Electrically heated catalyzed sulfur passivation

Abstract

A process and reactor system for producing a CO-containing stream is provided. The process comprises the steps of: supplying a first carbonaceous feed (1) and optionally a co-feed (2) to an electrically heated reactor (10), causing them to undergo a CO-forming reaction while heating the electrically heated reactor by electric power; and outputting a CO-containing stream from the electrically heated reactor, wherein the content of sulfur-containing species in the total gas mixture supplied to the electrically heated reactor (measured as H2S) is in the range of 1-50 ppm.

Description

Technical Field

[0001] The present invention relates to a system and method for producing a CO-containing stream, the reactor system comprising: an electrically heated reactor; a first carbon-containing feed to the electrically heated reactor; and a co-feed containing a sulfur-containing substance to the electrically heated reactor. A self-regulating system / method is thereby obtained in which the sulfur uptake intensity of the catalyst bed of the reactor can be reduced.

[0002] Background

[0003] Syngas is a fundamental intermediate in most chemical industries and is typically produced by reforming natural gas and steam into CO and hydrogen through the endothermic steam methane reforming reaction (SMR). Alternatively, syngas can also be produced from CO 2 and excess hydrogen by the reverse water gas shift (RWGS).

[0004] Steam methane reforming CH 4 +H 2 O = CO + 3H 2

[0005] Reverse water gas shift CO 2 +H 2 = CO + H 2 O

[0006] Methanation reaction

[0007] CO 2 + 4H 2 = CH 4 + 2H 2 O

[0008] CO + 3H 2 = CH 4 + H 2 O

[0009] Avoiding carbon formation is crucial because carbon formation is detrimental to the activity and lifespan of the catalyst. For typical industrial reformers, carbon can be formed by one of the following mechanisms:

[0010] Methane decomposition CH 4 = C (s) + 2H 2

[0011] Boudouard reaction 2CO = C (s) + CO 2

[0012] CO reduction CO + H 2 = C (s) + H 2 O

[0013] Hydrocarbon decomposition

[0014] Industrial reforming typically uses nickel-type catalysts and operates at a high enough steam-to-carbon ratio (S / C) to reduce the thermodynamic carbon activity and thus inhibit carbon formation. However, this increases the energy consumption of the overall reaction. Noble metal catalysts have a higher resistance to carbon formation but result in a significant increase in cost. The amount of sulfur adsorbed depends on the sulfur concentration in the feed and the temperature of the catalyst. Sulfur concentrations above a few ppm can severely deactivate conventional reforming catalysts, which are usually not regenerable, requiring catalyst replacement and stricter cleaning of the feed gas.

[0015] In addition, the sulfur-passivated reforming process (SPARG) uses a small amount of sulfur to block the most active catalytic sites, which inhibits carbon formation but also reduces catalytic activity. Once sulfur is adsorbed on the catalyst, sulfur desorption cannot be carried out. The conventional sulfur-passivated reforming (SPARG) process can inhibit the possibility of carbon formation but severely affects catalytic activity. Sulfur is generally harmful to reforming catalysts, and when the sulfur capacity is reached, the catalyst load or catalyst material ultimately needs to be replaced.

[0016] WO2019228797A1 discloses a reactor system and method for steam reforming a feed gas containing hydrocarbons, wherein the heat for the endothermic reaction is provided by resistive heating.

[0017] It would be advantageous to provide a system and method for producing a CO-containing stream (especially a synthesis gas stream) that can inhibit carbon formation and decomposition. Another objective is to provide a system and method that is more tolerant to sulfur impurities in the feed. Yet another objective is to provide a self-regulating system and method that can automatically reduce intensity, for example, in the case of sulfur exposure. Summary of the Invention

[0018] In a first aspect, the present invention relates to a method for producing a CO-containing stream from a first carbonaceous feed in a reactor system of the present invention, optionally in the presence of a co-feed containing a sulfur-containing substance; the reactor system comprising:

[0019] - an electrically heated reactor (10) containing a catalyst capable of converting the first carbonaceous feed into a CO-containing stream;

[0020] - the first carbonaceous feed (1) to the electrically heated reactor;

[0021] - optionally, a co-feed (2) containing a sulfur-containing substance to the electrically heated reactor;

[0022] The method comprises the following steps

[0023] - Supplying the first carbonaceous feed (1) and, if present, the co-feed (2) to an electrically heated reactor (10) to carry out a CO formation reaction thereon while heating the electrically heated reactor by electricity; and

[0024] - Outputting a CO-containing stream from the electrically heated reactor,

[0025] wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1 - 50 ppm.

[0026] The present invention also relates to a reactor system for implementing the method for producing a CO-containing stream (11) according to the present invention, the reactor system comprising:

[0027] - An electrically heated reactor (10) containing a catalyst capable of converting the first carbonaceous feed into a CO-containing stream;

[0028] - The first carbonaceous feed (1) going to the electrically heated reactor;

[0029] - Optionally, a co-feed (2) containing sulfur-containing substances going to the electrically heated reactor;

[0030] wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is in the range of 1 - 50 ppm.

[0031] The present invention also provides a chemical engineering device comprising the reactor system of the present invention, and a heat exchange reformer or a feed-effluent heat exchanger, wherein the CO-containing stream from the reactor system is arranged to be fed to the heat exchange reformer or the feed-effluent heat exchanger.

[0032] More details of this technology are provided in the appended dependent claims, drawings and examples. Description of the Drawings

[0033] This technology is illustrated by the following drawings, wherein:

[0034] Figure 1 Shows the variation of the simulated temperature of the RWGS reaction with the axial position on the catalyst surface.

[0035] Figure 2 Shows the variation of the sulfur coverage of the RWGS reaction with the axial position on the catalyst surface.

[0036] Figure 3 Shows the variation of the simulated temperature of the SMR reaction with the axial position on the catalyst surface.

[0037] Figure 4Shows the variation of the sulfur coverage of the SMR reaction with the axial position on the catalyst surface.

[0038] Figure 5 Shows a schematic layout of the system of the present invention. Detailed description of the invention

[0040] Unless otherwise specified, any given percentage of gas content is by volume. All feeds are preheated as required.

[0041] The inventors of the present invention have found that, similar to the conventional sulfur passivation reforming (SPARG) process, sulfur passivation of the electroheated catalytic hardware can suppress carbon deposition. However, unexpectedly, due to the automatic regeneration achieved by the integrated ohmic / resistive heating, the negative impact on the catalyst activity is significantly reduced. Compared with the conventional combustion process, the reduction in the negative impact on the catalyst activity also increases the threshold for operating with feeds having a higher concentration of sulfur impurities.

[0042] By using catalytic hardware with integrated ohmic heating, the heat supplied is proportional to the resistance. The strongly endothermic SMR reaction consumes most of the supplied heat. Therefore, a local reduction in catalyst activity (e.g., through sulfur passivation) will result in local heating without the reaction consuming heat. This local temperature increase will desorb some of the sulfur-containing substances, thereby reducing the intensity of sulfur absorption. This is beneficial for three purposes: First, the system will automatically reduce the intensity in the presence of sulfur exposure (automatic regeneration); Second, overall, the system has a higher tolerance to sulfur impurities and changes in sulfur content in the feed; Third, it can achieve more local sulfur passivation near the feed inlet, thereby suppressing carbon formation by decomposition. The problem of carbon formation near the feed inlet is much more severe than at more downstream locations in the reformer due to the high methane content and low hydrogen content in the feed (which will drive the methane decomposition reaction).

[0043] The automatic regeneration from sulfur passivation reduces the overall impact on the catalyst activity and theoretically can effectively suppress carbon formation while minimizing the impact on conversion, which is in sharp contrast to the sulfur passivation method of the conventional reforming process using catalyst particles. Second, theoretically, it can operate with a lower purity feedstock, thereby relieving the pressure on gas purification and the prereformer (assuming the downstream process can tolerate it). In addition, the sulfur passivation method can also prevent / suppress the formation of metal dust in the downstream equipment behind the reformer.

[0044] Sulfur-containing substances in the feed adsorb to the catalytic sites in the electro-heated reactor, preferentially adsorbing to the sites with the highest activity, but having sufficient concentration for all active sites, thus completely deactivating the catalyst. Increasing the temperature causes the sulfur to desorb and tend towards an equilibrium concentration. For catalytic hardware with integrated ohmic heating for endothermic processes, the loss of catalyst activity leads to a local temperature increase. In essence, this causes the catalyst to automatically regenerate to a stage with reduced passivation strength. Compared to combustion reactors using catalyst particles, this significantly reduces the relative volume of the catalyst that is completely deactivated by sulfur. Thus, although the catalyst volume of the electro-heated reformer is much smaller than that of the combustion reformer with a catalyst particle bed, it has surprisingly been found that due to the auto-regeneration mechanism, the electro-heated reformer is not deactivated by SPARG.

[0045] Another advantage of the present invention is that a slight sulfur deactivation of the reformer will allow the reactor to operate at a significantly lower steam-to-carbon (S / C) ratio compared to non-passivated operation. The range of the S / C ratio depends on the pressure and feed composition. For non-passivated catalysts, when producing CO-rich gas by SMR, the S / C in the total gas mixture supplied to the electro-heated reactor is typically 1.3 - 2.5. After sulfur passivation, it can be operated at an S / C ratio of 0.6 - 1.0. The lower S / C ratio will allow for a reduction in the energy consumption of the reactor because less energy is required to heat the bulk gas. This is particularly attractive when producing CO-rich syngas (such as syngas with H 2 / CO < 3).

[0046] Another advantage of the present invention is as follows: In the feed-effluent heat exchanger downstream of the reformer (which operates at a lower temperature than the reformer), due to the operating temperature required for cooling the high-temperature CO-containing stream from the electro-heated reactor, metal dust corrosion is a problem in non-sulfur passivated systems. Another benefit of the presence of sulfur-containing substances in the gas is that it helps reduce the risk of metal dust formation in the cooler equipment downstream of the reformer. The presence of a small amount of sulfur in the gas allows the reformer to be integrated with a heat exchange reformer (such as catalytic conversion on the feed side) and a feed-effluent heat exchanger without the use of a boiler as in, for example, conventional CO-containing gas production processes. This is because sulfur can also inhibit carbon formation in the heat exchanger. By recovering heat from the product to preheat the feed, less total power is required. In a simple process, the heat exchanger can be placed before (feed) and after (effluent) the electro-heated reactor. In a full-scale plant, there will typically be multiple heat exchangers.

[0047] Method

[0048] The present invention provides a method for producing a CO-containing stream from a first carbon-containing feed in a reactor system, optionally in the presence of a co-feed containing a sulfur-containing substance; the reactor system comprising:

[0049] - An electric heating reactor (10) comprising a catalyst capable of converting a first carbonaceous feed into a CO-containing stream;

[0050] - A first carbonaceous feed (1) to the electric heating reactor;

[0051] - Optionally, a co-feed (2) containing a sulfur-containing substance to the electric heating reactor;

[0052] The method comprises the following steps

[0053] - Supplying the first carbonaceous feed (1) and, if present, the co-feed (2) to the electric heating reactor (10) to cause them to undergo a CO formation reaction while heating the electric heating reactor by electricity; and

[0054] - Outputting a CO-containing stream from the electric heating reactor,

[0055] - wherein the content of the sulfur-containing substance in the total gas mixture supplied to the electric heating reactor, measured as H 2 S, is 1-. In a preferred embodiment of the method of the present invention, the content of the sulfur-containing substance in the total gas mixture supplied to the electric heating reactor, measured as H 2 S, is 1-50 ppm, preferably 1-20 ppm, more preferably 1-10 ppm.

[0056] In a specific embodiment of the method of the present invention, the content of the sulfur-containing substance in the total gas mixture supplied to the electric heating reactor, measured as H 2 S, is 1-20 ppm, more preferably 1-10 ppm.

[0057] The method produces a CO-containing stream, which is preferably a synthesis gas stream, preferably wherein the CO-containing stream further contains H 2 、H 2 O、CO 2 、CH 4 and mixtures thereof.

[0058] In one aspect, the method further comprises the step of pressurizing the combined feed upstream of the inlet of the electric heating reactor, preferably to a pressure between 5 and 30 bar.

[0059] The combined feed can be pressurized upstream of the inlet of the electric heating reactor, preferably to a pressure between 30 and 200 bar, preferably between 80 and 180 bar.

[0060] The temperature of the feed gas entering the electric heating reactor is suitably between 200 °C and 700 °C.

[0061] In the process according to the invention, the space velocity is suitably between 0.6 and 60 Nm 3 / m 3 / h when evaluated with respect to the geometric surface area of the structured catalyst, or between 700 Nm 3 / m 3 / h and 70000 Nm 3 / m 3 / h when evaluated with respect to the occupied volume of the structured catalyst.

[0062] The first carbonaceous feed

[0063] The first carbonaceous feed is fed to an electrically heated reactor and converted into a CO-containing stream. The first feed can be a hydrocarbon-rich feed gas, a CO-containing feed gas, a CO-rich 2 feed gas or a feed gas comprising a mixture of hydrocarbons and CO. Preferably, the first feed is a hydrocarbon-rich feed gas. Herein, the expression that a gas is "rich in" a particular component means that the gas contains more than 50% v / v, such as more than 75% v / v, more than 80% v / v or more than 95% v / v of said component (in terms of dry matter percentage).

[0064] The choice of the first feed depends on the type of reaction to be carried out in the electrically heated reactor.

[0065] When the first feed is a methane-rich feed, the main reaction in the reactor is steam methane reforming, and the steam / hydrocarbon ratio in the first feed is preferably between 0.5 and 2.

[0066] When the first feed is biogas, the reaction in the reactor is mainly methanation or steam methane reforming, and the steam / methane ratio in the first feed is preferably between 0.5 and 2.

[0067] When the first feed is a CO-rich 2 feed, the main reaction in the reactor is the RWGS reaction, and the H 2 / CO 2 ratio in the first feed is preferably between 2 and 4.

[0068] On the one hand, the first feed is a hydrocarbon-rich feed gas, the electrically heated reactor is an electrically heated steam reforming reactor, in which the catalyst can catalyze the steam reforming reaction, and the reactor system further includes a steam feed to the electrically heated reactor. The structure and components suitable for the electrically heated steam reforming reactor have been described in WO2019228797A1.

[0069] On the other hand, the first feed is CO-rich 2The feed gas, wherein the electrically heated reactor is an electrically heated reverse water gas shift (e-RWGS) reactor, wherein the catalyst is capable of catalyzing the water gas shift reaction, and wherein the reactor system further comprises a hydrogen feed to the electrically heated reactor. The electrically heated reactor is an electrically heated reverse water gas shift (e-RWGS) reactor; preferably, wherein the e-RWGS reactor comprises a structured catalyst capable of catalyzing the reverse water gas shift reaction, steam reforming reaction, and methanation reaction, the structured catalyst comprising a macroscopic structure of a conductive material, and wherein the reactor system further comprises a hydrogen feed to the electrically heated reactor. More details regarding this aspect can be found in WO2022079098, which is incorporated herein by reference.

[0070] In this particular aspect, the first feed is advantageously a mixture of CO and CO 2 feed gas.

[0071] In a specific embodiment of the method of the present invention, before being supplied to the electrically heated reactor, the first feed undergoes a desulfurization step in a desulfurization section, which is arranged to remove sulfur-containing substances from the first feed.

[0072] Before being supplied to the electrically heated reactor (10), and before any desulfurization pretreatment (if any), the carbonaceous first feed may contain a small amount of sulfur-containing substances. Preferably, the content of sulfur-containing substances in the first feed (measured as H 2 S) is in the range of 1 - 10000 ppm, preferably in the range of 1 - 1000 ppm, preferably in the range of 1 - 100 ppm, preferably in the range of 1 - 50 ppm, and more preferably in the range of 1 - 10 ppm.

[0073] In a specific embodiment of the method of the present invention, the content of sulfur-containing substances in the first feed is controlled such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor (measured as H 2 S) is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm, and wherein no co-feed is supplied to the electrically heated reactor.

[0074] A co-feed containing sulfur-containing substances

[0075] In a specific embodiment of the method of the present invention, a co-feed containing sulfur-containing substances is supplied to the electrically heated reactor. The co-feed can be supplied to the electrically heated reactor as a separate stream, or it can be mixed with the first feed upstream of the electrically heated reactor to form a combined feed stream, and then the combined feed stream is supplied to the electrically heated reactor.

[0076] Control the content of sulfur-containing substances such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor (measured as H2 The sulfur content (S measurement) is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm (on a wet basis).

[0077] In a specific embodiment of the method of the present invention, before the first feed is supplied to the electrically heated reactor, it is subjected to a desulfurization step in a desulfurization section which is arranged to remove sulfur-containing substances (in terms of H 2 S measurement) in the first feed to a level below 1 ppm, preferably below 100 ppb, most preferably below 10 ppb; and wherein the supply amount of the co-feed is such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor (in terms of H 2 S measurement) is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm.

[0078] This embodiment has many advantages. First, this embodiment enables the use of the first feed from different sources and with a large difference in sulfur content before the desulfurization step, as well as the use of the first feed whose sulfur content varies over time during operation. In addition, this embodiment enables precise control of the exact sulfur level in the first feed to be supplied to the electrically heated reformer with high accuracy.

[0079] The desulfurization section can be any conventional desulfurization section, such as a hydrogenation reactor that converts sulfur in the feed to H 2 S and / or an absorption reactor that absorbs H 2 S onto an absorbent (such as a ZnO-based absorbent and a Cu-promoted ZnO-based absorbent). In addition to the hydrogenation reactor and / or the absorption reactor, the desulfurization section can also include a unit containing an activated carbon material suitable for absorbing sulfur substances. In addition to or as an alternative to the hydrogenation reactor and / or the absorption reactor and the optional activated carbon unit, the desulfurization section can also contain a prereformer, such as an adiabatic prereformer, such as a prereformer having a Ni-based catalyst.

[0080] The term "total gas mixture" refers to the total amount of all feed gases going to the reactor, including the carbon-containing first feed, the co-feed, and any additional feeds, such as hydrogen or steam.

[0081] The sulfur-containing substances in the co-feed can be one or more of methanethiol, dimethyl sulfide, sulfur dioxide, or hydrogen sulfide.

[0082] Preferably, the first feed and the co-feed containing sulfur-containing substances are arranged to be mixed into a combined feed and then supplied to the inlet of the electrically heated reactor.

[0083] CO-containing stream

[0084] The method and reactor system of the present invention provide a CO-containing stream. The CO-containing stream is preferably a synthesis gas stream, and preferably, the CO-containing stream further contains H 2 、H 2 O, CO 2 、CH 4 and mixtures thereof.

[0085] On the one hand, the CO-containing stream is a synthesis gas stream containing components within the following ranges (volume %):

[0086] 10 - 25% CO

[0087] 5 - 20% CO 2

[0088] 35 - 65% H 2

[0089] 5 - 30% H 2 O

[0090] 0.1–2.5% CH 4

[0091] 0–2% N 2

[0092] Trace amounts of other gases, such as Ar may also be present.

[0093] In one aspect of the method of the present invention, the CO formation reaction is steam methane reforming. In another aspect of the method of the present invention, the CO formation reaction is the reverse water gas shift (RWGS) reaction.

[0094] Preferably, the reactor system and method provide a CO-containing stream with an H 2 / CO ratio of 1 - 4, preferably 1.5 - 3, and most preferably 2 - 2.1.

[0095] The reactor system and method can provide a CO-containing stream with a methanol modulus between 1 - 3, preferably 2 - 2.1.

[0096] The methanol modulus is defined as Based on mole %. The ideal modulus is 2.

[0097] In one embodiment, the method and reactor system of the present invention further include a desulfurization section, which is arranged to receive the CO-containing stream from the electrically heated reactor and remove sulfur-containing substances from the CO-containing stream. In this way, usually after temperature adjustment, and usually by absorption in a chemical absorbent, any sulfur-containing substances are removed from the CO-containing stream downstream of the reformer. This can be carried out before and / or after condensation and removal of water from the product stream.

[0098] Electrically heated reactor

[0099] The reactor system of the present invention includes an electrically heated reactor, which contains a catalyst capable of converting a first carbon-containing feed into a CO-containing stream. The electrically heated reactor can be an induction heating reactor or a resistance heating reactor. The electrically heated reactor suitably contains a structured catalyst, which preferably contains Ni, Pt, Ru, Co, Ir, Rh, Mn or a mixture thereof as catalytically active metals, wherein the structured catalyst is arranged to be electrically heated.

[0100] Resistance-heated reactor

[0101] By integrated ohmic heating, the locally supplied heat is proportional to the resistance and is independent of temperature for the alloys used.

[0102] Suitably, the electrically heated reactor is of the type having a structured catalyst, which contains a macroscopic structure of a conductive material, and the macroscopic structure supports a ceramic coating, wherein the ceramic coating supports the catalytically active material. In a specific embodiment, the electrically heated reactor includes:

[0103] · A structured catalyst, which includes a macroscopic structure of a conductive material, and the macroscopic structure supports a ceramic coating, wherein the ceramic coating supports the catalytically active material;

[0104] · A pressure-resistant shell for accommodating the structured catalyst, the pressure-resistant shell includes an inlet for introducing the feed gas and an outlet for discharging the product gas, wherein the inlet is positioned such that the feed gas enters the structured catalyst from a first end of the structured catalyst and the product gas leaves the structured catalyst from a second end of the structured catalyst;

[0105] · A heat-insulating layer between the structured catalyst and the pressure-resistant shell; and

[0106] · At least two conductors, which are electrically connected to the structured catalyst and a power source placed outside the pressure-resistant shell, wherein the size of the power source is designed to heat at least a part of the structured catalyst to a temperature of at least 500 °C by passing an electric current through the macroscopic structure, wherein the at least two conductors are connected to the structured catalyst at a position closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to guide the electric current from one conductor substantially to the second end of the structured catalyst and return to the second of the at least two conductors.

[0107] More details of such an electrically heated reactor are described in WO2019228797A1, the content of which is incorporated herein by reference.

[0108] In another type of electrically heated reactor, the catalytically active material (e.g., coated on a ceramic support) can be heated by physical close contact with an electrical wire (e.g., in a meandering manner) arranged in the catalyst bed. Thus, the ceramic material is not coated on the conductive material. Here, the catalyst can be granular or a structured catalyst. See WO21209509 (Pauletto) and WO2019228798.

[0109] Induction heating reactor

[0110] The electrically heated reactor can be an induction heating reactor. WO2017036794 describes one such induction heating reactor, which is incorporated herein by reference. Here, the reactor unit includes a catalyst material having one or more ferromagnetic macrocarriers susceptible to induction heating. The ferromagnetic macrocarriers are ferromagnetic at temperatures up to the upper limit of a given temperature range T. The ferromagnetic macrocarriers are coated with an oxide, where the oxide is impregnated with catalytically active particles. The induction coil is powered by a power source providing alternating current and is positioned to generate an alternating magnetic field within the reactor unit after being powered by the power source, thereby heating the catalyst material to a temperature within the temperature range T through the alternating magnetic field.

[0111] WO2017186437 describes another such induction heating reactor, which is incorporated herein by reference. Here, the tubular heat exchange reactor includes:

[0112] - An outer tube having a first end and a second end, where the first end is the inlet end and the second end is the closed end,

[0113] - An inner tube arranged coaxially within the outer tube and spaced apart from the outer tube, where at least a portion of the inner tube houses a bed of catalyst material susceptible to induction heating, and where the inner tube has an inlet end and an outlet end,

[0114] - An induction coil placed in the annular space between the outer tube and the inner tube, and

[0115] - A power source arranged to supply alternating current to the induction coil so as to generate an alternating magnetic field within at least a portion of the bed of catalyst material within the inner tube,

[0116] - Wherein the tubular heat exchange reactor is arranged to allow a process gas stream to be directed into the inlet end of the outer tube, flow in the annular space defined between the outer tube and the inner tube towards the second end of the outer tube, and then enter the inner tube to reach the bed of catalyst material and undergo an endothermic reaction to produce a product gas. Specific embodiments

[0117] Figure 1Shows the variation curve of temperature with increasing sulfur concentration in the feed gas in the RWGS reaction with all other parameters constant. RWGS on nickel-based catalysts enables methanation (reverse SMR), which is a strongly exothermic reaction, as Figure 1 shown, and this reaction has an improvement effect on sulfur passivation. This is an effect in addition to the effect of integrated ohmic heating.

[0118] Figure 2 Shows the sulfur coverage corresponding to the Figure 1 temperature curve in.

[0119] Figure 3 Shows the CFD simulation results with increasing sulfur concentration in the feed gas under SMR conditions. Compared with the sulfur-free (0 ppm) baseline case, the temperature rises faster when the sulfur content in the feed increases. When the sulfur concentration in the feed is 5 ppm, the point where the reaction starts is clearly visible because the endothermic reaction reaches equilibrium with the heat supply, forming a small region with a constant temperature.

[0120] Figure 4 Shows the sulfur coverage corresponding to the Figure 3 temperature curve in.

[0121] Figure 5 Shows a reactor system according to the present invention, which includes an electrically heated reactor (10), a first carbon-containing feed (1) going to the electrically heated reactor; and a co-feed (2) containing a sulfur-containing substance going to the electrically heated reactor.

[0122] The present invention has been described with reference to multiple embodiments and drawings. However, those skilled in the art can select and combine various embodiments within the scope of the present invention, which is defined by the appended claims. All documents cited herein are incorporated by reference.

[0123] Aspect

[0124] The present invention provides the following aspects:

[0125] Aspect 1. A method for producing a CO-containing stream from a first carbon-containing feed in a reactor system, optionally in the presence of a co-feed containing a sulfur-containing substance; the reactor system includes:

[0126] - An electrically heated reactor (10) containing a catalyst capable of converting the first carbon-containing feed into a CO-containing stream;

[0127] - A first carbon-containing feed (1) going to the electrically heated reactor;

[0128] - Optionally, a co-feed (2) containing a sulfur-containing substance going to the electrically heated reactor;

[0129] The method comprises the following steps

[0130] - Supplying the first carbon-containing feed (1) and, if present, the co-feed (2) to an electrically heated reactor (10) to carry out a CO formation reaction thereon while heating the electrically heated reactor by electricity; and

[0131] - Outputting a CO-containing stream from the electrically heated reactor,

[0132] - wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1 - 50 ppm.

[0133] Aspect 2. The method according to aspect 1, wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1 - 20 ppm, more preferably 1 - 10 ppm.

[0134] Aspect 3. The method according to any one of aspects 1 - 2, wherein the CO formation reaction is steam methane reforming.

[0135] Aspect 4. The method according to any one of aspects 1 - 2, wherein the CO formation reaction is a reverse water gas shift (RWGS) reaction.

[0136] Aspect 5. The method according to any one of the preceding aspects, wherein the reactor system provides a CO-containing stream, and the H 2 / CO ratio of the CO-containing stream is 1 - 4, preferably 1.5 - 3, and most preferably 2 - 2.1.

[0137] Aspect 6. The method according to any one of the preceding aspects, wherein the reactor system provides a CO-containing stream, and the methanol modulus of the CO-containing stream is 1 - 3, preferably 2 - 2.1.

[0138] Aspect 7. The method according to any one of the preceding aspects, wherein the CO-containing stream is a synthesis gas stream, preferably wherein the CO-containing stream further comprises H 2 S, H 2 , H 2 O, CO 2 , CH 4 and mixtures thereof.

[0139] Aspect 8. The method according to any one of the preceding aspects, further comprising the step of pressurizing the combined feeds upstream of the inlet of the electrically heated reactor, preferably to a pressure between 5 and 30 bar.

[0140] Aspect 9. The method according to any one of the preceding aspects further comprises the step of pressurizing the combined feed upstream of the inlet of the electrically heated reactor, preferably to a pressure between 30 and 200 bar, more preferably to a pressure between 80 and 180 bar.

[0141] Aspect 10. The method according to any one of the preceding aspects, wherein the temperature of the feed gas entering the electrically heated reactor is between 200 °C and 700 °C.

[0142] Aspect 11. The method according to any one of the preceding aspects, wherein the space velocity is suitably between 0.6 and 60 Nm 3 / m 3 / h when evaluated based on the gas flow rate relative to the geometric surface area of the structured catalyst, or the space velocity is suitably between 700 Nm 3 / m 3 / h and 70000 Nm 3 / m 3 / h when evaluated based on the gas flow rate relative to the occupied volume of the structured catalyst.

[0143] Aspect 12. The method according to any one of the preceding aspects, wherein the first feed is subjected to a sulfur removal step in a sulfur removal section before being supplied to the electrically heated reactor; the sulfur removal section is arranged to remove sulfur-containing substances in the first feed.

[0144] Aspect 13. The method according to any one of the preceding aspects, wherein before the carbon-containing first feed is supplied to the electrically heated reactor (10) and if there is a sulfur removal pretreatment, the carbon-containing first feed contains sulfur-containing substances, preferably, wherein the content of sulfur-containing substances in the first feed, measured as H 2 S, is 1 - 5000 ppb, preferably 1 - 1000 ppb, preferably 1 - 100 ppb, more preferably 1 - 10 ppb.

[0145] Aspect 14. The method according to any one of the preceding aspects, wherein a co-feed is supplied to the electrically heated reactor (10).

[0146] Aspect 15. The method according to aspect 14, wherein the first feed is subjected to a desulfurization step in a desulfurization section before being supplied to the electrically heated reactor, the desulfurization section is arranged to remove sulfur-containing substances in the first feed, measured as H 2 S, to a level below 1 ppm, preferably below 100 ppb, most preferably below 10 ppb; and wherein the supply amount of the co-feed is such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2The S measurement is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm.

[0147] Aspect 16. The method according to any one of aspects 1 - 13, wherein the content of sulfur-containing substances in the first feed is controlled such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, in terms of H 2 S measurement, is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm; and wherein no co-feed is supplied to the electrically heated reactor.

[0148] Aspect 17. A reactor system for implementing the method according to aspect 1 for producing a CO-containing stream (11), the reactor system comprising:

[0149] - An electrically heated reactor (10) containing a catalyst capable of converting a first carbon-containing feed into a CO-containing stream;

[0150] - A first carbon-containing feed (1) to the electrically heated reactor;

[0151] - Optionally, a co-feed (2) containing sulfur-containing substances to the electrically heated reactor;

[0152] wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, in terms of H 2 S measurement, is in the range of 1 - 50 ppm.

[0153] Aspect 18. The reactor system according to aspect 17, wherein the reactor system includes a co-feed, and wherein the first feed and the co-feed containing sulfur-containing substances are arranged to be mixed into a combined feed before being supplied to the inlet of the electrically heated reactor.

[0154] Aspect 19. The reactor system according to any one of aspects 17 - 18, wherein the electrically heated reactor is an induction heating reactor or a resistance heating reactor.

[0155] Aspect 20. The reactor system according to any one of aspects 17 - 19, wherein the electrically heated reactor includes a structured catalyst, the structured catalyst preferably contains Ni, Pt, Ru, Co, Ir, Mn, Rh or a mixture thereof as catalytically active metals, and wherein the structured catalyst is arranged to be electrically heated.

[0156] Aspect 21. The reactor system according to any one of aspects 17 - 20, wherein the electrically heated reactor includes:

[0157] · A structured catalyst, the structured catalyst comprising a macroscopic structure of a conductive material, the macroscopic structure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material;

[0158] · A pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for introducing the feed gas and an outlet for discharging the product gas, wherein the inlet is positioned such that the feed gas enters the structured catalyst from a first end of the structured catalyst and the product gas exits the structured catalyst from a second end of the structured catalyst;

[0159] · An insulating layer between the structured catalyst and the pressure-resistant shell; and

[0160] · At least two conductors, which are electrically connected to the structured catalyst and a power source placed outside the pressure-resistant shell, wherein the size of the power source is designed to heat at least a portion of the structured catalyst to a temperature of at least 500 °C by passing an electric current through the macroscopic structure, wherein the at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct the electric current from one conductor substantially towards the second end of the structured catalyst and back to the second of the at least two conductors.

[0161] Aspect 22. The reactor system according to any one of aspects 17 - 21, wherein the first feed is a hydrocarbon-rich feed gas, a CO-containing feed gas, a CO-rich feed gas, or a feed gas comprising a mixture of hydrocarbons and CO. 2 The feed gas of.

[0162] Aspect 23. The reactor system according to any one of aspects 17 - 22, wherein the first feed is a hydrocarbon-rich feed gas, and the electrically heated reactor is an electrically heated steam reforming reactor, wherein the catalyst is capable of catalyzing a steam reforming reaction, and wherein the reactor system further comprises a steam feed to the electrically heated reactor.

[0163] Aspect 24. The reactor system according to any one of aspects 17 - 22, wherein the first feed is a CO-rich feed gas, and the electrically heated reactor is an electrically heated water gas shift reactor, wherein the catalyst is capable of catalyzing a reverse water gas shift reaction, and wherein the reactor system further comprises a hydrogen feed to the electrically heated reactor. 2 The feed gas of.

[0164] Aspect 25. The reactor system according to aspect 24, wherein the catalyst is capable of catalyzing a reverse water gas shift reaction, a steam reforming reaction, and a methanation reaction.

[0165] Aspect 26. The reactor system according to any one of aspects 17 - 25 further comprises a sulfur removal section upstream of the electrically heated reactor, wherein the sulfur removal section is arranged to remove sulfur-containing substances therefrom before supplying a first feed to the electrically heated reactor.

[0166] Aspect 27. The reactor system according to any one of aspects 17 - 26, wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1 - 20 ppm, more preferably 1 - 10 ppm.

[0167] Aspect 28. The reactor system according to any one of aspects 17 - 27, wherein before supplying the carbon-containing first feed to the electrically heated reactor (10) and if any, before sulfur removal pretreatment, the carbon-containing first feed contains sulfur-containing substances, preferably wherein the content of sulfur-containing substances in the first feed, measured as H 2 S, is 1 - 5000 ppb, preferably 1 - 1000 ppb, preferably 1 - 100 ppb, more preferably 1 - 10 ppb.

[0168] Aspect 29. The reactor system according to any one of aspects 17 - 28, wherein the CO-containing stream is a synthesis gas stream, preferably wherein the CO-containing stream further contains H 2 S, H 2 , H 2 O, CO 2 , CH 4 and mixtures thereof.

[0169] Aspect 30. The reactor system according to any one of aspects 17 - 29 further comprises a sulfur removal section, which is arranged to receive the CO-containing stream from the electrically heated reactor and remove sulfur-containing substances from the CO-containing stream.

[0170] Aspect 31. A chemical equipment, which comprises the reactor system according to any one of aspects 17 - 30, and a heat exchange reformer or a feed-effluent heat exchanger, wherein the CO-containing stream (11) from the reactor system is arranged to be fed to the heat exchange reformer or the feed-effluent heat exchanger.

Claims

1. A method for producing a CO-containing stream from a first carbonaceous feed in a reactor system, optionally in the presence of a co-feed comprising a sulfur-containing substance ； The reactor system comprises: - an electrically heated reactor (10) containing a catalyst capable of converting the first carbonaceous feed into a CO-containing stream; - the first carbonaceous feed (1) to the electrically heated reactor; - optionally, a co-feed (2) comprising a sulfur-containing substance to the electrically heated reactor; The method comprises the following steps - supplying the first carbonaceous feed (1) and, if present, the co-feed (2) to the electrically heated reactor (10) to cause them to undergo a CO formation reaction while heating the electrically heated reactor by electricity; and - outputting the CO-containing stream from the electrically heated reactor, - The content of sulfur-containing substances in the total gas mixture supplied to the electro-heated reactor, measured as H 2 S, is 1 - 50 ppm.

2. The method according to claim 1, wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrothermal reactor, measured as H 2 S, is 1-20 ppm, more preferably 1-10 ppm.

3. The method according to any one of the preceding claims, wherein the CO formation reaction is steam methane reforming.

4. The method according to any one of claims 1-2, wherein the CO formation reaction is the reverse water gas shift (RWGS) reaction.

5. The method according to any one of the preceding claims, wherein the reactor system provides a CO-containing stream, and the H 2 / CO ratio of the CO-containing stream is 1-4, preferably 1.5-3, and most preferably 2-2.

1.

6. The method according to any one of the preceding claims, wherein the reactor system provides a CO-containing stream having a methanol modulus of 1-3, preferably 2-2.

1.

7. The method according to any one of the preceding claims, wherein the CO-containing stream is a synthesis gas stream, preferably wherein the CO-containing stream further comprises H 2 S, H 2 , H 2 O, CO 2 , CH 4 and mixtures thereof.

8. The method according to any one of the preceding claims, wherein the first carbonaceous feed contains sulfurous substances before being supplied to the electrically heated reactor (10) and, if any, before sulfur removal pretreatment. Preferably, the content of sulfurous substances in the first feed, measured as H 2 S, is 1 - 10000 ppm, preferably 1 - 1000 ppm, preferably 1 - 100 ppm, preferably 1 - 50 ppm, more preferably 1 - 10 ppm.

9. The method according to any one of the preceding claims, wherein a co-feed is supplied to the electrically heated reactor (10).

10. The method according to claim 9, wherein before the first feed is supplied to the electrically heated reactor, it is subjected to a desulfurization step in a desulfurization section which is arranged to remove sulfur-containing substances in the first feed to a level of less than 1 ppm, preferably less than 100 ppb, most preferably less than 10 ppb, as measured by H 2 S; and wherein the supply rate of the co-feed is such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, as measured by H 2 S, is 1 - 50 ppm, preferably 1 - 20 ppm, more preferably 1 - 10 ppm.

11. The method according to any one of claims 1-8, wherein the content of sulfur-containing substances in the first feed is controlled such that the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1-50 ppm, preferably 1-20 ppm, more preferably 1-10 ppm; and wherein no co-feed is supplied to the electrically heated reactor.

12. A reactor system for implementing the method for producing a CO-containing stream (11) according to claim 1, the reactor system comprises: - an electrically heated reactor (10) containing a catalyst capable of converting the first carbonaceous feed into a CO-containing stream; - the first carbonaceous feed (1) to the electrically heated reactor; - optionally, a co-feed (2) comprising a sulfur-containing substance to the electrically heated reactor; wherein The content of sulfur-containing substances in the total gas mixture supplied to the electro-heated reactor, measured as H 2 S, is in the range of 1 - 50 ppm.

13. The reactor system according to claim 12, wherein the electrically heated reactor comprises: · a structured catalyst comprising a macroscopic structure of a conductive material that supports a ceramic coating, wherein the ceramic coating supports a catalytically active material; · a pressure-resistant shell containing the structured catalyst, the pressure-resistant shell comprising an inlet for introducing the feed gas and an outlet for discharging the product gas, wherein the inlet is positioned such that the feed gas enters the structured catalyst from a first end of the structured catalyst and the product gas exits the structured catalyst from a second end of the structured catalyst; · a heat-insulating layer between the structured catalyst and the pressure-resistant shell; and · At least two conductors, which are electrically connected to the structured catalyst and a power source placed outside the pressure-resistant shell, wherein the size of the power source is designed to heat at least a portion of the structured catalyst to a temperature of at least 500 °C by passing an electric current through the macrostructure, wherein the at least two conductors are connected to the structured catalyst at a position closer to the first end of the structured catalyst than to the second end of the structured catalyst, and wherein the structured catalyst is configured to direct the electric current from one conductor substantially to the second end of the structured catalyst and back to the second of the at least two conductors.

14. The reactor system according to any one of claims 12 - 13, wherein the first feed is a hydrocarbon-rich feed gas, a CO-containing feed gas, a CO-rich 2 feed gas, or a feed gas comprising a mixture of hydrocarbons and CO.

15. The reactor system according to any one of claims 12 - 13, wherein the first feed is a hydrocarbon-rich feed gas, and the electrically heated reactor is an electrically heated steam reforming reactor, wherein the catalyst is capable of catalyzing a steam reforming reaction, and wherein the reactor system further comprises a steam feed to the electrically heated reactor.

16. The reactor system according to any one of claims 12 - 13, wherein the first feed is a feed gas rich in CO 2 and the electrically heated reactor is an electrically heated water gas shift reactor, wherein the catalyst is capable of catalyzing the reverse water gas shift reaction, and wherein the reactor system further comprises a hydrogen feed to the electrically heated reactor.

17. The reactor system according to any one of claims 12-16, wherein the content of sulfur-containing substances in the total gas mixture supplied to the electrically heated reactor, measured as H 2 S, is 1-20 ppm, more preferably 1-10 ppm.

18. The reactor system according to any one of claims 12 - 17, wherein the first carbonaceous feed contains a sulfur-containing substance before being supplied to the electrically heated reactor (10) and, if any, before sulfur removal pretreatment, preferably wherein the content of the sulfur-containing substance in the first feed, measured as H 2 S, is 1 - 5000 ppb, preferably 1 - 1000 ppb, preferably 1 - 100 ppb, more preferably 1 - 10 ppb.

19. The reactor system according to any one of claims 12 - 18, wherein the CO-containing stream is a synthesis gas stream, preferably wherein the CO-containing stream further comprises H 2 S, H 2 , H 2 O, CO 2 , CH 4 and mixtures thereof.

20. The reactor system according to any one of claims 12 - 19, further comprising a sulfur removal section, which is arranged to receive a CO-containing stream from the electrically heated reactor and remove sulfur-containing substances from the CO-containing stream.

21. A chemical engineering device, which comprises the reactor system according to any one of claims 12 - 20, and a heat exchange reformer or a feed-effluent heat exchanger, wherein the CO-containing stream (11) from the reactor system is arranged to be fed to the heat exchange reformer or the feed-effluent heat exchanger.

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