
[0193] In this example, the same device as for Example 1 is used, but with injection of O.sub.2 into the inner tube (space A), injection of H.sub.2 into the annular space between the median tube and the inner tube (space B), and injection of a CO.sub.2/CH.sub.4 equimolar mixture into the annular space between the outer tube and the median tube (space C). The input flow rates (standard liters at 25° C., 1 atm per min) are as follows: [0194] CO.sub.2: 0.40 SL/min [0195] CH.sub.4: 0.40 SL/min [0196] O.sub.2: 0.9 SL/min [0197] H.sub.2: 3.3 SL/min
[0198] These three flows are injected separately into the mini reactor. The following results were obtained: [0199] CO concentration in the dry gas: 13.3% [0200] CO.sub.2 molar concentration in the gas: 10.2% [0201] Hydrocarbon molar concentration in the gas: 2135 ppm [0202] CO/CO.sub.2 ratio in the produced gas: 1.30 [0203] CO.sub.2 conversion rate: 13.1% [0204] CH.sub.4 conversion rate: 98.2% [0205] Average temperature: 855° C. [0206] Velocity of the O.sub.2 at the inlet (at average temperature, 1 atm): 7.77 m/s [0207] Velocity of the H.sub.2 at the inlet (at average temperature, 1 atm): 13.4 m/s [0208] Velocity of the CO.sub.2/CH.sub.4 mixture at the inlet (at average temperature, 1 atm): 7.46 m/s [0209] Reagent residence time: <0.07 s [0210] R2=(H.sub.2—CO.sub.2)/(CO+CO.sub.2): 2.87
[0211] For the calculation of the ratio R2, the concentration of H.sub.2 is calculated from an atomic balance.
Example 3
[0212] In this example, the same reactor as for Example 1 is used, but the outer Inconel™ tube is replaced by a quartz tube. The length of the reaction chamber is the same. For this example, the CO.sub.2 and O.sub.2 flows are premixed. The resulting mixture is injected inside the inner tube (space A), while hydrogen is injected inside space B. The operating pressure is nearly 1 atm. Since the temperature cannot be measured directly, the temperature used is a thermodynamic equilibrium temperature value calculated to obtain a gas with the same CO/CO.sub.2 ratio as what has been measured.
[0213] Les débits des intrants (litres standard à 25° C., 1 atm par min) sont les suivants: [0214] CO.sub.2: 1.3 SL/min [0215] O.sub.2: 0.93 SL/min [0216] H.sub.2: 6.2 SL/min
[0217] The input flow rates (standard liters at 25° C., 1 atm per min) are as follows: [0218] CO concentration in the gas: 22.9% [0219] CO.sub.2 concentration in the gas: 7.30% [0220] Hydrocarbon molar concentration: trace [0221] CO/CO.sub.2 ratio in the produced gas: 3.14 [0222] CO.sub.2 to CO conversion rate: 75.8% [0223] Equilibrium temperature T: 1230° C. [0224] Velocity of O.sub.2/CO.sub.2 mixture at the inlet (at temperature T, 1 atm): 25.6 m/s [0225] Velocity of H.sub.2 at the inlet (at temperature T and 1 atm): 33.7 m/s [0226] Reagent residence time: <0.04 s [0227] R2=(H.sub.2—CO.sub.2)/(CO+CO.sub.2): 2.34
[0228] For the calculation of the ratio R2, the H.sub.2 concentration of the gas leaving the reactor is calculated from an atomic balance. Comparison of the results of Example 1 with those of Example 3 shows that the nature of the materials of the reactor (Inconel™ versus quartz) has no significant influence on the CO.sub.2 conversion rate.
Example 4
[0229] This example uses the same equipment as Example 3, i.e., based on using a quartz tube as the outer tube. In this example, O.sub.2 is injected into space A, H.sub.2 is injected into space B and CO.sub.2 into space C. Since the temperature cannot be measured directly, the temperature used is a thermodynamic equilibrium temperature value calculated to obtain a gas having the same CO/CO.sub.2 ratio as what has been measured. The input flow rates (standard liters (SL) at 25° C., 1 atm) per min) are as follows: [0230] CO.sub.2: 1.3 SL/min [0231] O.sub.2: 0.93 SL/min [0232] H.sub.2: 6.1 SL/min
[0233] The following results were obtained: [0234] CO concentration in the gas: 18.21% [0235] CO.sub.2 concentration in the gas: 11.5% [0236] Hydrocarbon concentration: trace [0237] CO/CO.sub.2 ratio in the gas: 1.58 [0238] CO.sub.2 to CO conversion rate: 61.2% [0239] Equilibrium temperature T: 877° C. [0240] O.sub.2 velocity (at temperature T): 8.20 m/s [0241] H.sub.2 velocity (at temperature T, 1 atm): 25.4 m/s [0242] CO.sub.2 velocity (at temperature T, 1 atm): 9.02 m/s [0243] Residence time in the reactor: <0.05 s [0244] R2=(H.sub.2—CO.sub.2)/(CO+CO.sub.2): 2.26
[0245] For the calculation of the ratio R2, the H.sub.2 concentration in the gas leaving the reactor is calculated from an atomic balance.
[0246] Applicability of the synthesis gas production process has been demonstrated in the above examples, inter alia, on the basis of the use of CO.sub.2 as a carbon source. CO.sub.2 is a very chemically stable molecule, and much more stable than a C.sub.αH.sub.βO.sub.γ molecule where α is between 1 and 5. Since the above examples have shown that the process is applicable for CO.sub.2 which turns out to be more difficult to transform chemically than a molecule of the C.sub.αH.sub.βO.sub.γ type, it is reasonable to conclude that the method is also applicable to molecules of the C.sub.αH.sub.βO.sub.γ type as a carbon source.
[0247] Although some embodiments of the present method, and of the reactor which can be used to perform this method, have been described above, the method and the reactor are not limited to these sole embodiments. Several modifications could be made to one or the other of the embodiments described above, without departing from the scope of the present technology as contemplated.