Chemical synthesis equipment

Abstract

An apparatus, such as a hydrocarbon apparatus, is provided that consists of a syngas stage for generating syngas and a synthesis stage in which the syngas is synthesized to produce a syngas-derived product, such as a hydrocarbon product. The device effectively utilizes various streams; in particular CO2 and H2. A process for producing a product stream (e.g., a hydrocarbon product stream) is also provided.

Description

[0001] This application is a divisional application of Chinese invention patent application filed on April 3, 2020, with application number 202080017634.1 and invention title "Chemical Synthesis Equipment". Technical Field

[0002] This invention relates to an apparatus for the efficient utilization of various streams (particularly carbon dioxide), such as hydrocarbon equipment. A method for generating product streams (e.g., hydrocarbon product streams) is also provided. The apparatus and method of this invention generally make better use of carbon dioxide. Background Technology

[0003] Given the increase in atmospheric CO2 since the Industrial Revolution, carbon capture and utilization (CCU) has become increasingly important. In one way of utilizing CO2, CO2 and H2 can be converted into syngas (a gas rich in CO and H2), which can be further converted into valuable products such as alcohols (including methanol), fuels (such as gasoline, jet fuel, kerosene, and / or diesel produced, for example, via the Fischer-Tropsch (FT) process), and / or olefins.

[0004] Existing technologies primarily focus on stand-alone reverse water gas shift (rWGS) processes that convert CO2 and H2 into syngas. The syngas can then be converted into valuable products in downstream processes as described above. The reverse water gas shift reaction proceeds according to the following reaction: CO2 + H2 CO + H2O (1) The rWGS reaction (1) is an endothermic process that requires a large energy input for the desired conversion. Very high temperatures are needed to achieve sufficient conversion of carbon dioxide to carbon monoxide, making the process economically viable. Undesirable byproducts, such as methane, may also form. High carbon dioxide conversion can obviously also be achieved through a high H2 / CO2 ratio. However, this often results in syngas with a (very) excessively high H2 / CO ratio, making it unusable for downstream synthesis.

[0005] Technologies relying on rWGS reactions present additional challenges. In some cases, hydrocarbons can be obtained as co-feeds. One example is the availability of hydrocarbons from downstream synthesis stages (e.g., propane and butane-rich streams from FT stages; tail gas from FT stages containing various hydrocarbons; naphtha streams from FT stages; propane and butane-rich streams from gasoline synthesis stages; hydrocarbon streams from olefin synthesis, etc.). Such hydrocarbons cannot be processed in an rWGS reactor. If the hydrocarbon streams from downstream synthesis stages are not at least partially used for the additional production of syngas, the entire process may be economically infeasible. The same applies if the hydrocarbon stream (e.g., natural gas) is available as a co-feed for the plant.

[0006] To address the problems of existing technologies, this paper proposes a novel method for syngas preparation, which then synthesizes the syngas into one or more syngas derivatives primarily derived from CO2, H2, and O2 feedstocks. The proposed layout has at least the following advantages: 1. CO2, H2, and O2 can be converted into syngas with the desired H2:CO ratio, appropriately without using any hydrocarbon feedstock destined for the equipment. If desired, one or more hydrocarbon feedstocks destined for the equipment may also be used as a co-feed.

[0007] 2. Use any hydrocarbons produced in the synthesis stage for syngas production.

[0008] 3. Higher utilization of CO2 feed is possible compared to a standalone rWGS section. A specific goal is to use more CO2 feed instead of hydrocarbon feed as the carbon source.

[0009] 4. Conversion of any hydrocarbon co-feed stream fed into the syngas stage is possible.

[0010] 5. If the electrolytic cell is used as part or all of the hydrogen feed source for the process, then part or all of the oxygen generated in the electrolytic cell together with H2 can be used as the oxygen source required in the proposed process layout. Summary of the Invention

[0011] Therefore, in a first aspect, a method for producing a product flow is provided. The method includes the following steps: - Provides a plant, the plant comprising: a. A syngas stage, said syngas stage comprising an autothermal reforming (ATR) section, and; b. Synthetic stage; The device includes: - The first feedstock containing hydrogen leading to the syngas stage; - A second feed containing carbon dioxide leading to the syngas stage; - A third feedstock containing hydrocarbons, located upstream of the ATR section, leading to the syngas stage; and - The fourth feed containing oxygen to the ATR section; The syngas stage is arranged to provide a syngas flow and supply the syngas flow to the synthesis stage (B); - Supply the first feed containing hydrogen to the syngas stage; - Supply a second feed containing carbon dioxide to the syngas stage; - A third feed containing hydrocarbons is supplied upstream of the ATR section to the syngas stage; - Supply a fourth feed containing oxygen to the ATR section; - A syngas stream is provided in the syngas stage from at least the first, second, third and fourth feeds, and the syngas stream is supplied to the syngas stage; - In the synthesis stage, the synthesis gas stream is converted into at least a product stream and a hydrocarbon-containing waste gas stream; When the equipment is outside, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 in the second feed is less than 0.5.

[0012] Various devices are provided for carrying out the methods of the present invention.

[0013] Further details of the apparatus and method are described in detail in the following description, drawings and claims. Attached Figure Description

[0014] Figure 1-5 The illustration shows a schematic layout of various implementation schemes for the equipment. Invention Details

[0016] Unless otherwise stated, any given percentage of gas content is by volume. Detailed Implementation

[0017] As described above, an apparatus, such as a hydrocarbon apparatus, is provided. The apparatus includes: a. A syngas stage, said syngas stage comprising an autothermal reforming (ATR) section, and; b. Synthetic stage; The equipment includes various feeds. For the avoidance of doubt, when applied to the equipment, the term "supply" refers to the means of supplying the gas to the appropriate stage, reactor, or unit; such as pipelines, pipes, etc.

[0018] A first feed comprising hydrogen is provided to the syngas stage. Suitably, the first feed consists primarily of hydrogen. The first hydrogen feed is suitably “hydrogen-rich,” meaning that the main component of the feed is hydrogen; that is, more than 75%, for example, more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the feed is hydrogen. One source of the first hydrogen feed can be one or more electrolyzer units. In addition to hydrogen, the first feed may also contain, for example, steam, nitrogen, argon, carbon monoxide, carbon dioxide, and / or hydrocarbons. The first feed suitably contains only small amounts of hydrocarbons, for example, less than 5% or less than 3% or less than 1%.

[0019] A second feed comprising carbon dioxide is provided to the syngas stage. Suitably, the second feed consists primarily of CO2. The CO2 second feed is suitably “CO2-rich,” meaning that the main component of the feed is CO2; that is, more than 75%, for example, more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the feed is CO2. One source of the carbon dioxide second feed can be one or more exhaust gas streams from one or more chemical plants. Another source of the carbon dioxide second feed can also be carbon dioxide captured from one or more process streams or the atmosphere. Another source of the second feed can be CO2 captured or recovered from, for example, flue gas from flame heaters, steam reformers, and / or power plants. In addition to CO2, the second feed may also include, for example, steam, oxygen, nitrogen, oxygenated compounds, amines, ammonia, carbon monoxide, and / or hydrocarbons. The second feed suitably contains only small amounts of hydrocarbons, for example, less than 5% or less than 3% or less than 1%.

[0020] The first and second feeds can be mixed before being added to the syngas stage.

[0021] The H2:CO2 ratio provided at the equipment inlet varies between 1.0 and 9.0, preferably 2.5 to 8, and more preferably 3.0 to 7.0. The actual ratio will depend on the desired final product downstream of the synthesis stage. This ratio is defined as any H2 and CO2 in the external stream (i.e., excluding any hydrogen and / or carbon dioxide in the recirculated stream).

[0022] When the synthesis stage is an FT synthesis stage, the desired H2 / CO ratio of the syngas is typically around 2. Using a simple perspective, one unit of hydrogen is needed to convert one unit of CO2 to CO. The addition of O2 will also require some hydrogen, and hydrogen will be needed as an energy source for ancillary uses, such as power generation. In summary, this means that for an FT synthesis stage, the H2:CO2 ratio at the plant inlet (i.e., excluding any hydrogen and / or carbon dioxide in the recycle stream) should be in the range of 3-7, more preferably 3-6, and most preferably 3-5. Similar considerations can be made if the desired final product is methanol or gasoline (via methanol synthesis and methanol-to-gasoline routes), and in these cases, the H2:CO2 ratio at the plant inlet should also be in the range of 3-7, more preferably 3-6, and most preferably 3-5.

[0023] It should be noted that in some cases, an H2:CO2 ratio less than 3, such as between 2 and 3, can be used. This might be the case, for example, if the third stream contains hydrogen or is reformed by steam to produce hydrogen. However, other scenarios where the H2:CO2 ratio is less than 3 are also conceivable.

[0024] Upstream of the ATR stage, a third feed containing hydrocarbons is provided to the syngas stage. The third feed may additionally contain other components such as CO2 and / or CO and / or H2 and / or steam and / or other components such as nitrogen and / or argon. Suitably, the third feed consists primarily of hydrocarbons. A hydrocarbon-rich third feed is suitably “hydrocarbon-rich,” meaning that the majority of the feed is hydrocarbons; that is, more than 50%, for example, more than 75%, for example, more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the feed is hydrocarbons. The concentration of hydrocarbons in the third feed (i.e., determined as “dry concentration”) is determined prior to steam addition.

[0025] On the one hand, a third feed is supplied directly upstream of the ATR section to the syngas stage (i.e., without any intermediate stages or units). A “stage” includes one or more “units” that alter the chemical composition of the feed and may additionally include elements such as, for example, heat exchangers, mixers, or compressors that do not alter the chemical composition of the feed or stream.

[0026] An example of such a third feed could also be a natural gas stream from outside the equipment. In one aspect, the third feed comprises one or more hydrocarbons selected from methane, ethane, propane, or butane.

[0027] The source of the hydrocarbon-containing third feedstock is external to the facility. "External to the facility" means that the source is not a recycled stream (or a recycled stream from further processing or conversion) from any of the synthesis stages within the facility. Possible sources of hydrocarbon-containing third feedstocks external to the facility include natural gas, LPG, refinery tail gas, naphtha, and renewable energy, but other options are also conceivable.

[0028] In some cases, the hydrocarbon-containing stream may be pre-reformed before being supplied as a third feed to the syngas stage. For example, when the third feed is, for example, an LPG and / or naphtha product stream or a natural gas feed, the unit may also include a pre-reforming section located in the third feed, upstream of the syngas stage.

[0029] In the pre-reforming step, the following (endothermic) steam reforming reaction and reaction (3) (exothermic) occur to convert higher hydrocarbons. Additional water-gas shift and methanation occur via reactions (1) and (3): C n H m + n H2O nCO + (n + m / 2)H2 (where n ≥ 2, m ≥ 4) (2) CO2 + 4H2 CH4 + 2H2O (3) The pre-reforming unit outlet stream will contain CO2, CH4, H2O, and H2, as well as typically smaller amounts of CO and possibly other components. The pre-reforming step is typically carried out at 350-600°C, or more preferably between 400 and 550°C. Steam is added to the hydrocarbon feed stream upstream of the pre-reforming step. The pre-reforming step can be carried out adiabatically or in a heated reactor filled with a catalyst, including but not limited to a Ni-based catalyst. Heating of the pre-reforming unit can be achieved by hot gas (e.g., ATR effluent gas) or by using, for example, a flame heater in the heating section. Hydrogen or other combustible components can be used to obtain the necessary heat input.

[0030] The hydrocarbon stream may also contain olefins. In this case, the olefins can be hydrogenated into the corresponding alkanes before being added as a third feed to the pre-reformer or syngas stage.

[0031] In some cases, hydrocarbons contain trace amounts of toxic substances, such as sulfur. In such cases, one or more purification steps, such as desulfurization, can be performed on the hydrocarbons.

[0032] The third feed may consist of one or more hydrocarbon-containing streams, which are added to the syngas stage either mixed or separately. The hydrocarbon-containing streams may be recycled from the syngas stage, or they may be one or more separate streams outside the plant that are not recycled from the syngas stage.

[0033] A fourth feed containing oxygen is supplied to the ATR section. Suitably, the fourth feed consists primarily of oxygen. The fourth feed of O2 is suitably “O2-rich,” meaning that the main component of the feed is O2; that is, more than 75%, for example, more than 90%, or more than 95%, for example, more than 99%, of the feed is O2. The fourth feed may also contain other components, such as nitrogen, argon, CO2, and / or steam. The fourth feed typically includes a small amount of steam (e.g., 5-10%). The source of the fourth feed oxygen can be at least one air separation unit (ASU) and / or at least one membrane unit. The oxygen source can also be at least one electrolytic cell unit. Some or all of the first feed and some or all of the fourth feed can come from at least one electrolytic cell. An electrolytic cell is a unit that converts steam or water into hydrogen and oxygen using electrical energy. Steam can be added to the oxygen-containing fourth feed upstream of the ATR section.

[0034] On the one hand, the equipment also includes a steam feed (fifth feed) leading to the syngas stage.

[0035] Suitablely, when outside the equipment, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 of the second feed is low; for example, less than 0.3, preferably less than 0.25, more preferably less than 0.2 or even less than 0.1. Values ​​of less than 0.05 or 0.02 are also acceptable. The lower this value is when the external hydrocarbon stream is a fossil fuel stream, the lower the fossil fuel consumption for a given production.

[0036] Syngas stage

[0037] The syngas stage (A) is arranged to provide a syngas flow (from at least the first to fourth feeds) and supply the syngas flow to the synthesis stage (B). For the avoidance of doubt, the terms "syngas" and "synthesis gas" are synonyms. Furthermore, the term "provide syngas flow" in this context must be understood as "generate syngas flow".

[0038] The syngas stage includes an autothermal reforming (ATR) section. Additional sections may be included as needed. The individual sections are described below.

[0039] ATR segment

[0040] On one hand, the syngas stage consists of an autothermal reforming (ATR) section comprising one or more autothermal reactors (ATRs), wherein first, second, third, and fourth feeds are supplied to the ATR section. Part or all of the third feed may be desulfurized and pre-reformed. All feeds are preheated as needed. The key component of the ATR section is the ATR reactor. An ATR reactor typically includes a burner, a combustion chamber, and a catalyst bed contained within a refractory-lined pressure vessel. In the ATR reactor, after the hydrocarbon feed is partially combusted by substoichiometric amounts of oxygen, the partially combusted hydrocarbon feed stream undergoes steam reforming in a fixed bed of steam reforming catalyst. Due to the high temperature, some degree of steam reforming also occurs in the combustion chamber. The steam reforming reaction is accompanied by a water-gas shift reaction. Typically, for both steam reforming and the water-gas shift reaction, the gas is at or near equilibrium at the reactor outlet. More details and a complete description of ATR can be found in the field, for example, “Studies in Surface Science and Catalysis, Vol. 152, “Synthesis gas production for FT synthesis”; Chapter 4, pp. 258-352, 2004.

[0041] Typically, the effluent gas from the ATR reactor has a temperature of 900–1100°C. The effluent gas usually contains H2, CO, CO2, and vapor. Other components such as methane, nitrogen, and argon may also be present in small amounts. The operating pressure of the ATR reactor will be 5 to 100 bar, or more preferably 15 to 60 bar.

[0042] The syngas stream from the ATR is cooled in a cooling train, which typically includes one or more waste heat boilers (WHBs) and one or more additional heat exchangers. The cooling medium in the WHB is water evaporated into steam (boiler feed). The syngas stream is further cooled below the dew point, for example, by preheating the facility and / or partially preheating one or more feed streams and cooling them in air coolers and / or water coolers. The condensed H2O is removed as process condensate in a separator to provide a syngas stream with a low H2O content, which is then sent to the synthesis stage.

[0043] The "ATR section" can be a partially oxidized "POX" section. The POX section is similar to the ATR section, except that the ATR reactor is replaced by a POX reactor. The POX reactor typically includes a burner and a combustion chamber contained within a refractory-lined pressure vessel.

[0044] The ATR segment can also be a catalytic partial oxidation (cPOX) segment.

[0045] Methanation section

[0046] On one hand, the syngas stage further includes a methanation section disposed upstream of the ATR section. The methanation section is in fluid communication with the ATR section. Part or all of the first feed is supplied to the methanation section; part or all of the second feed is supplied to the methanation section; and part or all of the third feed is supplied to the syngas stage upstream of the methanation section and / or between the methanation section and the ATR section.

[0047] The heat generated during methanation completely eliminates or significantly reduces the need for external preheating of the feed to the autothermal reforming section. This external preheating can be performed, for example, in a flame heater. The heat required in such a flame heater is generated by the combustion of, for example, hydrogen and / or hydrocarbons. In the former case, this consumes a portion of the feed, and in the latter, it leads to CO2 emissions. Furthermore, flame heaters are expensive devices and can occupy a considerable floor space. Finally, for example, a methanation section preceding the ATR section improves overall equipment efficiency compared to a standalone ATR section.

[0048] As previously mentioned, existing technologies for producing syngas from CO2 and hydrogen are based on selective RWGS. Compared to this approach, the combination of methanation and ATR offers several advantages. These include the possibility of utilizing hydrocarbon-containing streams from both external and internal recirculation flows. Furthermore, the outlet temperature of the ATR reactor in the ATR section is typically in the range of 900–1100 °C. In most cases, this is higher than the temperatures achievable by standalone RWGS units. This increases carbon monoxide production, as higher temperatures are thermodynamically favorable for the process. It should also be noted that even when methane is formed in the methanation section, the final syngas delivered to the synthesis stage contains a lower methane content due to the high outlet temperature of the ATR reaction in the ATR section. Advantageously, the outlet temperature of the ATR is 1000–1100 °C.

[0049] For most applications, a low methane content in the syngas fed to the synthesis stage is an advantage. For most types of synthesis stages, methane is inert, or even a byproduct of the synthesis stage. Therefore, in a preferred embodiment, the methane content in the syngas fed to the synthesis stage is less than 5%, for example less than 3% or even less than 2%.

[0050] Inserting a methanation section upstream of the ATR section seems counterintuitive. Methane is formed in the methanation section, and then most of the formed methane is converted in the ATR section. However, the applicant has discovered that the heat from methanation can be used to preheat the feed heading to the ATR section. This avoids or reduces the need for a dedicated feed preheater. In the case where the preheater is a flame heater using hydrocarbon fuels, reducing the preheating load will also reduce the combustion required to provide the necessary energy, thereby reducing CO2 emissions. The methanation section may include one or more methanation units arranged in series, such as two or more, three or more, four or more methanation units. In such methanation units, CO2 and H2 are converted primarily into methane and vapor through an exothermic methanation reaction. Each methanation unit may be adiabatic or cooled by, for example, boiling water or by heating, for example, the feed gas. Depending on the degree of methanation and cooling, the effluent temperature from each methanation unit can be 250-900°C, preferably 600-850°C, and more preferably 650-840°C. Parallel methanation units are also possible.

[0051] Multiple portions of the first feed containing hydrogen can be fed separately to different methanation units in the methanation section; or the entire first feed containing hydrogen can be fed together to the upstream methanation unit in the methanation section. Similarly, multiple portions of the second feed containing carbon dioxide can be fed separately to different methanation units in the methanation section; or the entire second feed containing carbon dioxide can be fed together to the upstream methanation unit in the methanation section. Furthermore, multiple portions of the third feed containing hydrocarbons can be fed separately to different methanation units in the methanation section; or the entire third feed containing hydrocarbons can be fed together to one methanation unit in the methanation section.

[0052] In one specific implementation, all of the first feed containing hydrogen is fed together with a portion of the second feed containing carbon dioxide into the first methanation unit. The remaining carbon dioxide is distributed among the remaining methanation units, and the final methanation unit exits at a temperature of 650-900°C, for example, 750-850°C.

[0053] Additional H2 and / or CO2 feeds can be added to different sections of the methanation section. For example, a portion of the hydrogen or CO2 feed can be provided to a second (or even a third…) methanation unit. Furthermore, a portion of the effluent from one methanation unit can be cooled and recycled to the inlet of that methanation unit and / or the inlet of any additional methanation unit located upstream of that methanation unit. Optionally, the effluent from the methanation section can be cooled below its dew point, and a portion of the water can be removed from the effluent before it is recycled to the inlet of a methanation unit or any upstream methanation unit.

[0054] Steam can also be added to the methanation section and / or between the methanation section and the ATR section.

[0055] In this respect, the exothermic nature of the methanation reaction can be used to preheat the ATR feed. For example, for control purposes, it may be necessary or desirable to heat the ATR section by external means. Therefore, the heat of reaction of the methanation reaction may only cause a partial temperature increase upstream of the ATR section.

[0056] Methanation can be represented by the following formula: CO2 + 4H2 CH4 + 2H2O (3) Typically, rWGS (reaction (1) and / or water-gas shift reaction (the reverse reaction of reaction (1)) also occur in the methanation unit. In many cases, the gas composition at the outlet of each methanation unit will be at or near chemical equilibrium with respect to the water-gas shift / reverse water-gas shift and methanation reactions at the outlet temperature and pressure of the methanation unit.

[0057] Methanation reaction (3) is strongly exothermic. In some cases, it is desirable to regulate the temperature at the outlet of the methanation unit or away from the methanation section to a given value, which can be in the range of 250-900°C, for example 600-850°C. If a third feed containing some or all of hydrocarbons is added to the methanation unit, this will lower the outlet temperature due to the fact that steam reforming (the reverse of reaction (3) and / or reaction (2)) will occur.

[0058] Conversely, if the effluent from the pre-reforming step is added to the methanation unit, the same effect is achieved. The methane in the pre-reforming effluent will react according to the endothermic steam reforming reaction: CH4 + H2O CO + 3H2 (4) Due to chemical equilibrium, the presence of methane in the feed will limit the extent of the methanation reaction. The output of the methanation section is a stream containing CO2, H2, CO, H2O, and CH4.

[0059] Tail gas from the FT synthesis stage is typically not added to the methanation unit, but is instead supplied directly to the ATR stage. If excess tail gas from the FT synthesis stage is available, it can be hydrogenated and supplied to the methanation stage.

[0060] In some cases, it may be desirable to avoid excessively high temperatures in the methanation unit, for example, to limit the degree of catalyst deactivation due to sintering. This is especially true if the methanation unit or reactor is adiabatic. The highest temperature in an adiabatic methanation unit is typically at the outlet. Therefore, it may be desirable to control the outlet temperature of one or more methanation units within a range of, for example, 600-750°C, such as about 650°C, 675°C, 700°C, or 725°C. If there is more than one methanation unit, this can be achieved by controlling the feed streams entering the individual methanation units in the methanation section. The outlet temperature of the adiabatic methanation unit can be controlled by controlling the molar ratio between the first and second feed portions added to the methanation unit, and the molar ratio between the first feed portion and the fifth feed portion (if present). Obviously, the inlet temperature of the feed stream can also be used for this purpose.

[0061] In one embodiment, the inlet temperature of at least one methanation unit is 300-500°C.

[0062] The proportions of each feed stream going to each methanation unit, as well as the proportions of each feed stream supplied to the methanation section and directly to the ATR section, can also be used to influence the composition of the syngas.

[0063] The degree of methanation (and consequently the composition of the gas leading to the ATR) depends on several factors, including the proportion of the feed stream going to the methanation stage, the inlet and outlet temperatures of each methanation unit, and the extent to which water (if any) is removed from the methanation stage. For a given gas composition and temperature leading to the ATR, the syngas from the ATR depends on the amount of oxygen added. Increasing the amount of oxygen increases the ATR reactor outlet temperature, thereby decreasing the H2 / CO ratio.

[0064] In another implementation scheme (such as) Figure 4c As shown, the syngas stage (A) includes a methanation stage (II) arranged in parallel with the ATR stage (I). At least a portion of the first feed and at least a portion of the second feed are arranged to be supplied to the methanation stage (II), and the methanation stage (II) is arranged to convert the at least a portion of the first feed and at least a portion of the second feed into a first syngas stream. A third feed containing hydrocarbons and a fourth feed containing oxygen are arranged to be supplied to the ATR stage (I); and the ATR stage (I) is arranged to convert the third feed containing hydrocarbons and the fourth feed containing oxygen, together with the remainders of the first and second streams, into a second syngas stream. The first syngas stream from the methanation stage (II) is arranged to be combined with the second syngas stream from the ATR stage (I); and the combined syngas stream is arranged to be supplied to the synthesis stage (B).

[0065] Compared to a tandem methanation and ATR stage, this implementation reduces the amount of oxygen required.

[0066] Reverse Water Gas Shift (rWGS) Section

[0067] On the other hand, the syngas stage includes a reverse water gas shift (rWGS) section upstream of the ATR section. The rWGS section is in fluid communication with the ATR section. Part or all of the first feed is supplied to the rWGS section; part or all of the second feed is supplied to the rWGS section; and a part or preferably all of the third feed may be supplied to the syngas stage between the rWGS section (III) and the ATR section.

[0068] As previously mentioned, existing technologies for producing syngas from CO2 and hydrogen are based on selective RWGS. Compared to this approach, the combination of RWGS and ATR offers several advantages. These include the possibility of utilizing both external and internal recirculated hydrocarbon streams. Such streams can be added to the ATR section and used for additional syngas production, compared to what can be achieved with independent and selective RWGS. Furthermore, the outlet temperature of the ATR reactor in the ATR section is typically in the range of 900–1100°C. In most cases, this is higher than the temperatures that can be achieved by independent RWGS units. This increases carbon monoxide production, as higher temperatures are thermodynamically favorable for the process.

[0069] On one hand, the rWGS section includes one or more rWHS units arranged in series, such as two or more rWGS units, or even three or more rWGS units. In such rWGS units, CO2 and H2 are converted into CO and H2 through the reaction (1) described above. Parallel reverse water gas shift units can also be considered.

[0070] Multiple portions of the first feed containing hydrogen can be supplied separately to different rWGS units within the rWGS section; or the entire first feed containing hydrogen can be supplied together to the upstream inverse WGS unit within the rWGS section. Similarly, multiple portions of the second feed containing carbon dioxide can be supplied separately to different rWGS units within the rWGS section; or the entire second feed containing carbon dioxide can be supplied together to the upstream inverse WGS unit within the rWGS section.

[0071] Each rWGS unit can be an adiabatic or heated reactor. Heating can be achieved through the hot effluent from the ATR or by utilizing the heat of combustion of, for example, a stream containing hydrocarbons and / or a stream containing hydrogen. The effluent from the rWGS section is a stream containing CO2, H2, CO, and H2O. The temperature of the rWGS effluent from each rWGS unit can be 400-900°C, preferably 500-900°C, more preferably 500-750°C, depending on the degree of rWGS and the degree of heating.

[0072] The effluent from the rWGS section is supplied to the ATR section. In one specific embodiment, the methanation section may be located between the rWGS section and the ATR section. In this case, the effluent from the rWGS section is supplied to the methanation section, and the effluent from the methanation section is supplied to the ATR.

[0073] Reverse Water Gas Shift (rWGS) Section – Alternative Arrangement

[0074] On the other hand, the syngas stage includes a reverse water gas shift (rWGS) section arranged in parallel with the ATR section. The rWGS section is in fluid communication with the ATR section. Part or all of the first feed is supplied to the rWGS section; part or all of the second feed is supplied to the rWGS section; wherein the rWGS section is arranged to convert at least a portion of the first feed and at least a portion of the second feed into a syngas stream containing H2, CO, CO2, and H2O.

[0075] A third feed containing hydrocarbons and a fourth feed containing oxygen, together with an optional portion of a first feed containing hydrogen and / or an optional portion of a second feed containing carbon dioxide, are arranged to be supplied to an ATR section; wherein the ATR section is arranged to convert the feed stream into another synthesis stream containing H2, CO, CO2, CH4 and H2O.

[0076] In this respect, the synthesis gas streams from the rWGS and ATR segments are arranged to be combined to obtain the final synthesis gas stream; wherein the final synthesis gas stream is supplied to the synthesis stage.

[0077] As previously mentioned, existing technologies for producing syngas from CO2 and hydrogen are based on selective rWGS. Compared to this approach, a combination of parallel rWGS and ATR offers several advantages. These include the possibility of utilizing both external and internal recirculated hydrocarbon streams. The advantage of converting a portion of the CO2 in the rWGS section is that it reduces overall oxygen consumption.

[0078] As described above, the rWGS segment may include one or more rWHS units arranged in series, such as two or more rWGS units, or even three or more rWGS units. In such rWGS units, CO2 and H2 are converted into CO and H2 through the reaction (1) described above. Parallel reverse water gas shift units are also conceivable.

[0079] Multiple portions of the first feed containing hydrogen can be supplied separately to different rWGS units within the rWGS section; or the entire first feed containing hydrogen can be supplied together to the upstream inverse WGS unit of the rWGS section. Similarly, multiple portions of the second feed containing carbon dioxide can be supplied separately to different rWGS units within the rWGS section; or the entire second feed containing carbon dioxide can be supplied together to the upstream inverse WGS unit of the rWGS section.

[0080] Each rWGS unit can be an adiabatic or heated reactor. Heating can be achieved through the hot effluent from the ATR or by utilizing the heat of combustion of, for example, a stream containing hydrocarbons and / or a stream containing hydrogen. The effluent from the rWGS section is a stream containing CO2, H2, CO, and H2O. The temperature of the rWGS effluent from each rWGS unit can be 400-900°C, preferably 500-900°C, more preferably 500-750°C, depending on the degree of rWGS and the degree of heating.

[0081] CO after ATR 2 Transformation Unit

[0082] On the other hand, the equipment includes a post-conversion (ATR post-conversion, PAC) unit or reactor located downstream of the ATR section.

[0083] The PAC unit can be an adiabatic or heated reactor, using, for example, a Ni-based catalyst and / or a catalyst containing noble metals such as Ru, Rh, Pd, and / or Ir as the active material. In such a PAC unit, a stream containing carbon dioxide, for example a portion of the second feed, and part or all of the syngas from the ATR section are mixed and directed to the PAC unit. In the PAC unit, the mixed stream is converted into syngas with a higher carbon monoxide content through the two reactions (3) and (1) described above. Reactions (3) and (1) are typically at or near chemical equilibrium at the PAC unit outlet. The effluent from the PAC section is a stream containing CO2, H2, CO, H2O, and CH4. The PAC effluent temperature of each PAC unit can be 700-1000°C, preferably 800-950°C, more preferably 850-920°C. Compared to the effluent stream from the ATR section, the advantage of the PAC unit is that it can produce syngas with a lower H2 / CO ratio. Furthermore, the fact that a stream containing carbon dioxide, such as a portion of a second feed, is directed to a PAC unit (e.g., an adiabatic PAC unit) instead of an ATR section reduces the size of the ATR section. In some cases, this may reduce the overall cost.

[0084] The effluent stream from the PAC unit is cooled as described above to provide a synthesis gas flow for the synthesis stage.

[0085] The CO2 conversion (PAC) unit may be included in any of the above aspects.

[0086] Synthetic grade

[0087] The synthesis stage is typically arranged to convert the synthesis gas stream into at least the product stream.

[0088] Hydrocarbon-containing waste gas stream is typically generated in the synthesis stage. Suitablely, in addition to the hydrocarbon-containing third feed, at least a portion of the hydrocarbon-containing waste gas stream is also supplied to the synthesis stage.

[0089] In addition to the third feed containing hydrocarbons, several examples (not exhaustive) of possible waste gas streams to be fed to the syngas stage are provided in the table below; and the corresponding syngas stages are provided in the table below.

[0090]

[0091] By supplying the waste gas stream to the syngas stage in addition to the third feed containing hydrocarbons, the need for external hydrocarbon feedstock can be reduced.

[0092] The synthesis gas flow at the inlet of the synthesis stage suitably has an H2:CO ratio in the range of 1.00-4.00; preferably 1.50-3.00, more preferably 1.50-2.10. If the synthesis stage is an FT stage, the H2:CO ratio is preferably in the range of 1.50-2.10.

[0093] In another embodiment, the synthesis gas flow at the inlet of the synthesis stage suitably has a (H2 - CO2) / (CO + CO2) ratio in the range of 1.50-2.50; preferably 1.80-2.30, more preferably 1.90-2.20. This stoichiometry is suitable for methanol synthesis.

[0094] This technology and the composition of syngas can be applied to various synthesis processes and synthesis stages. Some potential examples of synthesis stages are provided below.

[0095] Fischer-Tropsch synthesis stage

[0096] On one hand, the synthesis stage is the Fischer-Tropsch (FT) stage. The FT stage includes a Fischer-Tropsch (FT) synthesis section, where the syngas from the syngas stage is first converted into a crude product containing at least hydrocarbons and a hydrocarbon-containing waste gas stream in the form of an FT tail gas stream, followed by a hydrotreating and hydrocracking section, where the crude product is converted into at least one or more hydrocarbon product streams. The composition of the crude product from the FT synthesis section depends on the type of catalyst used in the process, the reaction temperature, etc.

[0097] Hydrocarbon-containing waste gas streams in the form of FT tail gas are generated as byproducts. FT tail gas streams typically contain carbon monoxide (10-40 vol. %), hydrogen (10-40 vol. %), carbon dioxide (10-50 vol. %), and methane (10-40 vol. %). Other components such as argon, nitrogen, alkenes, and alkanes with two or more carbon atoms may also be present in smaller quantities.

[0098] In addition to the third feed containing hydrocarbons, at least a portion of the FT tail gas stream can be supplied to the syngas stage. Suitablely, to avoid excessive accumulation of inert components that may be present in the FT tail gas, only a portion of the FT tail gas stream is supplied to the syngas stage; and the remaining portion of the FT tail gas can be purged and / or used as fuel and / or converted into power. In one embodiment, if present, the power can be used as a (partial) source for the electrolysis unit. Alternatively, the power can be output.

[0099] In one implementation, the primary products from the FT synthesis stage are typically jet fuel and / or kerosene (e.g., primarily containing C). 12 – C 15 ) and / or diesel (e.g., mainly containing C) 15 – C 20 In addition, naphtha (e.g., mainly containing C5–C) 12 Streams of LPG (e.g., primarily C3–C4) are also generated in the FT synthesis stage. Some or all of these LPG and / or naphtha streams from the FT synthesis stage may also be used in the syngas stage in addition to the third feed containing hydrocarbons. Some or all of these LPG and / or naphtha streams may be added to the methanation stage and / or directly to the ATR stage. In another embodiment, some or all of these LPG and / or naphtha may undergo a pre-reforming stage before being added to the methanation stage and / or ATR stage.

[0100] Therefore, in one particular embodiment, the synthesis stage is a Fischer-Tropsch (FT) synthesis stage, which is arranged to convert the syngas stream from the syngas stage into at least a hydrocarbon product stream, i.e., a diesel stream; and / or an LPG and / or naphtha product stream and / or a kerosene or jet fuel product stream, and wherein, in addition to the hydrocarbon-containing third feed, at least a portion of the LPG and / or naphtha product stream is also supplied to the syngas stage. On one hand, at least a portion of the FT tail gas, at least a portion of the LPG, and at least a portion of the naphtha product stream are supplied to the syngas stage. On the other hand, at least a portion of the FT tail gas and at least a portion of the LPG are supplied to the syngas stage. The LPG and / or naphtha stream may be pre-reformed before being supplied to the syngas stage.

[0101] Methanol synthesis grade

[0102] In another embodiment, the synthesis stage is a methanol (MeOH) synthesis stage. This stage includes a MeOH synthesis section where syngas from the syngas stage is first converted into a crude MeOH stream, followed by a purification section where the crude MeOH stream is purified to obtain a MeOH product stream. The MeOH synthesis stage produces a purge stream, which typically contains hydrogen, carbon dioxide, carbon monoxide, and methane. Additional components such as argon, nitrogen, or oxygen-containing compounds having two or more carbon atoms may also be present in smaller quantities.

[0103] In addition to the third feed containing hydrocarbons, at least a portion of the MeOH purge gas stream can be supplied to the syngas stage. The MeOH purge gas stream can be purified before being supplied to the syngas stage. Suitablely, to avoid excessive accumulation of inert components that may be present in the MeOH purge gas, only a portion of the MeOH purge gas stream can be supplied to the syngas stage; and the remaining portion of the MeOH purge gas can be purged and / or used as fuel.

[0104] Specifically, when the synthesis stage is a methanol synthesis stage, the syngas flow at the outlet of the syngas stage has a modulus in the range of 1.80-2.30, preferably 1.90-2.20, as defined herein. The term "modulus" is defined as:

[0105] Methanol-to-Gasoline (MTG) Synthetic Grade

[0106] In another embodiment, the synthesis stage is a methanol-to-gasoline (MTG) synthesis stage, including a MeOH synthesis section, wherein the synthesis gas from the synthesis gas stage is first converted into a crude MeOH stream, and then into a gasoline synthesis section, wherein the crude MeOH stream is converted into a gasoline product stream.

[0107] The MTG synthesis stage also produces a purge stream. This purge stream can be used in a similar manner to that explained in the previous section, "Methanol Synthesis Stage".

[0108] The MTG synthesis stage produces an LPG (e.g., primarily C3–C4) stream. Part or all of this LPG stream from the MTG synthesis stage can also be supplied to the syngas stage in addition to the hydrocarbon-containing third feed. Part or all of the LPG stream can be added to the methanation section and / or directly to the ATR section. In another embodiment, the LPG stream can be pre-reformed before being added to the methanation section and / or ATR section.

[0109] Synthesis of higher alcohols (HA)

[0110] In another embodiment, the synthesis stage is a higher alcohol (HA) synthesis stage, including an HA synthesis section, wherein the syngas from the syngas stage is first converted into a crude alcohol stream, followed by a purification section, wherein the crude alcohol stream is purified to obtain an HA product stream.

[0111] The HA synthesis stage produces a tail gas stream, which typically contains hydrogen, carbon dioxide, and carbon monoxide. Additional components such as argon, nitrogen, methane, or oxygen-containing compounds with two or more carbon atoms may also be present in smaller quantities.

[0112] The HA synthesis stage can also produce a methane-rich stream, which typically contains methane, hydrogen, and carbon monoxide. Additional components such as argon, nitrogen, carbon dioxide, or oxygen-containing compounds with two or more carbon atoms may also be present in smaller quantities.

[0113] In addition to the third feed containing hydrocarbons, at least a portion of the tail gas and / or the methane-rich stream may be supplied to the syngas stage. Suitablely, to avoid excessive accumulation of inert components that may be present in the tail gas and / or the methane-rich stream, only a portion of the tail gas and / or the methane-rich stream may be supplied to the syngas stage; and the other portion may be purged and / or used as fuel.

[0114] Synthesis of olefins from syngas (STO)

[0115] In another embodiment, the synthesis stage is a syngas to olefins (STO) synthesis stage, including an STO synthesis section, wherein the syngas from the syngas stage is first converted into a crude olefin-rich stream, followed by a purification section, wherein the crude olefin-rich stream is purified to obtain an olefin product stream.

[0116] The STO synthesis stage produces a tail gas stream, which typically contains hydrogen, carbon dioxide, and carbon monoxide. Additional components such as argon, nitrogen, or hydrocarbons with two or more carbon atoms may also be present in smaller quantities.

[0117] The STO synthesis stage can also produce a hydrocarbon-rich stream, which typically contains methane and higher hydrocarbons with two or more carbon atoms. These higher hydrocarbons can be both alkenes and alkanes. Additional components such as hydrogen, carbon dioxide, carbon monoxide, argon, and nitrogen may also be present in smaller quantities.

[0118] In addition to the third feed containing hydrocarbons, at least a portion of the tail gas and / or the hydrocarbon-rich stream may be supplied to the syngas stage. Suitablely, to avoid excessive accumulation of inert components that may be present in the tail gas and / or the hydrocarbon-rich stream, only a portion of the tail gas and / or the hydrocarbon-rich stream may be supplied to the syngas stage; and the other portion may be purged and / or used as fuel.

[0119] Synthesis of Ethylene Oxide from Syngas (STEtO)

[0120] In another embodiment, the synthesis stage is a syngas-to-ethylene oxide (STEtO) synthesis stage. The STEtO stage includes a syngas-to-olefins (STO) synthesis section, in which the syngas is first converted into olefin products (mainly ethylene), and then into an ethylene oxide synthesis section.

[0121] The STO synthesis stage produces a tail gas stream, which typically contains hydrogen, carbon dioxide, and carbon monoxide. Additional components such as argon, nitrogen, or hydrocarbons with two or more carbon atoms may also be present in smaller quantities.

[0122] The STO synthesis stage can also produce a hydrocarbon-rich stream, which typically contains methane and higher hydrocarbons with two or more carbon atoms. These higher hydrocarbons can be both alkenes and alkanes. Additional components such as hydrogen, carbon dioxide, carbon monoxide, argon, and nitrogen may also be present in smaller quantities.

[0123] In addition to the third feed containing hydrocarbons, at least a portion of the tail gas and / or the hydrocarbon-rich stream may be supplied to the syngas stage. Suitablely, to avoid excessive accumulation of inert components that may be present in the tail gas and / or the hydrocarbon-rich stream, only a portion of the tail gas and / or the hydrocarbon-rich stream may be supplied to the syngas stage; and the other portion may be purged and / or used as fuel.

[0124] The ethylene oxide synthesis stage can utilize at least a portion of the fourth feed (O2). During ethylene oxide synthesis, a significant amount of CO2 is generated as a byproduct. This CO2 byproduct can be recycled, and at least a portion can be used as the first feed to the syngas stage.

[0125] Gasoline and diesel co-production

[0126] In another embodiment, the synthesis stage can be a combination of an FT (Fuel Transfer) stage and a methanol-to-gasoline (MTG) synthesis stage connected in parallel with a common syngas feed from the syngas stage. The FT stage produces middle distillate products (diesel / jet fuel / kerosene, etc.), and the MTG produces gasoline with a desired octane number. In this embodiment, the syngas stage supplies syngas of suitable quality to the FT and MTG stages, which operate in parallel with each other. At least a portion of the recycle gas from the FT and / or at least a portion of the LPG stream from the MTG stage and / or at least a portion of the purge stream from the MeOH synthesis stage can be used as a third feed to the syngas stage.

[0127] Electrolytic cell

[0128] The apparatus may also include an electrolytic cell arranged to convert water or steam into at least a hydrogen-containing gas stream and an oxygen-containing gas stream, wherein at least a portion of the hydrogen-containing gas stream from the electrolytic cell is supplied to a syngas stage as the first feed and / or wherein at least a portion of the oxygen-containing gas stream from the electrolytic cell is supplied to the syngas stage as the fourth feed. The electrolytic cell may include one or more electrolysis units, such as solid oxide electrolysis.

[0129] Therefore, in a preferred embodiment, the apparatus further includes an electrolyzer located upstream of the syngas stage. The electrolyzer is arranged to convert water or steam into at least a hydrogen-containing gas stream and an oxygen-containing gas stream.

[0130] At least a portion of the hydrogen-containing gas stream from the electrolyzer is supplied to the syngas stage as the first feed. Alternatively or additionally, at least a portion of the oxygen-containing gas stream from the electrolyzer is supplied to the syngas stage as the fourth feed. This provides efficient sources of both the first and fourth feeds.

[0131] In a preferred embodiment, all hydrogen in the first feed and all oxygen in the fourth feed are produced by electrolysis. In this way, the hydrogen and oxygen required by the equipment are produced by steam and electricity. Furthermore, if the electricity is produced solely from renewable energy sources, the hydrogen and oxygen in the first and fourth feeds are produced without fossil fuels or fuels.

[0132] Preferably, the water or steam supplied to the electrolytic cell is obtained from one or more units or stages in the equipment.

[0133] The use of an electrolytic cell can be combined with any of the implementation schemes described in this document.

[0134] Additional aspects

[0135] Optionally, the apparatus may include a sixth feed containing hydrogen upstream of the synthesis stage, which leads to the synthesis gas stream. The sixth feed may have the same composition as the first feed containing hydrogen, i.e., the sixth feed is substantially composed of hydrogen, and more than 75%, for example more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the feed may be hydrogen.

[0136] If needed, the sixth feed can be used to adjust the composition of the syngas in the syngas stream (e.g., the H2 / CO ratio). In a preferred aspect, at least a portion of the hydrogen-containing gas stream from the electrolyzer is supplied to the syngas stream as the sixth hydrogen feed upstream of the synthesis stage. This provides additional opportunities for systems that do not require additional external gas input and allow for final adjustment of the gas composition upstream of the synthesis stage.

[0137] The composition of the syngas from the syngas stage can be adjusted in other ways. For example, the apparatus may also include a hydrogen removal section located between the syngas stage and the syngas stage, which is arranged to remove at least a portion of the hydrogen from the syngas stream. In this case, at least a portion of the hydrogen removed from the syngas stream in the hydrogen removal section can be compressed and supplied to the syngas stage as part of the first feed. The hydrogen removal unit may be, but is not limited to, a pressure swing adsorption (PSA) unit or a membrane unit.

[0138] Furthermore, the device may also include a carbon dioxide removal section located between the syngas stage and the synthesis stage, which is arranged to remove at least a portion of the carbon dioxide from the syngas stream. In this case, at least a portion of the carbon dioxide removed from the syngas stream in the carbon dioxide removal section can be compressed and supplied to the syngas stage as part of the second feed. The carbon dioxide removal unit may be, but is not limited to, an amine-based unit or a membrane unit.

[0139] Before the feedstock reaches the syngas stage, the exhaust gas stream can be treated to remove one or more components or alter the chemical properties of one or more components. The exhaust gas, such as FT exhaust gas, may contain olefins. At high temperatures, olefins increase the risk of carbon deposition and / or metal dust formation. Therefore, the apparatus may also include a hydrogenator arranged in the FT exhaust gas recirculation stream. The hydrogenator is arranged to hydrogenate the third feedstock before it enters the syngas stage. In this way, olefins can be efficiently converted to saturated hydrocarbons before entering the syngas stage.

[0140] Waste gas streams or portions that are not recirculated to the syngas stage or used for other purposes can be used to generate additional syngas in a separate syngas generator. Such a syngas generator may include techniques known in the art, such as ATR, steam reforming (SMR), and / or adiabatic pre-reforming, but other techniques are also known. This additional syngas can be supplied to the synthesis stage. For example, tail gas from the Fischer-Tropsch synthesis stage can be converted into additional syngas by means known in the art, such as hydrogenation, subsequent water-gas shift, and autothermal reforming.

[0141] method

[0142] A method for producing a product flow is provided, the method comprising the following steps: - Provides an apparatus (X) comprising: a. A syngas stage (A), said syngas stage comprising an autothermal reforming (ATR) section (I), and b. Synthetic grade (B); The device includes: - The first feed containing hydrogen to the syngas stage (1); - Second feed containing carbon dioxide to the syngas stage (2); - A third feed (3) containing hydrocarbons, located upstream of the ATR section, leading to the syngas stage; and - The fourth feed containing oxygen to the ATR section (4); The syngas stage (A) is arranged to provide a syngas flow (100) and supply the syngas flow (100) to the syngas stage (B); - Supply a first feed containing hydrogen to the syngas stage (1); - A second feed containing carbon dioxide is supplied to the syngas stage (2); - A third feed (3) containing hydrocarbons is supplied upstream of the ATR section (I) to the syngas stage; - Supply the fourth feed containing oxygen to the ATR section (4); - A synthesis gas stream (100) is provided in the synthesis gas stage (A) from at least the first, second, third and fourth feeds, and the synthesis gas stream (100) is supplied to the synthesis stage (B); - In the synthesis stage (B), the synthesis gas stream (100) is converted into at least a product stream (500) and a hydrocarbon-containing waste gas stream (3b); and - Optionally, in addition to the third feed (3) containing hydrocarbons, at least a portion of the hydrocarbon-containing waste gas stream (3b) is also supplied to the syngas stage (I); upstream of the ATR stage (I); When the equipment is outside, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 in the second feed is less than 0.5.

[0143] All aspects relating to the aforementioned equipment also apply to the methods of using the equipment. When applied to the methods of the present invention, the term "supply" means providing a flow of gas to a suitable stage, reactor, or unit. In particular, note the following aspects that are especially important to the methods of the present invention: - In addition to the third feed containing hydrocarbons, the method may also include the additional step of supplying at least a portion of the hydrocarbon-containing waste gas stream to the syngas stage.

[0144] - The synthesis stage can be a Fischer-Tropsch (FT) stage, which is arranged to convert the synthesis gas stream into a hydrocarbon-containing waste gas stream in the form of at least a hydrocarbon product stream and an FT tail stream.

[0145] - The electrolyzer may be located upstream of the syngas stage, and the method may further include converting water or steam into at least a hydrogen-containing gas stream and an oxygen-containing gas stream. The method may further include the steps of supplying at least a portion of the hydrogen-containing gas stream from the electrolyzer as a first hydrogen feed to the syngas stage and / or supplying at least a portion of the oxygen-containing gas stream from the electrolyzer as a fourth oxygen feed to the syngas stage. The method may further include obtaining water or steam supplied to the electrolyzer as condensate from one or more units or stages in the hydrocarbon plant.

[0146] - When outside the equipment, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 in the second feed is less than 0.3, preferably less than 0.25, and more preferably less than 0.20 or even less than 0.10.

[0147] - The synthesis gas flow at the inlet of the synthesis stage has a hydrogen / carbon monoxide ratio in the range of 1.00-4.00; preferably 1.50-3.00, more preferably 1.50-2.10.

[0148] - The H2:CO2 ratio provided at the equipment inlet is between 1.0 and 9.0, preferably between 2.5 and 8.0, and more preferably between 3.0 and 7.0.

[0149] - The synthesis stage is an FT synthesis stage, and the H2:CO2 ratio at the equipment inlet is in the range of 3.0-7.0, or more preferably 3.0-6.0, and most preferably 3.0-5.0.

[0150] - The syngas stage (A) consists of the self-heating reforming (ATR) section (I), wherein the first, second, third and fourth feeds are supplied to the ATR section.

[0151] - The syngas stage also includes a methanation stage (II) arranged upstream of the ATR stage (I); wherein part or all of the first feed is supplied to the methanation stage; part or all of the second feed is supplied to the methanation stage; and wherein part or all of the third feed is supplied to the syngas stage; upstream of the methanation stage or between the methanation stage and the ATR stage.

[0152] - The syngas stage also includes a reverse water gas shift (rWGS) stage (III) located upstream of the ATR stage (I), wherein part or all of the first feed (1d) is supplied to the rWGS stage; part or all of the second feed is supplied to the rWGS stage; and wherein part or all of the third feed is supplied to the syngas stage between the rWGS stage (III) and the ATR stage.

[0153] - The syngas stage (A) includes a reverse water gas shift (rWGS) stage (III) arranged in parallel with the ATR stage (I); wherein at least a portion of the first feed and at least a portion of the second feed are arranged to be supplied to the rWGS stage and the rWGS stage is arranged to convert the at least a portion of the first feed and the at least a portion of the second feed into a first syngas stream; a third feed containing hydrocarbons and a fourth feed containing oxygen are arranged to be supplied to the ATR stage (I); and wherein the ATR stage (I) is arranged to convert the third feed containing hydrocarbons and the fourth feed containing oxygen into a second syngas stream, wherein the first syngas stream from the rWGS stage (III) is arranged to be combined with the second syngas stream from the ATR stage (I); and the combined syngas stream is arranged to be supplied to the syngas stage.

[0154] Detailed description of the attached figures

[0155] Figure 1 A schematic layout of the first embodiment of the device is shown.

[0156] A Syngas Stage

[0157] B Synthetic Grade

[0158] 1. First feed (containing hydrogen) to the syngas stage

[0159] 2. Second feed (containing carbon dioxide) to the syngas stage

[0160] 3. The third feed to the syngas stage (which may be hydrocarbons flowing from outside and / or inside the equipment).

[0161] 4. The fourth feed (containing oxygen) to the syngas stage

[0162] 100 Syngas products from the syngas stage

[0163] 500 products from synthetic grade

[0164] Figure 1a A schematic diagram of a first embodiment of the device is shown, wherein the hydrocarbon feed can come from an external source or from the synthesis stage, for example, more than one, such as three hydrocarbon streams from the synthesis stage. (The reference numerals are...) Figure 1 Same as above, plus: 3a A portion of the third feed to the syngas stage from an external source (e.g., an external hydrocarbon stream, such as natural gas). 3b A portion of the third feed from the synthesis stage to the syngas stage (e.g., exhaust gas from the FT). 3c Another portion of the third feed from the synthesis stage to the syngas stage (e.g., the LPG stream from the FT). 3d Another portion of the third feed from the synthesis stage to the syngas stage (e.g., naphtha stream from FT). Figure 2 A schematic layout of another embodiment of the equipment is shown, in which the syngas stage includes a pre-reforming section (Ia) and an ATR section (I), and steam is shown as the fifth feed (5). Reference numerals are... Figure 1 and 1a Same as above, plus: (Ia) Pre-reforming segment (I) ATR segment 1a A portion of the first feed heading to the pre-reforming section 1b A portion of the first feed heading to the ATR section 5. Fifth feed (steam) 10. Hydrocarbons destined for the ATR stage (pre-reforming) Figure 3 A schematic layout of another embodiment of the equipment is shown, wherein the syngas stage includes a methanation section (II) and an ATR section (I). The effluent from the methanation section (II) is fed to the ATR section (I). The reference numerals are the same as in the previous figures, plus: (II) Methanation segment 30 Effluent from the methanation section to the ATR section Figure 3a It shows Figure 3 A variant of the schematic layout described herein. In this embodiment of the equipment, the hydrocarbon feed is processed in the pre-reforming section (Ia) and then fed to the methanation section (II), followed by the ATR section (I). A fifth feed steam (5) is introduced into the pre-reforming section. The reference numerals are the same as in the previous figures, plus: 20 Hydrocarbons destined for the methanation stage (pre-reforming) Figure 3b It shows Figure 3a A variation of the schematic layout described herein. This is one embodiment of the device, in which a portion of the steam (5a) is added and fed to the pre-reforming section, and another portion of the steam (5b) is added and fed to the methanation section. The reference numerals are the same as in the previous figures, plus: 5a A portion of the fifth feed heading to the pre-reforming section. 5b A portion of the fifth feed to the methanation section. Figure 4 A schematic layout of another embodiment of the equipment is shown, in which the syngas stage comprises an rWGS section (III) plus an ATR section (I). The reference numerals are the same as in the previous figures, plus: (III) rWGS segment 1d Part of the first feed heading to the rWGS section 40. Synthetic flow from rWGS segment (III) Figure 4a A schematic layout of another embodiment of the equipment is shown, in which the syngas stage comprises an rWGS section (III) and an ATR section (I). In this layout, the rWGS section (III) and the ATR section (I) are connected in parallel. The reference numerals are the same as in the previous figures, plus: 50. Composite airflow from ATR segment (I) Figure 4b It shows according to Figure 4a A schematic layout of another embodiment of the device. Figure 4b In the layout, the syngas flow 50 from the ATR section (I) is arranged to heat the rWGS section (III). The effluent from the ATR section (I) is cooled by heat exchange with the rWGS section to become the syngas flow 60, which is then merged with the syngas flow 40 from the rWGS section (III).

[0165] 60 After cooling in the rWGS section (III), the synthetic gas flow from the ATR section (I) is cooled.

[0166] Figure 4c Corresponding to Figure 4a The methanation stage (II) is present instead of the rWGS stage (III).

[0167] Figure 5 A schematic layout of another embodiment of the equipment is shown, wherein a component recovery stage (C), i.e., the recycling of hydrogen or more CO2, exists between the syngas stage (A) and the synthesis stage (B). The reference numerals are the same as in the previous figures, plus: C Component Recovery Grade 150 liters of recirculated gas from the component recovery stage 200 syngas from the component recovery stage Example Different syngas stages are compared based on their efficiency in utilizing carbon feedstocks and energy. In recent years, CO2 emissions from these syngas stages have also been compared to minimize environmental impact.

[0168] Traditionally, hydrocarbon-based feedstocks are primarily used in the syngas stage (A). Typical values ​​for the distinguishing factors mentioned above for such syngas stages, which consist of an autothermal reforming (ATR) stage (I), are shown in Table 1.

[0169] In C1, values ​​for the hydrocarbon-based syngas stage (A) from a conventional design without a CO2 feed are shown. In C2, some H2 and CO2 feeds are used alongside the hydrocarbon feed. The hydrocarbon feed is still higher than the CO2 feed. In C3, even more CO2 and H2 feeds are used, making the CO2 feed consumption higher than the hydrocarbon feed consumption.

[0170] Table 1

[0171] It can be seen that CO2 emissions improve with increasing CO2 feed consumption. However, the conversion rate decreases to some extent.

[0172] This challenge can be addressed by including a methanation stage (II) in the syngas stage (A) in addition to the ATR stage (I). Table 2 provides the key parameters for the syngas stage (A), which consists of the methanation stage (II) followed by the ATR stage (I). The syngas produced in the syngas stage (A) is supplied to the synthesis stage (B), which includes the Fischer-Tropsch synthesis stage and the product post-processing stage. Some of the recycle stream from the synthesis stage (B) is used internally within the syngas stage (A).

[0173] Table 2

[0174] In this concept, no hydrocarbon combustion occurs, and no CO2 is emitted.

[0175] The specific net energy consumption of the syngas stage is based on 1 Nm of product flow. 3 The (H2 + CO) estimates are used. In Tables 1 and 2, the relative CO2 emissions are estimated relative to C1-based CO2 emissions.

[0176] The following aspects are provided: Aspect 1. An apparatus comprising: a. A syngas stage, said syngas stage comprising an autothermal reforming (ATR) section, and; b. Synthetic stage; The device includes: -The first feed containing hydrogen to the syngas stage; - A second feed containing carbon dioxide leading to the syngas stage; - A third feed containing hydrocarbons, located upstream of the ATR section, leading to the syngas stage; and - The fourth feed containing oxygen to the ATR section; The syngas stage is arranged to provide a syngas flow and supply the syngas flow to the syngas stage.

[0177] Aspect 2. The apparatus according to aspect 1, wherein the third feed containing hydrocarbons is directly supplied to the syngas stage upstream of the ATR section.

[0178] Aspect 3. The apparatus according to any one of the preceding aspects, wherein the synthesis gas stream is directly supplied from the synthesis gas stage to the synthesis stage.

[0179] Aspect 4. The apparatus according to any one of Aspects 1-2, wherein the apparatus includes a post-conversion section located between the syngas stage and the syngas stage, and a CO2 feed to the post-conversion section, the CO2 feed being arranged to mix with the syngas stream between the syngas stage and the post-conversion section.

[0180] Aspect 5. The apparatus according to any one of the preceding aspects further includes a fifth steam feed to the syngas stage.

[0181] Aspect 6. The apparatus according to any one of the preceding aspects, wherein the syngas stage comprises the autothermal reforming (ATR) section, and wherein the first, second, third and fourth feeds are supplied to the ATR section.

[0182] Aspect 7. The apparatus according to any one of Aspects 1-5, wherein the syngas stage further comprises a methanation section disposed upstream of the ATR section; wherein a portion or all of the first feed is supplied to the methanation section; a portion or all of the second feed is supplied to the methanation section; and wherein a portion or all of the third feed is supplied to the syngas stage; upstream of the methanation section and / or between the methanation section and the ATR section.

[0183] Aspect 8. The apparatus according to aspect 7, wherein the methanation section comprises two or more methanation units, such as three or more methanation units.

[0184] Aspect 9. The apparatus according to aspect 8, wherein multiple portions of the first feed containing hydrogen are respectively supplied to different methanation units in the methanation section; or the first feed containing hydrogen is supplied together to the most upstream methanation unit in the methanation section.

[0185] Aspect 10. The apparatus according to any one of Aspects 8-9, wherein multiple portions of the second feed containing carbon dioxide are respectively supplied to different methanation units in the methanation section; or the second feed containing carbon dioxide is supplied together to the most upstream methanation unit in the methanation section.

[0186] Aspect 11. The apparatus according to any one of Aspects 8-10, wherein multiple portions of the third feed containing hydrocarbons are respectively fed to different methanation units in the methanation section; or the third feed containing hydrocarbons is fed together to one methanation unit in the methanation section.

[0187] Aspect 12. The apparatus according to any one of Aspects 8-11, wherein a portion of the effluent from a methanation unit is cooled and recycled to the inlet of the methanation unit and / or the inlet of any additional methanation unit located upstream of the methanation unit.

[0188] Aspect 13. The apparatus according to any one of Aspects 1-5 and 7-12, wherein the syngas stage further comprises a reverse water gas shift (rWGS) section located upstream of the ATR section, wherein part or all of the first feed is supplied to the rWGS section; part or all of the second feed is supplied to the rWGS section; and wherein part or all of the third feed is supplied to the syngas stage between the rWGS section (III) and the ATR section.

[0189] Aspect 14. The device according to aspect 13, wherein the rWGS segment includes two or more rWGS units, such as three or more rWGS units.

[0190] Aspect 15. The apparatus according to aspect 14, wherein multiple portions of the first feed containing hydrogen are respectively supplied to different rWGS units in the rWGS section; or the first feed containing hydrogen is supplied together to the upstream inverse WGS unit in the rWGS section.

[0191] Aspect 16. The apparatus according to any one of Aspects 14-15, wherein multiple portions of the second feed containing carbon dioxide are respectively supplied to different rWGS units in the rWGS section; or the second feed containing carbon dioxide is supplied together to the most upstream rWGS unit in the rWGS section.

[0192] Aspect 17. The apparatus according to any one of the preceding aspects, wherein the synthesis gas flow at the synthesis stage inlet has a hydrogen / carbon monoxide ratio in the range of 1.00-4.00; preferably 1.50-3.00, more preferably 1.50-2.10.

[0193] Aspect 18. The apparatus according to any one of the preceding aspects, wherein the syngas flow at the outlet of the syngas stage has a modulus as defined above in the range of 1.50-2.50; preferably 1.80-2.30, more preferably 1.90-2.20.

[0194] Aspect 19. The apparatus according to any one of the preceding aspects, wherein the H2:CO2 ratio provided at the apparatus inlet is 1.0-9.0, preferably 2.5-8.0, more preferably 3.0-7.0.

[0195] Aspect 20. The apparatus according to any one of the preceding aspects, wherein the synthesis stage is a Fischer-Tropsch (FT) stage, and wherein the H2:CO2 ratio provided at the apparatus inlet is in the range of 3.0-7.0, or more preferably 3.0-6.0, and most preferably 3.0-5.0.

[0196] Aspect 21. The apparatus according to any one of the preceding aspects, wherein the first feed consists substantially of hydrogen, i.e., more than 75%, for example more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the first feed is hydrogen.

[0197] Aspect 22. The apparatus according to any one of the preceding aspects, wherein the second feed is substantially composed of carbon dioxide, i.e., more than 75%, for example more than 85%, preferably more than 90%, more preferably more than 95%, and even more preferably more than 99% of the second feed is carbon dioxide.

[0198] Aspect 23. The apparatus according to any one of the preceding aspects, wherein the third feed comprises one or more hydrocarbons selected from methane, ethane, propane or butane.

[0199] Aspect 24. The apparatus according to any one of the preceding aspects, wherein the third feed comprising hydrocarbons is a natural gas feed.

[0200] Aspect 25. The apparatus according to any one of the preceding aspects, wherein the third feed further comprises CO2 and / or CO and / or H2.

[0201] Aspect 26. The apparatus according to any one of the preceding aspects, wherein the fourth feed is substantially composed of oxygen, i.e., more than 75%, for example more than 90% or more than 95%, for example more than 99%, of the fourth feed is oxygen.

[0202] Aspect 27. The apparatus according to any one of the preceding aspects, wherein the fourth feed further comprises steam.

[0203] Aspect 28. The apparatus according to any one of the preceding aspects, wherein the synthesis stage is arranged to convert the synthesis gas stream into at least a product stream and optionally a hydrocarbon-containing waste gas stream.

[0204] Aspect 29. The apparatus according to aspect 28, wherein, in addition to the third feed containing hydrocarbons, at least a portion of the hydrocarbon-containing waste gas stream is also supplied to the syngas stage.

[0205] Aspect 30. The apparatus according to any one of the preceding aspects, wherein the synthesis stage is a Fischer-Tropsch (FT) stage, which is arranged to convert the synthesis gas stream into a hydrocarbon-containing waste gas stream in the form of at least a hydrocarbon product stream and an FT tail gas stream.

[0206] Aspect 31. The apparatus according to any one of the preceding aspects, wherein the synthesis stage is a Fischer-Tropsch (FT) stage, which is arranged to convert the synthesis gas stream into at least a hydrocarbon product stream, i.e., a diesel stream; and / or an LPG and / or naphtha product stream, and wherein, in addition to the third feed containing hydrocarbons, at least a portion of the LPG and / or naphtha product stream is also supplied to the synthesis gas stage.

[0207] Aspect 32. The apparatus according to any one of Aspects 1-31, wherein the synthesis stage includes at least one methanol synthesis stage arranged to provide at least a methanol product stream.

[0208] Aspect 33. The apparatus according to aspect 32, wherein the synthesis stage further includes a methanol-to-gasoline (MTG) synthesis stage, which is arranged to receive a methanol product stream from the methanol synthesis stage and convert it into at least a gasoline stream and an LPG product stream, and wherein optionally, in addition to the third feed containing hydrocarbons, a portion of the LPG product stream is also supplied to the synthesis gas stage.

[0209] Aspect 34. The apparatus according to any one of the preceding aspects, wherein when the third feed is an LPG and / or naphtha product stream or a natural gas feed, the apparatus further comprises a pre-reforming section upstream of the syngas stage, which is arranged in the third feed.

[0210] Aspect 35. The apparatus according to aspect 34, wherein the hydrocarbon product stream is an LPG and / or naphtha product stream from the FT stage, and wherein the LPG and / or naphtha product stream passes through the pre-reforming section before being supplied to the syngas stage.

[0211] Aspect 36. The apparatus according to any one of Aspects 34-35, wherein the exhaust gas from the ATR section is arranged as a heated pre-reformation section.

[0212] Aspect 37. The apparatus according to any one of the preceding aspects further includes an electrolytic cell arranged to convert water or steam into at least a hydrogen-containing gas stream and an oxygen-containing gas stream, wherein at least a portion of the hydrogen-containing gas stream from the electrolytic cell is supplied to the syngas stage as the first feed and / or wherein at least a portion of the oxygen-containing gas stream from the electrolytic cell is supplied to the syngas stage as the fourth feed.

[0213] Aspect 38. The apparatus according to aspect 37, wherein the water or steam supplied to the electrolytic cell is obtained from one or more units or stages of the apparatus.

[0214] Aspect 39. The apparatus according to any one of the preceding aspects, comprising a sixth hydrogen feed upstream of the synthesis stage, which is supplied to the synthesis gas stream.

[0215] Aspect 40. The apparatus according to aspect 39, wherein at least a portion of the hydrogen-containing gas stream from the electrolyzer is supplied as the sixth hydrogen feed to the synthesis gas stream upstream of the synthesis stage.

[0216] Aspect 41. The apparatus according to any one of Aspects 31-40, wherein when the third feed is an exhaust gas stream, the apparatus further includes a hydrogenator arranged to hydrogenate the third feed before it enters the syngas stage.

[0217] Aspect 42. The apparatus according to any one of the preceding aspects further includes a hydrogen removal section located between the syngas stage and the syngas stage, and arranged to remove at least a portion of the hydrogen from the syngas stream.

[0218] Aspect 43. The apparatus according to aspect 42, wherein at least a portion of the hydrogen removed from the syngas stream in the hydrogen removal section is compressed and supplied as the first feed to the syngas stage.

[0219] Aspect 44. The apparatus according to any one of the preceding aspects further includes a carbon dioxide removal section located between the syngas stage and the syngas stage, and arranged to remove at least a portion of the carbon dioxide from the syngas stream.

[0220] Aspect 45. The apparatus according to aspect 44, wherein at least a portion of the carbon dioxide removed from the synthesis gas stream in the carbon dioxide removal section is compressed and supplied as the second feed to the synthesis gas stage.

[0221] Aspect 46. The apparatus according to any one of the preceding aspects, wherein when outside the apparatus, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 in the second feed is less than 0.3, preferably less than 0.25, and more preferably less than 0.2 or even less than 0.1.

[0222] Aspect 47. The apparatus according to any one of the preceding aspects, wherein the syngas stage further includes a reverse water gas shift (rWGS) section and a methanation section; and wherein the reverse water gas shift (rWGS) section is arranged upstream of the methanation section, and the methanation section is arranged upstream of the ATR section.

[0223] Aspect 48. The device according to any one of the preceding aspects, wherein

[0224] - The syngas stage (A) includes a methanation stage (II) arranged in parallel with the ATR stage (I); - At least a portion of the first feed (1) and at least a portion of the second feed (2) are arranged to be supplied to the methanation section (II) and the methanation section (II) is arranged to convert the at least a portion of the first feed (1) and at least a portion of the second feed (2) into a first synthesis gas stream (40). - A third feed (3) containing hydrocarbons and a fourth feed (4) containing oxygen are arranged to be supplied to an ATR section (I); and wherein the ATR section (I) is arranged to convert the third feed (3) containing hydrocarbons and the fourth feed (4) containing oxygen into a second synthesis gas stream (50). -The first synthesis gas stream (40) from the methanation section (II) is arranged to be combined with the second synthesis gas stream (50) from the ATR section (I); and the combined synthesis gas stream (100) is arranged to be supplied to the synthesis stage (B).

[0225] Aspect 49. The device according to any one of the preceding aspects, wherein

[0226] -The syngas stage (A) includes a reverse water gas shift (rWGS) stage (III) arranged in parallel with the ATR stage (I); - At least a portion of the first feed (1) and at least a portion of the second feed (2) are arranged to be supplied to the rWGS (III) and the rWGS (III) is arranged to convert the at least a portion of the first feed (1) and at least a portion of the second feed (2) into a first synthesis gas flow (40). - A third feed (3) containing hydrocarbons and a fourth feed (4) containing oxygen are arranged to be supplied to an ATR section (I); and wherein the ATR section (I) is arranged to convert the third feed (3) containing hydrocarbons and the fourth feed (4) containing oxygen into a second synthesis gas stream (50). -The first synthesis flow (40) from the rWGS section (III) is arranged to be combined with the second synthesis flow (50) from the ATR section (I); and the combined synthesis flow (100) is arranged to be supplied to the synthesis stage (B).

[0227] Aspect 50. The apparatus according to aspect 48 or 49, wherein, prior to merging the first and second synthesis gas streams, a second synthesis gas stream (50) from the ATR section (I) is arranged to provide at least a portion of the required energy for an endothermic reaction in the rWGS section (III).

[0228] Aspect 51. A method for producing a product flow, the method comprising the following steps: - Provide a device as defined in any of the foregoing aspects; - Supply the first feed containing hydrogen to the syngas stage; - Supply a second feed containing carbon dioxide to the syngas stage; - A third feed containing hydrocarbons is supplied upstream of the ATR section to the syngas stage; - Supply the ATR section with a fourth feed containing oxygen; - A synthesis gas stream (100) is provided in the synthesis gas stage (A) from at least the first, second, third and fourth feeds, and the synthesis gas stream (100) is supplied to the synthesis stage (B); - In the synthesis stage (B), the synthesis gas stream (100) is converted into at least a product stream (500) and a hydrocarbon-containing waste gas stream (3b); and -Optionally, in addition to the third feed (3) containing hydrocarbons, at least a portion of the hydrocarbon-containing waste gas stream (3b) is also supplied to the syngas stage (I); upstream of the ATR stage (I).

[0229] Aspect 52. The method according to aspect 51, wherein the synthesis stage is a Fischer-Tropsch (FT) stage, which is arranged to convert the synthesis gas stream into a hydrocarbon-containing waste gas stream in the form of at least a hydrocarbon product stream and an FT tail gas stream.

[0230] Aspect 53. The method according to any one of Aspects 51-52, wherein the methane content in the synthesis gas fed to the synthesis stage is less than 5%, for example less than 3% or even less than 2%.

[0231] The invention has been described with reference to various features, aspects, and embodiments. These can be combined in any way by those skilled in the art within the scope of the invention without departing from the scope of the invention as defined by the claims.

Claims

1. A method for producing a product flow, the method comprising the following steps: - Provides an apparatus (X), the apparatus comprising: a. A syngas stage (A), said syngas stage comprising an autothermal reforming (ATR) stage (I), and; b. Synthetic grade (B); The device includes: -The first feed (1) containing hydrogen to the syngas stage; - A second feed (2) containing carbon dioxide is directed to the syngas stage; -A third feed (3) containing hydrocarbons upstream of the ATR section leading to the syngas stage; and -The fourth feed (4) containing oxygen to the ATR section; The syngas stage (A) is arranged to provide a syngas flow (100) and supply the syngas flow (100) to the syngas stage (B); - Supply the first feed (1) containing hydrogen to the syngas stage; - A second feed containing carbon dioxide (2) is supplied to the syngas stage; - A third feed (3) containing hydrocarbons is supplied to the syngas stage upstream of the ATR section (I); - A fourth feed containing oxygen (4) is supplied to the ATR section; -In the syngas stage (A), a syngas flow (100) is provided from at least the first, second, third, and fourth feeds, and - The synthesis gas flow (100) is supplied to the synthesis stage (B); - In the synthesis stage (B), the synthesis gas stream (100) is converted into at least a product stream (500) and a hydrocarbon-containing waste gas stream (3b). - Wherein, when outside the device, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in the CO2 in the second feed is less than 0.

5.

2. The method according to claim 1, wherein when outside the device, the ratio of the number of carbon moles in the third feed containing hydrocarbons to the number of carbon moles in CO2 in the second feed is less than 0.3, preferably less than 0.25, and more preferably less than 0.20 or even less than 0.

10.

3. The method according to any one of the preceding claims further includes the following step: In addition to the third feed (3) containing hydrocarbons, at least a portion of the hydrocarbon-containing waste gas stream (3b) is also supplied to the syngas stage (I); upstream of the ATR section (I).

4. The method according to any one of the preceding claims, wherein the synthesis gas flow at the inlet of the synthesis stage has a hydrogen / carbon monoxide ratio in the range of 1.00-4.00; preferably 1.50-3.00, more preferably 1.50-2.

10.

5. The method according to any one of the preceding claims, wherein the H2:CO2 ratio provided at the inlet of the device is 1.0-9.0, preferably 2.5-8.0, and more preferably 3.0-7.

0.

6. The method according to claim 5, wherein the synthesis stage is an FT synthesis stage, and the H2:CO2 ratio at the inlet of the device is in the range of 3.0-7.0, or more preferably 3.0-6.0, and most preferably 3.0-5.

0.

7. The method according to any one of the preceding claims, wherein the syngas stage (A) comprises the autothermal reforming (ATR) stage (I), and wherein the first (1), second (2), third (3) and fourth (4) feeds are directly supplied to the ATR stage.

8. The method according to any one of claims 1-6, wherein the syngas stage further comprises a methanation stage (II) disposed upstream of the ATR stage (I); wherein a portion or all of the first feed is supplied to the methanation stage; a portion or all of the second feed is supplied to the methanation stage; and wherein a portion or all of the third feed is supplied to the syngas stage; upstream of the methanation stage or between the methanation stage and the ATR stage.

9. The method according to any one of claims 1-6, wherein the syngas stage further comprises a reverse water gas shift (rWGS) stage (III) located upstream of the ATR stage (I), wherein part or all of the first feed (Id) is supplied to the rWGS stage; part or all of the second feed is supplied to the rWGS stage; and wherein part or all of the third feed is supplied to the syngas stage between the rWGS stage (III) and the ATR stage.

10. The method according to any one of claims 1-6, wherein the syngas stage (A) includes a reverse water gas shift (rWGS) stage (III) arranged in parallel with the ATR stage (I); - At least a portion of the first feed (1) and at least a portion of the second feed (2) are arranged to be supplied to the rWGS (III), and the rWGS (III) is arranged to convert the at least a portion of the first feed (1) and at least a portion of the second feed (2) into a first synthesis gas flow (40). - A third feed (3) containing hydrocarbons and a fourth feed (4) containing oxygen are arranged to be supplied to the ATR section (I); and the ATR section (I) is arranged to convert the third feed (3) containing hydrocarbons and the fourth feed (4) containing oxygen into a second synthesis gas stream (50). -The first synthesis flow (40) from the rWGS section (III) is arranged to be combined with the second synthesis flow (50) from the ATR section (I); and the combined synthesis flow (100) is arranged to be supplied to the synthesis stage (B).

11. An apparatus (X), said apparatus comprising: a. A syngas stage (A), said syngas stage (A) comprising an autothermal reforming (ATR) stage (I), and b. Synthetic grade (B); The device includes: - A first feed (1) containing hydrogen to the syngas stage (A); - A second feed (2) containing carbon dioxide is sent to the syngas stage (A); - A third feed (3) containing hydrocarbons, located upstream of the ATR section (I) and heading towards the syngas stage; and -The fourth feed (4) containing oxygen to the ATR section (I); The syngas stage (A) is arranged to provide a syngas flow (100) and supply the syngas flow (100) to the syngas stage (B); and wherein The syngas stage (B) further includes a methanation stage (II) disposed upstream of the ATR stage (I); wherein part or all of the first feed (1) is supplied to the methanation stage (II); part or all of the second feed (2) is supplied to the methanation stage (II); and wherein part or all of the third feed (3) is supplied to the syngas stage (A); upstream of the methanation stage (II) or between the methanation stage (II) and the ATR stage (I).

12. An apparatus (X), said apparatus comprising: a. A syngas stage (A), said syngas stage comprising an autothermal reforming (ATR) section (I), and b. Synthetic grade (B); The device includes: - A first feed (1) containing hydrogen to the syngas stage (A); - A second feed (2) containing carbon dioxide is sent to the syngas stage (A); - A third feed (3) containing hydrocarbons, located upstream of the ATR section (I) and heading towards the syngas stage; and -The fourth feed (4) containing oxygen to the ATR section (I); The syngas stage (A) is arranged to provide a syngas flow (100) and supply the syngas flow (100) to the syngas stage (B); and wherein The syngas stage (A) further includes a reverse water gas shift (rWGS) stage (III) located upstream of the ATR stage (I), wherein part or all of the first feed (1d) is supplied to the rWGS stage; part or all of the second feed is supplied to the rWGS stage; and wherein part or all of the third feed (3) is supplied to the syngas stage between the rWGS stage (III) and the ATR stage.

13. An apparatus (X), said apparatus comprising: a. A syngas stage (A), said syngas stage comprising an autothermal reforming (ATR) section (I), and b. Synthetic grade (B); The device includes: - A first feed (1) containing hydrogen to the syngas stage (A); - A second feed (2) containing carbon dioxide is sent to the syngas stage (A); - A third feed (3) containing hydrocarbons, located upstream of the ATR section (I) and heading towards the syngas stage; and -The fourth feed (4) containing oxygen to the ATR section (I); The syngas stage is arranged to provide a syngas flow and supply the syngas flow to the syngas stage; and wherein - The syngas stage (A) includes a methanation stage (II) arranged in parallel with the ATR stage (I); -At least a portion of the first feed (1) and at least a portion of the second feed (2) are arranged to be supplied to the methanation section (II), and the methanation section (II) is arranged to convert the at least a portion of the first feed (1) and at least a portion of the second feed (2) into a first synthesis gas stream (40). - A third feed (3) containing hydrocarbons and a fourth feed (4) containing oxygen are arranged to be supplied to the ATR section (I); and the ATR section (I) is arranged to convert the third feed (3) containing hydrocarbons and the fourth feed (4) containing oxygen into a second synthesis gas stream (50). -The first synthesis gas stream (40) from the methanation section (II) is arranged to be combined with the second synthesis gas stream (50) from the ATR section (I); and the combined synthesis gas stream (100) is arranged to be supplied to the synthesis stage (B).

14. An apparatus (X), said apparatus comprising: a. A syngas stage (A), said syngas stage comprising an autothermal reforming (ATR) section (I), and b. Synthetic grade (B); The device includes: - A first feed (1) containing hydrogen to the syngas stage (A); - A second feed (2) containing carbon dioxide is sent to the syngas stage (A); - A third feed (3) containing hydrocarbons, located upstream of the ATR section (I) and heading towards the syngas stage; and -The fourth feed (4) containing oxygen to the ATR section (I); The syngas stage is arranged to provide a syngas flow and supply the syngas flow to the syngas stage; and wherein - The syngas stage (A) includes an rWGS stage (III) arranged in parallel with the ATR stage (I); - At least a portion of the first feed (1) and at least a portion of the second feed (2) are arranged to be supplied to the rWGS (III), and the rWGS (III) is arranged to convert the at least a portion of the first feed (1) and at least a portion of the second feed (2) into a first synthesis gas flow (40). - A third feed (3) containing hydrocarbons and a fourth feed (4) containing oxygen are arranged to be supplied to the ATR section (I); and the ATR section (I) is arranged to convert the third feed (3) containing hydrocarbons and the fourth feed (4) containing oxygen into a second synthesis gas stream (50). -The first synthesis flow (40) from the rWGS section (III) is arranged to be combined with the second synthesis flow (50) from the ATR section (I); and the combined synthesis flow (100) is arranged to be supplied to the synthesis stage (B).

15. The method according to any one of claims 1-10, or the apparatus according to any one of claims 11-14, wherein the third feed (3) containing hydrocarbons is supplied directly upstream of the ATR section (I) to the syngas stage.

16. The method according to any one of claims 1-10 or 15, or the apparatus according to any one of claims 11-15, further comprising a fifth steam feed (5) supplied to the syngas stage (A).

17. The method according to any one of claims 1-10 or 14-16, or the apparatus according to any one of claims 11-16, wherein the third feed (3) containing hydrocarbons is a natural gas feed.

18. The method according to any one of claims 1-10 or 14-17, or the apparatus according to any one of claims 11-17, wherein the synthesis stage (B) is arranged to convert the synthesis gas stream (100) into at least a product stream (500) and optionally a hydrocarbon-containing waste gas stream (3b).

19. The method according to any one of claims 1-10 or 14-18, or the apparatus according to any one of claims 11-18, wherein, in addition to the third feed (3) containing hydrocarbons, at least a portion of the hydrocarbon-containing waste gas stream (3b) is supplied to the syngas stage (I).

20. The method according to any one of claims 1-10 or 14-19, or the apparatus according to any one of claims 11-19, wherein the synthesis stage (B) is a Fischer-Tropsch (FT) stage, the Fischer-Tropsch (FT) stage being arranged to convert the synthesis gas stream (100) into a hydrocarbon-containing waste gas stream in the form of at least a hydrocarbon product stream and an FT tail gas stream.

21. The method according to any one of claims 1-10 or 14-20, or the apparatus according to any one of claims 10-20, wherein the synthesis stage (B) comprises a methanol synthesis stage arranged to provide at least a methanol product stream.

22. The method according to any one of claims 1-10 or 14-21, or the apparatus according to any one of claims 10-20, further comprising an electrolytic cell arranged to convert water or steam into at least a hydrogen-containing gas stream and an oxygen-containing gas stream, wherein at least a portion of the hydrogen-containing gas stream from the electrolytic cell is supplied to the syngas stage as the first feed and / or wherein at least a portion of the oxygen-containing gas stream from the electrolytic cell is supplied to the syngas stage as the fourth feed.

23. The method according to any one of claims 1-10 or 14-22, or the apparatus according to any one of claims 10-22, further comprising a sixth feed containing hydrogen supplied upstream of the synthesis stage to the synthesis gas stream.

24. The method according to any one of claims 1-10 or 14-23, or the apparatus according to any one of claims 10-23, wherein the synthesis gas flow (50) from the ATR section (I) is arranged to provide at least a portion of the energy required for the endothermic reaction in the rWGS section (III) before being combined with the first and second synthesis gas flows (40, 50).

25. The method according to any one of claims 1-10 or 14-24, or the apparatus according to any one of claims 10-24, wherein the synthesis stage is a Fischer-Tropsch (FT) stage, the Fischer-Tropsch (FT) stage being arranged to convert the synthesis gas stream (100) into a hydrocarbon-containing waste gas stream (3c) in the form of at least a hydrocarbon product stream (500) and an FT tail gas stream.

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