Improvements in or related to monitoring of Fischer-Tropsch chemical reactors

Abstract

1. A chemical reactor system comprising: a) a primary reactor (10) comprising: i) a reaction chamber containing a catalyst; ii) an inlet (11) for supplying a feed gas from a feed source (1) to the reaction chamber to contact the catalyst; and iii) an outlet (12) for reaction products produced in the reaction chamber from the reaction of the feed gas in the presence of the catalyst; and a reaction test module (20) comprising: b) i) an inlet (21) configured to receive a feed gas from the same feed source (1) that supplies the feed gas to the primary reactor; and ii) at least one test reactor (23) in fluid communication with the inlet (21), each test reactor (23) comprising a reaction chamber containing a catalyst; wherein the primary reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

Description

[Technical Field]

[0001] This disclosure relates to improvements in monitoring Fischer-Tropsch chemical reactors. In particular, this disclosure relates to a chemical reactor system, a method for detecting catalyst poisoning in a reaction chamber, a reaction test module configured to be connected to a raw material source of a main reactor, and a microreactor configured to be detachably inserted into the reaction test module.

[0002] This disclosure applies to the Fischer-Tropsch process. [Background technology]

[0003] The Fischer-Tropsch process is a series of chemical reactions that convert a mixture of carbon monoxide and hydrogen into a liquid hydrocarbon. These reactions are carried out in a reaction chamber, typically at temperatures of 150-300°C and pressures of 1-tens of atmospheres, in the presence of a metal catalyst. The Fischer-Tropsch process is ideally based on the formula (C n H 2n+2 This includes a series of chemical reactions that produce various hydrocarbons having ). More useful reactions produce alkanes as follows: (2n+1)H2+nCO→C n H 2n+2 +nH2O In the formula, n is typically 1 to 100 or greater. The formation of methane (n=1) is undesirable. Most of the alkanes produced tend to be straight chains and are suitable for the production of middle distillate fuels such as diesel and jet fuels through upgrading. In addition to alkane formation, small amounts of alkenes, as well as alcohols and other oxygenated hydrocarbons, are produced by competitive reactions. The Fischer-Tropsch reaction is a highly exothermic reaction because it involves a mixture with CO, which has a standard reaction enthalpy (ΔH) of -165 kJ / mol.

[0004] The feedstock gases supplied to Fischer-Tropsch reactors, such as synthesis gas, can be derived from a variety of sources, including natural gas from steam reforming and / or autothermal reforming, municipal solid waste and biomass from high-temperature gasification, or carbon dioxide and hydrogen from reverse water-gas shift. The synthesis gases produced by these processes typically contain toxins or impurities such as hydrogen cyanide and ammonia at ppm levels, which can damage the Fischer-Tropsch catalyst if they reach it in the reactor. For example, relatively high levels of hydrogen cyanide or ammonia can cause acute poisoning of the catalyst in a short time. Alternatively, relatively low levels of hydrogen cyanide or ammonia may not poison the catalyst immediately but can gradually deactivate it over time. Catalyst poisoning and deactivation lead to reduced operating efficiency and may require the reactor to be taken offline to allow for catalyst replacement and / or regeneration. This, in turn, leads to increased operating costs, further negatively impacting the economic viability of the process.

[0005] Therefore, ideally, hydrogen cyanide and ammonia (and any other related toxins or impurities that may be present) should be removed to single-digit ppb levels before the synthesis gas reaches the Fischer-Tropsch reactor. To remove these species from the synthesis gas, a purification unit may be installed upstream of the reactor. For example, the purification unit may include one or more purification beds for processing the synthesis gas. In some examples, purification may involve converting hydrogen cyanide to ammonia by hydrolysis, and then removing the ammonia using a wet scrubber.

[0006] However, despite the use of upstream purification, the risk of catalyst contamination in the reactor by toxins and impurities in the source gas, such as synthesis gas, still remains. For example, the purification bed in the purification unit may malfunction or become saturated. For example, there may be unexpected toxins or impurities that the purification unit is not designed to remove.

[0007] This disclosure seeks to address at least some of the problems related to the prior art or to provide at least a commercially acceptable alternative solution. [Overview of the project]

[0008] In a first aspect of this disclosure, a chemical reactor system is provided, a) The main reactor, i) A reaction chamber containing the catalyst, ii) An inlet for supplying the raw material gas from the raw material source to the reaction chamber and bringing it into contact with the catalyst, iii) Output of reaction products generated in the reaction chamber from the reaction of raw material gases in the presence of a catalyst, The main reactor, b) A reaction test module, i) an inlet configured to receive raw material gas from the same raw material source that supplies raw material gas to the main reactor, and ii) At least one test reactor having an inlet and fluid communication, each comprising a reaction chamber containing a catalyst, A reaction test module equipped with, Equipped with, A chemical reactor system is provided in which the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0009] In some preferred examples, the reaction test module is: iii) Further comprising an analyzer configured to determine the level of catalytic activity of a catalyst in at least one test reactor by analyzing gases emanating from or originating from the reaction chamber of at least one test reactor.

[0010] For example, an analyzer can determine the level of catalytic activity by analyzing the synthesis gas components of a gas. Such analysis may involve measuring the values ​​and / or rates of change of one or more parameters, which may include, for example, CO conversion rate, methane selectivity, and C5+ productivity.

[0011] In some examples, the analyzer comprises a mass spectrometer or a gas chromatograph.

[0012] In some preferred examples, the analyzer is configured to issue an alert indicating poisoning of the catalyst in the at least one test reactor when a decrease in the level of catalytic activity of the catalyst in the at least one test reactor is detected.

[0013] In some examples, the chemical reactor system further comprises a controller configured to take corrective action when an alert is issued by the analyzer.

[0014] Preferably, the corrective action comprises changing the composition of the feed gas, reducing the flow rate of the feed gas to the reaction chamber of the main reactor, or blocking the supply of the feed gas to the reaction chamber of the main reactor.

[0015] In some examples, the reaction test module further comprises a separator for separating gas exiting the reaction chamber of the at least one test reactor into one or more wax and / or liquid and / or gas fractions.

[0016] In some examples, the wax and liquid fractions are separated into a first product stream comprising a wax product and a second product stream comprising light hydrocarbon products and water.

[0017] In some examples, the catalyst in the reaction chamber of the at least one test reactor is the same catalyst as that present in the reaction chamber of the main reactor.

[0018] In some other examples, the catalyst in the reaction chamber of the at least one test reactor is one or more catalysts different from the catalyst present in the reaction chamber of the main reactor.

[0019] In some preferred examples, the at least one test reactor comprises a plurality of test reactors arranged in parallel.

[0020] Preferably, one or more of the plurality of test reactors, more preferably each, is removable from the reaction test module while the remainder of the plurality of test reactors remains in operation.

[0021] In some examples, the at least one test reactor comprises 3, 4, 5, 6, or more test reactors.

[0022] In some examples, each of the at least one test reactor is a microreactor, i) 250 cm 3 or less, optionally 200 cm 3 or less, optionally 150 cm 3 or less, optionally 100 cm 3 or less, optionally 50 cm 3 or less reaction chamber volume, and / or ii) a reaction chamber containing less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, optionally less than 5 g of catalyst, and / or iii) a reaction chamber length of 30 to 120 cm and / or a reaction chamber diameter of 5 to 20 mm, comprising a microreactor having.

[0023] In some examples, the reaction test module further comprises a heating chamber accommodating the at least one test reactor. Advantageously, this may allow the operating conditions of the catalyst in the at least one test reactor to closely match the operating conditions of the catalyst in the main reactor. In some examples, one or more, more preferably each test reactor is independently controlled via an electric heating block, and the temperature profile of that test reactor or each test reactor is measured. For example, the catalyst bed temperature profile can be measured using a multipoint thermocouple housed in a central thermowell. Alternatively, the temperature can be measured by a thermocouple housed in the wall of the test reactor.

[0024] Preferably, the reaction test module is configured as a side flow unit positioned parallel to the gas flow path through the main reactor.

[0025] In some examples, the chemical reactor system further includes a flow divider downstream of the raw material source and upstream of the main reactor, the flow divider receiving the raw material gas from the raw material source, and the flow divider having a first outlet for supplying to the reaction chamber of the main reactor and a second outlet for supplying to at least one test reactor of the reaction test module.

[0026] In some preferred examples, the reaction test module is configured to combine the gas exiting the reaction test module with the gas exiting the main reactor at a point downstream of the main reactor's reaction chamber, such that the gas passing through the reaction test module bypasses at least the main reactor's reaction chamber.

[0027] In a preferred example, piping in a chemical reactor system exposed to the raw material gas is coated internally with a protective coating to prevent toxic components from being retained on the surface of the piping. The protective coating may be applied to the piping upstream of the reaction test module and to the internal piping of the reaction test module.

[0028] According to this specification, the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0029] A second aspect of this disclosure provides a method for detecting poisoning of a catalyst in a reaction chamber, a) By passing the raw material gas through the reaction chamber and bringing it into contact with the catalyst, the main reactor, which is equipped with a reaction chamber containing the catalyst, is operated to generate a reaction product from the reaction of the raw material gas in the presence of the catalyst. b) Operating the reaction test modules simultaneously by passing a raw material gas through at least one test reactor of the reaction test module, wherein each test reactor is equipped with a reaction chamber containing the same catalyst or a suitable equivalent thereof as that present in the reaction chamber of the main reactor, c) Using an analyzer, determine the level of catalytic activity of the catalyst in at least one test reactor by analyzing the gases exiting the reaction chamber of at least one test reactor and / or analyzing the catalyst in at least one test reactor, Includes, A method is provided in which the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0030] Preferably, the raw material gas supplied to the reaction chamber of the main reactor and the raw material gas supplied to at least one test reactor of the reaction test module come from the same raw material source.

[0031] In some preferred examples, the gas flow from the raw material source is split into a first flow that supplies the reaction chamber of the main reactor and a second flow that supplies at least one test reactor in the reaction test module.

[0032] In some preferred examples, the analysis of the gases exiting the reaction chamber of at least one test reactor is performed in real time while the main reactor is operating.

[0033] In some cases, the analysis of the gases exiting the reaction chamber of at least one test reactor is performed by mass spectrometry or gas chromatography.

[0034] In some cases, the gases exiting the reaction chamber of at least one test reactor are dried and / or cooled before being passed through a mass spectrometer or gas chromatograph.

[0035] In some preferred examples, the method further includes issuing an alert indicating poisoning of the catalyst in at least one test reactor when a decrease in the catalytic activity level of the catalyst in at least one test reactor is detected.

[0036] In some preferred examples, the method further includes taking corrective action when an alert is issued by the analyzer.

[0037] Preferably, corrective measures include changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor.

[0038] In some cases, the catalyst in the reaction chamber of at least one test reactor is the same catalyst present in the reaction chamber of the main reactor.

[0039] In some other examples, the catalyst in the reaction chamber of at least one test reactor is one or more catalysts that are different from the catalyst present in the reaction chamber of the main reactor.

[0040] In some preferred examples, at least one test reactor includes multiple test reactors arranged in parallel.

[0041] In some preferred examples, the analysis of the catalyst in at least one test reactor is performed remotely by removing the test reactor from the reaction test module.

[0042] The reaction test module may be configured to allow real-time analysis of the gases exiting the reaction chamber of at least one test reactor during the operation of the main reactor, and to allow post-analysis of the catalyst by removing the test reactor from the reaction test module.

[0043] In some cases, catalyst analysis includes elemental analysis of the catalyst to identify the accumulation of toxins in the catalyst.

[0044] In some preferred examples, at least one test reactor includes multiple test reactors arranged in parallel, and catalyst analysis includes allowing sequential removal of the test reactors periodically to identify trends in toxin accumulation in the catalyst.

[0045] In some examples, the method further includes heating at least one test reactor in a heating chamber.

[0046] According to this specification, the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0047] This disclosure also relates to a reaction test module configured to be connected to the raw material source of the main reactor, i) an inlet configured to receive raw material gas from a raw material source, and ii) Multiple test reactors arranged in parallel, each having a reaction chamber containing a catalyst and connected to an inlet and fluid, We provide a reaction test module equipped with the following features.

[0048] In some preferred examples, the reaction test module further comprises an analyzer configured to determine the level of catalytic activity of catalysts in multiple test reactors by analyzing the gases exiting the reaction chambers of multiple test reactors.

[0049] In some examples, the reaction test module further comprises a heating chamber housing at least one test reactor.

[0050] The catalyst in each reaction chamber is a Fischer-Tropsch catalyst.

[0051] This disclosure also relates to a microreactor configured to be removably inserted into a reaction test module, i) 250cm 3 Less than 200cm (optional choice) 3 Less than 150cm (optional choice) 3 Less than 100cm (optional choice) 3 Less than 50cm (optional selection) 3 Reaction chamber volume less than, and / or ii) A reaction chamber accommodating less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, or optionally less than 5 g of catalyst. We provide a microreactor equipped with the following features.

[0052] In some examples, the reaction chamber has a length of 30 to 120 cm and / or a diameter of 5 to 20 mm.

[0053] The catalyst in the reaction chamber is a Fischer-Tropsch catalyst.

[0054] In some cases, the catalyst is pre-loaded into the reaction chamber of the microreactor and sealed before the reaction test module is inserted. If the catalyst has an oxidation form that requires activation by reduction, it is preferable to activate the catalyst before pre-loading. This makes the operation of the side flow unit easier, eliminates the need to activate the catalyst in-situ, saves time, and reduces the complexity of the apparatus.

[0055] Beneficially, these aspects of the present disclosure can enable the detection and / or analysis of catalyst contamination by toxins and impurities in the source gas.

[0056] If the system is configured for the detection and / or analysis of catalyst contamination by toxins and impurities, it is most preferable that the catalyst in the reaction chamber of at least one test reactor is the same catalyst present in the reaction chamber of the main reactor. In this way, a suitable correspondence can be ensured between the effect on the catalyst in the main reactor exposed to the feedstock gas and the effect on the catalyst in the reaction test module.

[0057] A sudden decrease in catalyst activity inside at least one test reactor can be used, for example, to indicate that the level of toxins or other contaminants in the feed gas is higher than expected.

[0058] Beneficial in this regard, each test reactor can accommodate a much smaller weight / volume of catalyst than is present in the main reactor, allowing for much faster detection of catalytic degradation due to poisoning compared to monitoring catalyst activity in the main reactor. For example, in the main reactor, a poisoning event may first preferentially affect the catalyst closest to the feedstock gas inlet. However, the overall catalytic activity of the reactor may initially mask this poisoning, and the gas output from the main reactor may appear largely unaffected by the large amount of catalyst that remains unpoisoned. By the time a decrease in the total catalytic activity of the main reactor is detected, a considerable amount of catalyst toward the inlet may have been poisoned and may require replacement or regeneration.

[0059] A fast catalyst response time in at least one test reactor may also enable the detection of the transient period of poisoning. During the transient event, the feedstock gas to the main reactor may be diverted to flare or shut off while still being supplied to the reaction test module, allowing for assessment of when the transient poisoning event has ended.

[0060] The reaction test module can function as a warning sensor for the presence of toxins or other contaminants in the feedstock gas. Beneficially, the reaction test module allows for rapid intervention, thus protecting larger quantities of catalyst present in the main reactor's reaction chamber.

[0061] Preferably, the initiation of corrective action may be automatic or semi-automatic and may be initiated without human intervention. Alternatively, an alert may be presented to the human operator of the reactor (e.g., by an audible and / or visual alert) to prompt the operator to take corrective action.

[0062] The use of a reaction test module can be beneficial throughout all phases of the main reactor's operation. For example, catalyst activity can be monitored for part, or preferably all, of the main reactor's operating period. The reaction test module can also be advantageously used during the commissioning phase, for example, during the main reactor's startup. For example, during startup, the raw material gas may be supplied only to the reaction test module for the period before it is supplied to the main reactor. Thus, the reaction test module can be used to ensure that the raw material gas is within specifications before the catalyst in the main reactor is exposed to the raw material gas. For example, by confirming the expected performance of the catalyst in the test reactor, damage to the catalyst in the main reactor at the start of its life can be avoided.

[0063] Furthermore, the reaction test module allows for the evaluation of novel catalyst formulations under conditions that closely match those in the main reactor, advantageously requiring only small amounts of catalyst and no modifications to the main reactor.

[0064] For example, the system may be configured such that the catalyst in the reaction chamber of at least one test reactor is one or more catalysts different from the catalyst present in the reaction chamber of the main reactor. In this way, the test reactor can be used to evaluate or screen one or more novel catalyst candidates for a process and / or to monitor and evaluate the vulnerability of one or more novel catalyst candidates to potential poisoning events under "real-world" conditions, which can yield more accurate and useful results compared to small-scale laboratory-based testing. Beneficially, by using the reaction test module as a screening / testing aid, the need to reconfigure the main reactor with the novel catalyst is avoided, which is a process that is very expensive in terms of time and materials, and can only evaluate one catalyst at a time.

[0065] In one operating mode, the gas outputs from each of at least one test reactor may be combined before being passed through the analyzer. However, in the preferred operating mode, the gas outputs from each of at least one test reactor are analyzed separately. For example, the output from the first test reactor may be analyzed over a first period, followed by the output from the second test reactor over a second period.

[0066] Beneficially, by providing multiple test reactors, it may be possible to periodically remove the test reactors over the duration of the main reactor's operation. By analyzing the catalyst in the test reactors over time, a deeper understanding of poison accumulation in the catalyst in both the test reactors and the main reactor can be obtained. Since catalyst poisoning can sometimes be a slow process, periodically removing and analyzing the catalyst from the reaction test module may allow for confirmation of poisoning trends. Beneficially, the use of the reaction test module means that the main reactor can be left undisturbed and that it is not necessary to shut down the main reactor to extract catalyst samples from it.

[0067] Furthermore, the use and analysis of multiple test reactors can increase the statistical confidence that catalyst poisoning events are occurring or have already occurred.

[0068] The analysis may be performed near the main reactor, or the test reactor may be moved to a different location for analysis.

[0069] The types of toxins and contaminants accumulated in the catalyst can be identified, for example, by elemental analysis of the catalyst. Beneficially, analyzing the catalyst itself overcomes the difficulties of directly analyzing ppb-level toxins and contaminants in the source gas. In addition, catalyst analysis may enable the detection of previously unanalyzed toxins and contaminants in the source gas.

[0070] Using a parallel arrangement of test reactors, it is possible to ensure that all test reactors within a reaction test module are exposed to the same feedstock gas for the same duration (or at least until the test reactor is optionally selectively removed for post-analysis). In addition, the parallel arrangement may also allow for the removal of one test reactor while other test reactors remain operational.

[0071] In this disclosure, the main reactor is a Fischer-Tropsch reactor housing a Fischer-Tropsch catalyst. Therefore, the following description of this disclosure relates to a Fischer-Tropsch process and reactor as an example. However, it will be understood that the systems, methods, and apparatus of this disclosure are applicable to other processes and reactors. In other examples, the main reactor may be configured for methanol synthesis, aqueous-gas shift, and the like.

[0072] The catalyst for the main reactor may be provided in different forms known in the art. For example, the catalyst may be provided as one or more catalyst beds. The beds may be fluidized beds, fixed beds, or a combination thereof. For example, the main reactor may be a fluidized bed reactor or a fixed bed reactor. Alternatively, the catalyst may be housed in a plurality of catalyst supports received within the reactor tube of the main reactor. For example, the main reactor may be a tubular reactor. Several examples of catalyst supports configured for use in tubular reactors are described in International Publication Nos. 2011 / 048361, 2012 / 136971, 2016 / 050520, and 2022064214(A1), the entire contents of which are incorporated herein by reference. [Brief explanation of the drawing]

[0073] Next, embodiments of the present disclosure will be described only as examples with reference to the attached drawings. [Figure 1] This figure shows a first example of a chemical reactor system according to the present disclosure. [Figure 2] This figure shows a second example of a chemical reactor system according to the present disclosure. [Figure 3] This figure shows a third example of a chemical reactor system according to the present disclosure. [Figure 4] This is a schematic diagram of the reaction test module for the third example. [Modes for carrying out the invention]

[0074] Figure 1 shows a schematic diagram of a first example of a chemical reactor system according to the present disclosure. This system comprises a main reactor 10 and a reaction test module 20, both of which are supplied with raw material gas from a common raw material source 1.

[0075] The main reactor 10 comprises a reaction chamber for housing a catalyst, an inlet 11 for supplying raw material gas from the raw material source 1 to the reaction chamber and bringing it into contact with the catalyst, and an outlet 12 for the reaction products generated in the reaction chamber from the reaction of the raw material gas in the presence of the catalyst.

[0076] The output 12 from the main reactor 10 can be supplied to one or more downstream modules (not shown) configured for further processing, recycling, or use. For example, the reaction product may include or consist of a liquid phase and a gas phase when it leaves the main reactor 10, and is then cooled downstream and separated into wax, liquid phase, and gas phase. The wax phase may contain heavier hydrocarbons, for example, having chain lengths of C10 to C100 or more. The liquid phase may contain lighter hydrocarbons and / or a water fraction. The gas phase may be dry or may have some residual water content.

[0077] The reaction test module 20 includes an inlet 21 configured to receive raw material gas from the same raw material source 1 that supplies raw material gas to the main reactor 10, and at least one test reactor that is in fluid communication with the inlet 21 and each has a reaction chamber that contains a catalyst. The catalyst may be the same catalyst as the catalyst present in the reaction chamber of the main reactor 10, or it may be a different catalyst.

[0078] The reaction test module 20 may have an output 22 for reaction products generated in the reaction chamber of at least one test reactor.

[0079] Figure 2 shows a schematic diagram of a second example of the chemical reactor system according to the present disclosure. This example is the same as the first example, except that the output 22 of the reaction test module 20 is fed back and merges with the feed from the output 12 of the main reactor at point 13. This can be beneficially improved in system efficiency by enabling simplification of downstream processing of reaction products using a single set of modules, such as a condenser and a separator.

[0080] Figure 3 shows a schematic diagram of a third example of a chemical reactor system according to the present disclosure. This example is similar to the previous example. At least one test reactor, indicated by reference numeral 23, receives the raw material gas from input 21. The reaction test module 20 further comprises a separator 25 and an analyzer 26. The analyzer 26 may include a mass spectrometer or a gas chromatograph.

[0081] The separator 25 may be configured to obtain a gas fraction from the reaction products output from one or more test reactors 23 and send it to the analyzer 26. The separator 25 may include means for cooling the reaction products and / or for separating them into wax and / or liquid and / or gas fractions. For example, the separator 25 may include one or more knockout pots. A first knockout pot may be provided to remove the wax fraction and heavier HC fractions. A subsequent second knockout pot may be provided to remove lighter HC fractions and / or water. Preferably, the gas fraction sent to the analyzer 26 contains dry gas.

[0082] The analyzer 26 may be configured to determine the level of catalytic activity of the catalyst in at least one test reactor 23 by analyzing the gas received from the separator 25. For example, the analyzer may determine the CO conversion rate, methane selectivity, product selectivity, e.g., Cn, preferably C5+ selectivity, paraffin and olefin selectivity, and productivity, e.g., C5+ The catalytic activity may be determined by calculating performance parameters such as productivity.

[0083] The system may further include a controller 40 configured to take corrective action when an alert is issued by, for example, an analyzer 26 via the reaction test module 20. Corrective action may include changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor 10, or blocking the supply of the raw material gas to the reaction chamber of the main reactor 10, for example, by diverting it to a flare or completely shutting off the supply. The controller 40 may also be configured to maintain target performance parameters by increasing the temperature of one or more of the test reactors so that the catalyst deactivation rate can be quantified. For example, the deactivation rate can be quantified in terms of the extra temperature required to maintain the carbon monoxide conversion rate at a target level.

[0084] As schematically shown in Figure 4, the reaction test module 20 of the third example (or any of the other examples) may include a plurality of test reactors 23 arranged in parallel.

[0085] The illustrated example shows six test reactors 23 arranged in parallel.

[0086] The test reactors 23 can be supplied by a common inlet manifold 27. Isolation valves (not shown), such as solenoid valves, may be provided upstream of each test reactor 23 to selectively shut off the gas flow to each test reactor 23, allowing for purging, maintenance, and / or removal of the test reactors 23.

[0087] The outlets from each test reactor 23 may be supplied to a common outlet manifold 28. A tee-off valve 24 may be interposed between each of the test reactors 23 and the common outlet manifold 28. The tee-off valve 24 can function to selectively direct the gas leaving each test reactor 23 to either the common outlet manifold 28 or the output 22 of the reaction test module 20.

[0088] The common outlet manifold 28 can supply to the separator 25 of the reaction test module 20.

[0089] Each of the test reactors 23 may be detachable from the reaction test module 20 while the rest of the test reactors 23 remain in operation.

[0090] Each test reactor 23 is a microreactor, i) 250cm 3 Less than 200cm (optional choice) 3 Less than 150cm (optional choice) 3 Less than 100cm (optional choice) 3 Less than 50cm (optional selection) 3 Reaction chamber volume less than, and / or ii) The microreactor may be equipped with a reaction chamber that accommodates less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, or optionally less than 5 g of catalyst.

[0091] The reaction test module 20 may further include a heating chamber for housing the test reactor 23. For example, an oven or other heating chamber may be provided to maintain the test reactor 23 at a suitable high temperature.

[0092] Piping in a chemical reactor system exposed to the raw material gas may be coated internally with a protective coating to prevent toxic components from being retained on the surface of the piping. The protective coating may be applied to the piping upstream of the reaction test module 20 and to the internal piping of the reaction test module 20. In some examples, a silicone coating may be applied where necessary, in particular to any stainless steel piping present. In a non-limiting example, SilCoNert® coatings from SilcoTek®, Belfont, Pennsylvania, USA, may be used.

[0093] During use, the reaction test module 20 can enable a method for detecting the poisoning of the catalyst in the reaction chamber of the main reactor 10. The method is as follows: a) By passing the raw material gas through the reaction chamber and bringing it into contact with the catalyst, the main reactor 10, which is equipped with a reaction chamber containing the catalyst, is operated to generate a reaction product from the reaction of the raw material gas in the presence of the catalyst. b) Simultaneously operating the reaction test modules 20 by passing the raw material gas through the test reactors 23, wherein each test reactor 23 is equipped with a reaction chamber containing a catalyst, c) Using an analyzer 26, determine the level of catalytic activity of the catalyst in the test reactor 23 by analyzing the gases emanating from or originating from the reaction chamber of the test reactor 23 and / or analyzing the catalyst in the test reactor 23.

[0094] Analysis of gases emitted from or originating from the reaction chamber of the test reactor 23 may be performed in real time while the main reactor 10 is operating.

[0095] The gases emanating from or originating from the reaction chamber of the test reactor 23 may be dried and / or cooled by the separator 25 before being passed through the analyzer 26, for example, a mass spectrometer or a gas chromatograph.

[0096] The controller 40 can issue an alert indicating catalyst poisoning in the test reactor 23 when it detects a decrease in the catalytic activity level of the catalyst in the test reactor 23. This can be used as an analogy for detecting catalyst poisoning in the main reactor 10.

[0097] The detection or generation of an alert can prompt corrective measures such as changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor 10, or blocking the supply of the raw material gas to the reaction chamber of the main reactor 10.

[0098] The reaction test module 20 may, either additionally or alternatively, allow for remote analysis of the catalyst in the test reactor 23 by removing the test reactor 23 from the reaction test module 20.

[0099] Catalyst analysis may include elemental analysis of the catalyst to identify the accumulation of toxins in the catalyst.

[0100] The test reactors 23 can be arranged in parallel, and it may be possible to periodically remove selected test reactors 23 to identify trends in poison accumulation in the catalyst. For example, a test reactor 23 may be removed, for example, once a month, to analyze trends over a period of six months. The period between removals can be selected as desired. To replace the removed reactor, a replacement test reactor 23 can be inserted into the reaction test module 20.

[0101] Further aspects of this disclosure are described in the following clauses. Clause 1. A chemical reactor system, a) The main reactor, i) A reaction chamber containing the catalyst, ii) An inlet for supplying the raw material gas from the raw material source to the reaction chamber and bringing it into contact with the catalyst, iii) A main reactor comprising the output of reaction products generated in the reaction chamber from the reaction of the source gas in the presence of a catalyst, b) A reaction test module, i) an inlet configured to receive raw material gas from the same raw material source that supplies raw material gas to the main reactor, and ii) At least one test reactor having an inlet and fluid communication, each comprising a reaction chamber containing a catalyst, A chemical reactor system comprising a reaction test module and

[0102] Clause 2. The reaction test module is iii) The chemical reactor system according to Clause 1, further comprising an analyzer configured to determine the level of catalytic activity of a catalyst in at least one test reactor by analyzing gases emanating from or originating from the reaction chamber of at least one test reactor.

[0103] Clause 3. A chemical reactor system as described in Clause 2, wherein the analyzer includes a mass spectrometer or a gas chromatograph.

[0104] Clause 4. A chemical reactor system according to Clause 2 or Clause 3, wherein the analyzer is configured to issue an alert indicating poisoning of a catalyst in at least one test reactor when a decrease in the catalytic activity level of a catalyst in at least one test reactor is detected.

[0105] Clause 5. The chemical reactor system described in Clause 4, further comprising a controller configured to take corrective action when an alert is issued by the analyzer.

[0106] Clause 6. A chemical reaction system as described in Clause 5, wherein the corrective action includes changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor.

[0107] Clause 7. A chemical reactor system according to any one of Clauses 1 to 6, wherein the reaction test module further comprises a separator for separating liquids and gases exiting the reaction chamber of at least one test reactor into one or more wax and / or liquid and / or gas fractions.

[0108] Clause 8. The chemical reactor system according to Clause 7, wherein the wax and liquid fractions are separated into a first product flow containing wax products and a second product flow containing light hydrocarbon products and water.

[0109] Clause 9. A chemical reactor system according to any one of Clauses 1 to 8, wherein the catalyst in the reaction chamber of at least one test reactor is the same catalyst as the catalyst present in the reaction chamber of the main reactor.

[0110] Clause 10. A chemical reactor system according to any one of Clauses 1 to 8, wherein the catalyst in the reaction chamber of at least one test reactor is one or more catalysts different from the catalyst present in the reaction chamber of the main reactor.

[0111] Clause 11. A chemical reactor system according to any one of Clauses 1 to 10, wherein at least one test reactor comprises multiple test reactors arranged in parallel.

[0112] Clause 12. The chemical reactor system described in Clause 11, wherein each of the multiple test reactors is detachable from the reaction test module, but the remainder of the multiple test reactors remain operational.

[0113] Clause 13. A chemical reactor system according to Clause 11 or Clause 12, wherein at least one test reactor comprises three, four, five, six, or more test reactors.

[0114] Clause 14. Each of at least one test reactors is a microreactor, i) 250cm 3 Less than 200cm (optional choice) 3 Less than 150cm (optional choice) 3 Less than 100cm (optional choice) 3 Less than 50cm (optional selection) 3 Reaction chamber volume less than, and / or ii) A reaction chamber accommodating less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, or optionally less than 5 g of catalyst. A chemical reactor system according to any of the clauses 1 to 13, comprising a microreactor having a microreactor.

[0115] Clause 15. A chemical reactor system according to any one of Clauses 1 to 14, wherein the reaction test module further comprises a heating chamber housing at least one test reactor.

[0116] Clause 16. A chemical reactor system according to any one of Clauses 1 to 15, wherein the reaction test module is configured as a side flow unit positioned parallel to the gas flow path through the main reactor.

[0117] Clause 17. A chemical reactor system according to any one of Clauses 1 to 16, further comprising a flow divider downstream of the raw material source and upstream of the main reactor, wherein the flow divider receives raw material gas from the raw material source, and the flow divider has a first outlet for supplying to the reaction chamber of the main reactor and a second outlet for supplying to at least one test reactor of the reaction test module.

[0118] Clause 18. A chemical reactor system according to any one of Clauses 1 to 17, wherein the reaction test module is configured to combine the gas exiting the reaction test module with the gas exiting the main reactor at a point downstream of the reaction chamber of the main reactor, such that the gas passing through the reaction test module bypasses at least the reaction chamber of the main reactor.

[0119] Clause 19. A chemical reactor system according to any of Clauses 1 to 18, wherein the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0120] Article 20. A method for detecting poisoning of a catalyst in a reaction chamber, a) By passing the raw material gas through the reaction chamber and bringing it into contact with the catalyst, the main reactor, which is equipped with a reaction chamber containing the catalyst, is operated to generate a reaction product from the reaction of the raw material gas in the presence of the catalyst. b) Operating the reaction test modules simultaneously by passing a raw material gas through at least one test reactor of the reaction test module, wherein each test reactor is equipped with a reaction chamber containing a catalyst, c) A method comprising determining the level of catalytic activity of a catalyst in at least one test reactor by using an analyzer to analyze the gas emanating from or originating from the reaction chamber of at least one test reactor and / or the catalyst in at least one test reactor.

[0121] Clause 21. The method according to Clause 20, wherein the raw material gas supplied to the reaction chamber of the main reactor and the raw material gas supplied to at least one test reactor of the reaction test module come from the same raw material source.

[0122] Clause 22. The method according to Clause 21, wherein the gas flow from the raw material source is divided into a first flow that supplies the reaction chamber of the main reactor and a second flow that supplies at least one test reactor of the reaction test module.

[0123] Clause 23. The method according to any one of Clauses 20 to 22, wherein the analysis of gases emanating from or originating from the reaction chamber of at least one test reactor is performed in real time while the main reactor is operating.

[0124] Clause 24. The method according to any one of Clauses 20 to 23, wherein the analysis of gases emanating from or originating from the reaction chamber of at least one test reactor is performed by mass spectrometer or gas chromatograph.

[0125] Clause 25. The method according to any one of Clauses 20 to 24, wherein the gas emanating from or originating from the reaction chamber of at least one test reactor is dried and / or cooled before being passed through a mass spectrometer or gas chromatograph.

[0126] Clause 26. The method according to any one of Clauses 20 to 25, further comprising issuing an alert indicating poisoning of a catalyst in at least one test reactor when a decrease in the catalytic activity level of a catalyst in at least one test reactor is detected.

[0127] Clause 27. The method of Clause 26, further comprising taking corrective action when an alert is issued by the analyzer.

[0128] Clause 28. The method according to Clause 27, wherein the corrective action includes changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor.

[0129] Clause 29. The method according to any one of Clauses 20 to 28, wherein the catalyst in the reaction chamber of at least one test reactor is the same catalyst as the catalyst present in the reaction chamber of the main reactor.

[0130] Clause 30. The method according to any one of Clauses 20 to 28, wherein the catalyst in the reaction chamber of at least one test reactor is one or more catalysts different from the catalyst present in the reaction chamber of the main reactor.

[0131] Clause 31. The method according to any one of Clauses 20 to 30, wherein at least one test reactor comprises a plurality of test reactors arranged in parallel.

[0132] Clause 32. The method according to any one of Clauses 20 to 31, wherein the analysis of the catalyst in at least one test reactor is performed at a remote location by removing the test reactor from the reaction test module.

[0133] Clause 33. The method according to Clause 32, wherein the analysis of the catalyst includes elemental analysis of the catalyst to identify the accumulation of toxins in the catalyst.

[0134] Clause 34. The method according to any one of Clauses 20 to 33, wherein at least one test reactor comprises a plurality of test reactors arranged in parallel, and the analysis of the catalyst includes allowing the sequential test reactors to be periodically removed to identify a tendency for poison accumulation in the catalyst.

[0135] Clause 35. The method according to any one of Clauses 20 to 34, further comprising heating at least one test reactor in a heating chamber.

[0136] Clause 36. The method according to any one of Clauses 20 to 35, wherein the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst.

[0137] Article 37. A reaction test module configured to be connected to the raw material source of the main reactor, i) an inlet configured to receive raw material gas from a raw material source, and ii) Multiple test reactors arranged in parallel, each having a reaction chamber containing a catalyst and connected to an inlet and fluid, A reaction test module equipped with the following features.

[0138] Clause 38. The reaction test module described in Clause 37, further comprising an analyzer configured to determine the level of catalytic activity of catalysts in multiple test reactors by analyzing the gases exiting the reaction chambers of multiple test reactors.

[0139] Clause 39. The reaction test module according to Clause 37 or 38, further comprising a heating chamber housing at least one test reactor.

[0140] Clause 40. A reaction test module according to any one of Clauses 37-39, wherein the catalyst in each reaction chamber is a Fischer-Tropsch catalyst.

[0141] Clause 41. A microreactor configured to be removably inserted into a reaction test module, i) 250cm 3 Less than 200cm (optional choice) 3 Less than 150cm (optional choice) 3 Less than 100cm (optional choice) 3 Less than 50cm (optional selection) 3 Reaction chamber volume less than, and / or ii) A reaction chamber accommodating less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, or optionally less than 5 g of catalyst. A microreactor equipped with the following features.

[0142] Clause 42. The microreactor according to Clause 41, wherein the reaction chamber has a length of 30 to 120 cm and / or a diameter of 5 to 20 mm.

[0143] Clause 43. The microreactor according to Clause 41 or 42, wherein the catalyst in the reaction chamber is a Fischer-Tropsch catalyst.

[0144] Clause 44. A microreactor as described in any one of Clauses 41 to 43, wherein the reaction chamber of the microreactor is pre-loaded with catalyst and sealed before the insertion of the reaction test module. The disclosures in this specification may include the following aspects: (Aspect 1) A chemical reactor system, a) The main reactor, i) A reaction chamber containing the catalyst, ii) an inlet for supplying the raw material gas from the raw material source to the reaction chamber and bringing it into contact with the catalyst, iii) A main reactor comprising outputting a reaction product generated in the reaction chamber from the reaction of the raw material gas in the presence of the catalyst, b) A reaction test module, i) an inlet configured to receive raw material gas from the same raw material source that supplies raw material gas to the main reactor, and ii) A reaction test module comprising at least one test reactor having fluid communication with the inlet, each having a reaction chamber containing a catalyst, A chemical reactor system in which the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst. (Aspect 2) The reaction test module, iii) The chemical reactor system according to embodiment 1, further comprising an analyzer configured to determine the level of catalytic activity of the catalyst in the at least one test reactor by analyzing the gas emanating from or originating from the reaction chamber of the at least one test reactor. (Aspect 3) The chemical reactor system according to embodiment 2, wherein the analyzer is configured to issue an alert indicating poisoning of the catalyst in the at least one test reactor when a decrease in the catalytic activity level of the catalyst in the at least one test reactor is detected. (Aspect 4) The analyzer further comprises a controller configured to take corrective action when the alert is issued, The chemical reactor system according to embodiment 3, wherein the corrective action optionally includes changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor. (Appendix 5) A chemical reactor system according to any one of embodiments 1 to 4, wherein the catalyst in the reaction chamber of at least one test reactor is the same catalyst present in the reaction chamber of the main reactor. (Aspect 6) A chemical reactor system according to any one of embodiments 1 to 4, wherein the catalyst in the reaction chamber of at least one test reactor is one or more catalysts different from the catalyst present in the reaction chamber of the main reactor. (Aspect 7) The chemical reactor system according to any one of embodiments 1 to 6, wherein the at least one test reactor includes a plurality of test reactors arranged in parallel. (Pattern 8) The chemical reactor system according to embodiment 7, wherein each of the plurality of test reactors is detachable from the reaction test module, but the remaining plurality of test reactors remain in operation. (Aspect 9) Each of the at least one test reactors is a microreactor, i) 250cm 3 Less than 200cm (optional choice) 3 Less than 150cm (optional choice)3 Less than 100cm (optional choice) 3 Less than 50cm (optional selection) 3 Reaction chamber volume less than, and / or ii) A reaction chamber accommodating less than 25 grams of catalyst, optionally less than 20 g of catalyst, optionally less than 15 g of catalyst, optionally less than 10 g of catalyst, optionally less than 5 g of catalyst, and / or iii) A chemical reactor system according to any one of embodiments 1 to 8, comprising a microreactor having a reaction chamber length of 30 to 120 cm and / or a reaction chamber diameter of 5 to 20 mm. (Aspect 10) The chemical reactor system according to any one of embodiments 1 to 9, wherein the reaction test module further comprises a heating chamber housing the at least one test reactor. (Aspect 11) A method for detecting poisoning of a catalyst in a reaction chamber, a) By passing the raw material gas through the reaction chamber and bringing it into contact with the catalyst, the main reactor comprising the reaction chamber containing the catalyst is operated, and a reaction product is generated from the reaction of the raw material gas in the presence of the catalyst. b) Operating the reaction test module simultaneously by passing a raw material gas through at least one test reactor of the reaction test module, wherein each test reactor is equipped with a reaction chamber containing a catalyst, c) Determining the level of catalytic activity of the catalyst in the at least one test reactor by using an analyzer to analyze the gas emanating from or originating from the reaction chamber of the at least one test reactor and / or the catalyst in the at least one test reactor, The method wherein the main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst. (Aspect 12) The method according to embodiment 11, wherein the raw material gas supplied to the reaction chamber of the main reactor and the raw material gas supplied to the at least one test reactor of the reaction test module come from the same raw material source. (Aspect 13) The method according to embodiment 11 or 12, wherein the analysis of the gas emanating from or originating from the reaction chamber of the at least one test reactor is performed in real time while the main reactor is operating. (Aspect 14) The method according to any one of embodiments 11 to 13, further comprising issuing an alert indicating poisoning of the catalyst in the at least one test reactor when a decrease in the catalytic activity level of the catalyst in the at least one test reactor is detected. (Aspect 15) This further includes taking corrective action when the analyzer issues the alert, The method according to embodiment 14, wherein the corrective action optionally includes changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor. (Aspect 16) The method according to any one of embodiments 11 to 15, wherein the at least one test reactor includes a plurality of test reactors arranged in parallel. (Aspect 17) The method according to any one of embodiments 11 to 16, wherein the analysis of the catalyst in at least one test reactor is performed at a remote location by removing the test reactor from the reaction test module. (Aspect 18) The method according to embodiment 17, wherein the analysis of the catalyst includes elemental analysis of the catalyst to identify the accumulation of toxins in the catalyst. (Aspect 19) The method according to any one of embodiments 11 to 18, wherein the at least one test reactor comprises a plurality of test reactors arranged in parallel, and the analysis of the catalyst includes enabling the sequential removal of the test reactors periodically to identify a tendency for poison accumulation in the catalyst.

Claims

1. A method for detecting the poisoning of a catalyst in a reaction chamber, a) By passing the raw material gas through the reaction chamber and bringing it into contact with the catalyst, the main reactor comprising the reaction chamber containing the catalyst is operated, and a reaction product is generated from the reaction of the raw material gas in the presence of the catalyst. b) Operating the reaction test module simultaneously by passing a raw material gas through at least one test reactor of the reaction test module, wherein each test reactor is equipped with a reaction chamber containing a catalyst, c) Determining the level of catalytic activity of the catalyst in the at least one test reactor by using an analyzer to analyze the gas emanating from or originating from the reaction chamber of the at least one test reactor and / or the catalyst in the at least one test reactor, The main reactor is a Fischer-Tropsch reactor containing a Fischer-Tropsch catalyst, The raw material gas supplied to the reaction chamber of the main reactor and the raw material gas supplied to the at least one test reactor of the reaction test module are from the same raw material source. A method comprising: at least one test reactor or each of the test reactors containing a Fischer-Tropsch catalyst, wherein the volume of the Fischer-Tropsch catalyst is smaller than the volume of the Fischer-Tropsch catalyst in the main reactor, thereby using a decrease in the catalytic activity of the Fischer-Tropsch catalyst in the at least one test reactor to detect poisoning of the Fischer-Tropsch catalyst in the main reactor.

2. The method according to claim 1, wherein the analysis of the gas emanating from or originating from the reaction chamber of at least one test reactor is performed in real time while the main reactor is operating.

3. The method according to claim 1 or 2, further comprising issuing an alert indicating poisoning of the catalyst in the at least one test reactor when a decrease in the level of catalytic activity of the catalyst in the at least one test reactor is detected.

4. This further includes taking corrective action when the analyzer issues the alert, The method according to claim 3, wherein the corrective action includes changing the composition of the raw material gas, reducing the flow rate of the raw material gas to the reaction chamber of the main reactor, or blocking the supply of the raw material gas to the reaction chamber of the main reactor.

5. The method according to claim 1 or 2, wherein the at least one test reactor includes a plurality of test reactors arranged in parallel.

6. The method according to claim 1 or 2, wherein the analysis of the catalyst in at least one test reactor is performed at a remote location by removing the test reactor from the reaction test module.

7. The method according to claim 6, wherein the analysis of the catalyst includes elemental analysis of the catalyst to identify the accumulation of toxins in the catalyst.

8. The method according to claim 1 or 2, wherein the at least one test reactor comprises a plurality of test reactors arranged in parallel, and the analysis of the catalyst includes enabling the sequential removal of the test reactors periodically to identify a tendency for poison accumulation in the catalyst.

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