Patent Application
20230053936
This disclosure relates to dry reforming of methane and methanol synthesis.
Methane may be labeled as the simplest hydrocarbon. Methane may be subjected to steam reforming to generate synthetic gas (syngas) that includes hydrogen (H2) and carbon monoxide (CO). The syngas may be distributed to different facilities as a feedstock for generating chemicals or chemical intermediates. The hydrogen may be separated from the syngas to produce hydrogen.
Carbon dioxide is the primary greenhouse gas emitted through human activities. Carbon dioxide (CO2) may be generated in various industrial and chemical plant facilities. At such facilities, the utilization of CO2 as a feedstock may reduce CO2 emissions at the facility and therefore decrease the CO2 footprint of the facility. The conversion of the greenhouse gas CO2 into value-added feedstocks or products may be beneficial.
An aspect relates to a method of producing methanol via dry reforming and methanol synthesis, the method including providing feed including methane and carbon dioxide to a vessel, converting methane and carbon dioxide in the vessel into syngas including hydrogen and carbon monoxide via dry reforming in the vessel, cooling the syngas via a heat exchanger in the vessel, synthesizing methanol from the syngas in the vessel, and discharging effluent (including methanol) from the vessel.
Another aspect is a method of producing methanol, including converting (dry reforming) methane and carbon dioxide via a dry reforming catalyst in a dry reforming section in a reactor vessel into syngas including hydrogen and carbon monoxide, wherein the converting comprises dry reforming. The method includes flowing the syngas from the dry reforming section through a heat exchange section in the reactor vessel to cool the syngas with a cooling medium in the heat exchange section. The method includes flowing the syngas as cooled from the heat exchange section to a methanol synthesis section in the reactor vessel. The method includes synthesizing methanol from the syngas via a methanol synthesis catalyst in the methanol synthesis section.
Yet another aspect relates to a methanol production system including a reactor vessel having a feed inlet to receive a feed including methane and carbon dioxide. The reactor vessel includes a dry reforming section having a dry reforming catalyst in the reactor vessel to convert the methane and the carbon dioxide into syngas including hydrogen and carbon monoxide. The reactor vessel includes a heat exchange section having a heat exchanger in the reactor vessel to receive the syngas from the dry reforming section and cool the syngas with a cooling medium. The reactor vessel includes a methanol synthesis section having a methanol synthesis catalyst in the reactor vessel to synthesize methanol from the syngas and discharge an effluent including the methanol from the reactor vessel.
The details of one or more implementations are set forth in the accompanying drawings and the description below. Other features and advantages will be apparent from the description and drawings, and from the claims.
Some aspects of the present disclosure are directed to dry reforming and methanol synthesis in the same vessel to generate methanol. Overall, the methanol may be generated from methane and carbon dioxide in the vessel. Methane and carbon dioxide may be fed to the vessel, and the methanol generated in the vessel may discharge from the vessel.
The methanol generation may be via dry reforming of the methane in the vessel. In particular, the methanol may be synthesized in the vessel from the synthetic gas (syngas) generated by the dry reforming. Again, the dry reforming and the methanol synthesis may occur in the same vessel. Thus, methanol production can be by performing both dry reforming and methanol synthesis in the same vessel.
Dry reforming may be beneficial for consuming the two-greenhouse gases methane (CH4) and carbon dioxide (CO2). Dry reforming is a process that may react CH4 with CO2 to produce syngas with the aid of catalyst. The syngas may include hydrogen (H2) and carbon monoxide (CO). The dry reforming reaction may be characterized as CH4+CO2→2H2+2CO.
Embodiments of the present techniques include a reactor for methanol synthesis via dry reforming, and in which both the dry reforming reaction and the methanol synthesis reaction occur in the same reactor vessel. In certain embodiments, the reactor (reactor vessel) may have at least three sections including a dry reforming section, a heat exchanger section, and a methanol synthesis section. The reactor converts carbon dioxide and methane into methanol in the vessel of the reactor.
Due to the mounting concerns about climate change, CCUS (carbon capture, utilization, and storage) is a focus of research and development around the world. The utilization can include conversion. CO2 conversion technologies have attracted attention at least because of difficulties associated with geological storage of CO2. An aim of CO2 conversion may be to utilize concentrated CO2 (e.g. from CO2 capture) as a feedstock to produce valuable chemicals via various conversion processes.
In implementations herein, dry reforming of CH4 is a CO2 conversion technology for mitigating CO2 emissions. The dry reforming of methane (DRM) has relatively high CO2 utilization ratio (e.g., molar ratio CH4:CO2=1:1) and thus may facilitate CO2 reduction. The dry reforming of CH4 may also reduce emissions of CH4, which like CO2, is a greenhouse gas.
Embodiments herein utilize CO2 as feedstock via DRM to produce methanol. As presented herein in embodiments, the syngas produced from DRM is utilized directly in methanol production. Again, the syngas produced from DRM may be primarily H2 and CO at a molar ratio of 1:1 based on the ideal thermodynamic equilibrium.
The system 100 includes a reactor 106. The system 100 includes a downstream system 108 that processes effluent 110 from the reactor 106 to give the methanol 102 product. The reactor 106 may generally be a continuous reactor. The system 100 may generally be a continuous system.
The reactor 106 includes a reactor vessel 112 having sections (zones or portions) for performing multiple respective unit operations. In implementations, the three sections (dry reforming, heat exchange, and DME synthesis) discussed below are all generally in the interior of the vessel 112 to the inside of the vessel 112 wall. The reactor vessel 112 may be metal, such as stainless steel. The reactor vessel 112 may have a vertical orientation as depicted, or may have a horizontal orientation. In implementations, the vessel 112 may have elliptical heads. The reactor vessel 112 may have nozzles (e.g., flanged, threaded, etc.) at inlets and outlets for coupling to inlet supply conduits and outlet discharge conduits. The reactor vessel 112 may have vessel internals (e.g., plates, perforated plates, conduits, distributors, baffles, etc.) to provide for and accommodate the division or segregation of the vessel 112 into multiple sections. The three sections (parts) discussed below might be structurally separate in the vessel via, for example, divider plates or divider meshes. In operation, fluid flow occurs from one section to another section. Divider plates, if employed, may have holes. Distributers may also be employed to facilitate and distribute flow of fluid. These and other vessel internals may be, for example, a stainless steel, a Hastelloy®, or an Inconel®, and the like. The reactor 106 may be considered a single reactor for performing multiple operations at the same time, and may be labeled colloquially as a “single-step” reactor in performing multiple unit operations or steps contemporaneously (or simultaneously) in the same vessel 112.
In the illustrated embodiment, the reactor 106 is configured to perform two different reactions of dry reforming and methanol synthesis contemporaneously in two respective sections, as discussed below. While the methanol synthesis within the vessel 112 may be in sequence downstream of the dry reforming within the vessel 112, the two reactions may occur as the same time in the continuous operation of the reactor 106.
The reactor 106 includes a dry reforming section 114 to perform (via reforming catalyst 116) the dry reforming reaction represented by CH4+CO2→2 H2+2CO. The dry reforming section 114 may be labeled as a dry reforming zone, dry reforming part, dry reformer, etc. The dry reforming section 114 may be enclosed within the reactor vessel 112 of the reactor 106. The dry reforming section 114 has dry reforming catalyst 116 to convert CH4 and CO2 of the feed 104 into synthetic gas (syngas) that is H2 and CO. The dry reforming catalyst 116 may be a fixed bed of catalyst in the dry reforming section 114. In certain implementations, the dry reforming catalyst 116 is a nickel-based catalyst. The dry reforming can be conducted, for example, at less than 850° C., less than 800° C., in the range of 700° C. to 900° C., in the range of 750° C. to 875° C., or in the range of 800° C. to 850° C. The molar ratio of the CO2 and CH4 in the feed 104 to the dry reforming section 114 can vary, for example, in the range of 1:1 to 3:1. As can be seen from the above dry-reforming reaction equation, the molar ratio of H2 to CO in the generated syngas is 1:1 based on the ideal thermodynamic equilibrium, but in practice can be different from 1:1. The molar ratio of H2 to CO in the produced syngas is ideally 1 but in implemented production can be, for example, in the range of 0.4 to 1.
Moreover, as the dry reforming reaction is generally endothermic, heat may be added to the dry reforming section 114. For instance, electrical heaters may be associated with the dry reforming section 114, or the reactor vessel 112 may have a vessel jacket at the dry reforming section 114 for a heat transfer fluid (as a heating medium).
The reactor 106 includes a heat exchange section 118 that may be labeled as a heat exchange zone, heat exchange part, heat exchanger zone, heat exchanger portion, heat exchanger, etc. The heat exchanger is generally disposed within the vessel 112. The heat exchange section 118 may be enclosed within the reactor vessel 112 of the reactor 106. A purpose of the heat exchange section 118 may be to cool the syngas 120 to a desired temperature for feed to the methanol synthesis.
In operation, the heat exchange section 118 cools the syngas 120 discharged from the dry reforming section 114. In some implementations, the syngas 120 can include additional H2 added to increase the molar ratio of H2 to CO in the syngas 120. The heat exchange section 116 utilizes a cooling medium to cool the syngas 120. The cooling medium may be, for example, water such as cooling tower water. The cooling medium may flow through the heat exchange section 116 without change in composition and absorb heat from the syngas 120.
In operation, the cooling medium supply 124 enters the heat exchange section 118. The reactor vessel 112 may have a cooling-medium inlet (e.g., inlet nozzle) coupled to a supply conduit (external to the vessel 112) conveying the cooling medium supply 124 to the reactor vessel 112. The cooling medium return 126 discharges from the heat exchange section 118. The reactor vessel 112 may discharge the cooling medium return 126 through cooling-medium outlet (e.g., outlet nozzle of the vessel 112) into a return conduit coupled to the cooling-medium outlet. The return conduit 112 is general external to the vessel 112 and conveys the cooling medium return 126 to the cooling medium system.
With the cooling medium cooling (absorbing heat from) the syngas 120 in the heat exchange section 118, the cooling medium return 126 has a greater temperature than the cooling medium supply 124. Heat transfer occurs from the syngas 120 to the cooling medium in the heat exchange section 118. The cooling medium supply 124 may be, for example, less than 25° C. The cooling medium return 126 may be, for example, at least 100° C.
The heat exchange section 118 may be, for example, a shell-and-tube heat-exchanger type or configuration in which tubes are situated in the heat exchange section 118. The heat exchange section 118 can be configured to flow the cooling medium through the tubes, and flow the syngas 120 external to the tubes. On the other hand, the heat exchange section 118 can be configured to flow the syngas 120 through the tubes, and flow the cooling medium external to the tubes. Other heat exchange or heat exchanger configurations are applicable.
The reactor 106 includes a methanol synthesis section 128 that may be labeled as a methanol synthesis zone, methanol synthesis portion, methanol synthesis reactor, methanol reactor, etc. The methanol synthesis section 128 may be enclosed within the reactor vessel 112 of the reactor 106. The methanol synthesis section 128 receives the cooled syngas 120 discharged from the heat exchange section 118. The methanol synthesis section 128 has a methanol synthesis catalyst 130 to convert the syngas 120 to methanol (e.g., methanol 102).
The methanol synthesis catalyst 130 may be, for example, a copper-based catalyst, copper oxide (CuO) based catalyst, or a zinc oxide (ZnO) based catalyst. The catalyst 130 may include copper (Cu), CuO, ZnO, aluminum oxide (Al2O3) (alumina), or magnesia, or mixtures thereof. In certain implementations, the catalyst 130 includes a mixture of CuO and ZnO, supported on alumina. The catalyst 130 may be Cu—ZnO—Al2O3, sometimes modified with ingredients contributing to the increase of the copper dispersion and stability. Other catalysts are applicable. The reactor vessel 112 may have the catalyst 130 in a fixed bed. In implementations, the reactor 106 may be characterized as fixed-bed reactor with respect to both methanol synthesis and dry reforming.
Catalytic conversion of H2 and CO into methanol can be in the gas phase. The methanol synthesis section 128 may react the CO and H2 from the syngas 120, such as via flow over and/or through the bed of catalyst 130, to produce methanol (CH3OH). This methanol synthesis with respect to the CO can be characterized as a CO hydrogenation reaction: 2H2+CO→CH3OH. Thus, a molar ratio of H2 to CO of at least about 2 in the syngas 120 stream received at the methanol synthesis section 128 may be desirable. As appreciated by one of ordinary skill in the art, methanol synthesis can be favored over DME synthesis. Embodiments can limit DME synthesis and favor methanol synthesis. For instance, methanol synthesis may be favored over DME synthesis by selection of the catalyst 130. Certain catalyst and its component ratios can provide better selectivity for methanol production. For methanol synthesis, Cu-based catalyst may be employed. In contrast, for the DME synthesis, Cu-based catalyst combined with acid catalysts such as γ-Al2O3, zeolites, or silica-modified alumina, may be utilized.
Methanol can be produced by the hydrogenation of CO or CO2 via the catalyst 130. The methanol synthesis can be labeled as hydrogenation of carbon oxides (COx) to methanol. The carbon oxides (COx) are CO and CO2. The operation may add hydrogen 122 (see discussion later) to increase the molar ratio of H2 to CO in the syngas 120 stream by up to 3 or more to account for implementations in which CO2 enters with the syngas 120 flow. In implementations, the molar ratio of H2 to CO being larger than 2 in the entering syngas 12 stream may advance conversion of any CO2 that may enters in the syngas 120 stream in the methanol synthesis reaction and facilitate to suppress side reactions in the methanol synthesis.
The methanol synthesis can be conducted, for example, at a temperature in the range of 175° C. to 325° C. or in the range of 200° C. to 300° C., or at a temperature of at least 175° C., at least 200° C., or less than 350° C. The operating pressure can be, for example, in the range of 10 bars to 70 bars or in the range of 10 bars to 50 bars. The unit bar as used herein is bar absolute (bara). The H2:CO feed molar ratio (e.g., in the incoming syngas 120 stream) for methanol synthesis can be varied in the range, for example, of 1:1 to 3:1 or in the range of 1:1 to 3.5:1. In some instances, to optimize (increase) the feed H2/CO molar ratio, extra H2 (e.g., hydrogen 122) produced by water (H2O) electrolysis utilizing renewable power sources can be injected into the reactor vessel 112.
In general, the residence time in the dry reforming section 114 (dry reforming reaction) and in the methanol synthesis section 128 (methanol synthesis reaction) may be similar. However, the residence time in the methanol synthesis section 128 may be adjusted, for example, by injecting hydrogen after the dry reforming section 114, by changing the catalyst 130 volume (amount), and the like.
The methanol 102 synthesized may discharge from the methanol synthesis section 128 in effluent 110 from the reactor vessel 112. In some implementations, an online analytical instrument 131 (e.g., an online gas chromatograph instrument) may be disposed along the discharge conduit from the reactor vessel 112 to measure composition of the effluent 110. In some implementations, the control system 148 in response to the effluent 110 composition as measured by the online analytical instrument 131, may automatically adjust: (1) flow rate of the carbon dioxide 132 stream (see discussion later), (2) flow rate of the hydrogen 122, or (3) other operating conditions of the reactor 106.
In some implementations, the reactor vessel 112 may include a discharge portion 133 to facilitate discharge of the effluent 110 of the reactor 106. In other implementations, there is no independent discharge portion 133. Instead, the reactor 106 may discharge the effluent 110 of the reactor 106 generally directly from the methanol synthesis section 128.
The methanol synthesis reaction in the methanol synthesis section 128 that converts the syngas 120 to methanol 102 is typically exothermic. Therefore, the reactor vessel 112 at the methanol synthesis section 128 may have a vessel jacket for a heat-transfer fluid that is a cooling medium (e.g., cooling water). The reactor vessel 112 may have cooling coils (internally in the reactor vessel 112 at the methanol synthesis section 128) that route a cooling medium. To cool the reaction mixture and control temperature of the methanol synthesis section 128, heat transfer may occur from the reaction mixture in the methanol synthesis section 128 to the cooling medium in the reactor vessel jacket or in the cooling coils.
In the illustrated embodiment, carbon dioxide 132 is added to methane 134 to give the feed 104 for introduction to the reactor vessel 112. The carbon dioxide 132 stream may be, for example, at least 90 percent (%) of CO2 by volume (vol %) or on a molar basis (mol %). The methane 134 stream may be a methane-rich stream (e.g., at least 60 vol % CH4), such as natural gas, or a process stream or waste stream having CH4. The flow rate of the carbon dioxide 132 stream and/or the methane 134 stream may be controlled to give a desired or specified percent concentration (e.g., vol % or mol %) of CO2 in the feed 104 or a specified molar ratio of CO2 to CH4 in the feed 104. For example, the molar ratio of CO2 to CH4 in the feed 104 may be specified in the range of 1:1 to 3:1. In implementations, the amount of CO2 in the feed 104 is in the range of 30 vol % to 70 vol %, or at least 40 vol %. In the illustrated implementation, the system 100 includes a control valve 136 (e.g., flow control valve) to control (including adjusting) the flow rate of the carbon dioxide 132 stream to give the specified percent (e.g., at least 40 vol %) of CO2 in the feed 104 or the specified molar ratio (e.g., at least 1) of CO2 to CH4 in the feed 104. In implementations, the volume percent or molar percent of each of CO2 and CH4 in the feed 104 can be calculated based on the known flow rates and compositions of the carbon dioxide 132 steam and methane 134 stream. In one embodiment, an online analyzer instrument 136 (e.g., online gas chromatograph instrument) disposed along the conduit conveying the feed 104 measures the amounts (e.g., in vol %) of each of CO2 and CH4 in the feed 104.
In some implementations, the control system 148 may automatically adjust the set point of the control valve 136 in response to the composition of the feed 104 as calculated by the control system 148 or as measured by the online analyzer instrument 138. A human operator or user may enter into the control system 148 a specified value (a set point of a master controller) related to the amount of CO2 in the feed 104, such as for the specified concentration of CO2 in the feed or for the specified molar ratio of CO2 to CH4 in the feed 104. To maintain this entered set point (of the master controller), the master controller may direct the flow controller (FC) of the flow control valve 136 as a slave controller. In particular, the master controller may specify a slave set point (e.g., volume flow rate of CO2 132 stream or mass flow rate of CO2 132 stream) of the FC for the control valve 136 to give the desired set point of the master controller.
The feed 104 may be introduced to an inlet portion 140 of the reactor vessel 112 to facilitate introduction of the feed 104 into the dry reforming section 114. In other implementations, the feed 104 the reactor vessel 112 does not include an independent inlet portion 140, and the feed 104 is instead introduced generally directly into the dry reforming section 114. In some embodiments, the carbon dioxide 132 and methane 134 may be added in two respective separate streams to the reactor vessel 112 via two respective inlets of the reactor vessel 112.
In implementations, as mentioned, the molar ratio of H2 to CO in the syngas 120 as generated by the dry reforming section 114 may generally be approximated at the molar ratio of 1 for the ideal thermodynamic equilibrium or stoichiometric relationship for the dry reforming reaction in the dry reforming section 114. In practice, however, the molar ratio of H2 to CO in the syngas 120 as generated by the dry reforming section 114 may be, for example, in the range of 0.4:1 to 1:1. In implementations, the molar ratio of H2 to CO in the syngas 120 may be estimated based on, for example, the relative amounts of CO2 and CH4 in the feed 104, the operating conditions (e.g., pressure, temperature, etc.) of the dry reforming section 114, the condition of the dry reforming catalyst 116, and so forth. Again, in certain embodiments, the molar ratio of H2 to CO in the syngas 120 as generated by the dry reforming section 114 is in the range of 0.4 to 1. The hydrogen 122 (hydrogen gas H2) may be added to increase this molar ratio to greater than 1, such as in the ranges of 1 to 2, 1.1 to 2, 1 to 3, or 1 to 4, or at a value of least 1.1, at least 1.2, at least 1.8, at least 2, or at least 3. In certain implementations, an online analytical instrument (e.g., online gas chromatograph instrument) is disposed along the reactor vessel 112 to sample the syngas 120 (e.g., as cooled in the heat exchange section 118) to measure the composition of the syngas 120 (with or without the addition of the hydrogen 122) to give a measured value of the molar ratio of H2 to CO in the syngas 120.
A source 142 of hydrogen provides the hydrogen 122 that is added to the reactor vessel 112 to increase the molar ratio of H2 to CO in the syngas 120. The methanol synthesis in the methanol synthesis section 128 may benefit, for example, with the syngas 120 having a molar ratio of H2 to CO of at least 1, at least 1.1, or at least 2. The hydrogen 122 may be injected not only to adjust the molar ratio of the H2/CO, but also to reduce the temperature of the syngas 120. The injected hydrogen 122 may beneficially cool the syngas 120.
In implementations, the flow rate of the hydrogen 122 may be controlled (including adjusted) by a control valve 142 (e.g., flow control valve) to give the desired or specified molar ratio of H2 to CO in the syngas 120. In the illustrated embodiment, the addition point of the hydrogen 122 is depicted at the discharge portion of the dry reforming section 114. However, the hydrogen 122 may also be added to the heat exchange section 118 or at the introduction of the syngas 120 (as cooled in the heat exchange section 118) to the methanol synthesis section 128.
In certain implementations, the source 142 of hydrogen 122 is a water electrolysis unit. Electrolysis of water is the decomposition of water into oxygen and hydrogen gas due to the passage of an electric current. The water electrolysis unit may include at least one water-electrolysis electrochemical cell (electrolytic cell) having a pair of electrodes immersed in water. An electrolyte (e.g., sulfuric acid, potassium hydroxide, sodium hydroxide, etc.) may be added to the water. The pair of electrodes are a cathode and an anode. The cathode and anode may each be an inert metal, such as platinum, stainless steel, iridium, etc. In operation, an electric current may be provided to the cathode. The electrolysis of water may receive energy to overcome activation barriers. In implementations, energy for the electrolysis of water in the water electrolysis unit may be provided via renewable sources, such as energy sources relying on wind or solar.
In the electrochemical cell of the water electrolysis unit, reduction of the water at the cathode generates H2. Oxidation of water at the anode generates oxygen gas (O2). The H2 and O2 may be collected separately. The overall equation of the decomposition of the water in the electrolytic cell can be: 2 H2O→2 H2+O2. Therefore, the number of hydrogen molecules generated may be twice the number of oxygen molecules generated. The electrolysis of water via the water electrolysis unit may produce H2 and O2 at a H2/O2 molar ratio of 2 to 1. The number of electrons through the water can be at least twice the number of generated hydrogen molecules and four times the number of generated oxygen molecules.
As indicated, hydrogen 122 produced from the water electrolysis unit can be added to the syngas 120 to adjust the molar ratio of H2 to CO in the syngas 120. As mentioned for some implementations, a flow control valve 142 disposed along the conduit conveying the hydrogen 122 modulates the amount of hydrogen 122 added to give the desired or specified molar ratio of H2 to CO in the syngas 120. Again, the desired molar ratio may be specified based on the desired molar ratio of H2 to CO for the methanol synthesis. The addition of the hydrogen 122 may increase the H2:CO molar ratio, for example, to between 1 to 2, to between 1 to 3, or to between 1.5 to 3.5.
If needed, a hydrogen mechanical compressor can be disposed along the conduit conveying the hydrogen 122. The hydrogen compressor can provide motive force for flow (addition) of the hydrogen 122 into the reactor vessel 112.
In some implementations, the control system 148 may automatically adjust the set point of the control valve 142 in response to the composition of the syngas 120 as calculated by the control system 148 or as measured by an online analyzer instrument. A human operator or user may enter into the control system 148 a specified value (a set point of a master controller) for the molar ratio of H2 to CO in the syngas 120. To maintain this entered set point (of the master controller), the master controller may direct the flow controller (FC) of the flow control valve 142 as a slave controller. In particular, the master controller may specify a slave set point (e.g., volume flow rate of hydrogen 122 or mass flow rate of hydrogen 122) of the FC for the control valve 142 to give the desired set point of the master controller.
The effluent 110 discharged from the reactor 106 includes the methanol 102 generated in the methanol synthesis section 128. In addition to the methanol 102, the effluent 110 may include H2, CO, and CO2. The amount, e.g., mole percent (mol %), of CO2 in the effluent 110 may be correlative with (e.g., directly proportional with) the amount of CO2 in the feed 104, or correlative with (e.g., directly proportional with) with the molar ratio or volume ratio of CO2 to CH4 in the feed 104. In implementations, the effluent 110 can include unreacted CH4, such as when the conversion of the CH4 of the feed 104 less than 100% in the reactor 106 (including in the dry reforming section 114). In certain implementations, the effluent 110 includes less than 5 mol % of CH4, less than 1 mol % of CH4, less than 0.5 mol % CH4, or less than 0.1 mol % of CH4.
As mentioned, the effluent 110 of the reactor 106 may discharge from the reactor vessel 112 to a downstream system 108 for processing the effluent 110. The downstream system 108 may be a separation system to remove components 144 from the effluent 110 to give the product methanol 102. The components 144 may include, for example, H2, CO, CO2, H2O, and any unreacted CH4. Water can be produced by reverse water gas shift reaction in the methanol synthesis section including under higher CO2-amount dry-reforming condition. The components 144 may be recycled to the reactor 106 or sent to other users.
To separate the components 144 from the effluent 110, the downstream system 106, e.g., separation system(s), may include membrane separator vessel(s), distillation column(s), stripper column(s) having packing or trays, or vessel(s) having adsorbent (that adsorbs and can be regenerated), or any combinations thereof. Various configurations are applicable. The separation of the components 144 from the effluent 110 in the downstream system 108 may involve multi-stage cooling (including partial condensation). The cooling and partial condensation may utilize heat exchanger(s)), refrigeration compressor(s), and the like. The multi-stage cooling may involve separation, such as via flash separation vessels, and the like.
The system 100 for producing methanol may include a control system 148 that may facilitate or direct operation of the system 100, such as in the operation of equipment and the supply or discharge of flow streams (including flow rate and pressure) and associated control valves. The control system 148 may receive data from sensors (e.g., temperature, pressure, etc.) and online analytical instruments in the system 100. The control system 148 may perform calculations. The control system 148 may specify set points for control devices in the system 100. The control system 148 may be disposed in the field or remotely in a control room. The control system 148 may include control modules and apparatuses distributed in the field.
The control system 148 may include a processor 150 and memory 152 storing code (e.g., logic, instructions, etc.) executed by the processor 150 to perform calculations and direct operations of the system 100. The control system 148 may be or include one or more controllers. The processor 150 (hardware processor) may be one or more processors and each processor may have one or more cores. The hardware processor(s) may include a microprocessor, a central processing unit (CPU), a graphic processing unit (GPU), a controller card, circuit board, or other circuitry. The memory 152 may include volatile memory (e.g., cache and random access memory), nonvolatile memory (e.g., hard drive, solid-state drive, and read-only memory), and firmware. The control system 148 may include a desktop computer, laptop computer, computer server, programmable logic controller (PLC), distributed computing system (DSC), controllers, actuators, or control cards.
The control system 148 may receive user input that specifies the set points of control devices or other control components in the system 100. The control system 148 typically includes a user interface for a human to enter set points and other targets or constraints to the control system 148. In some implementations, the control system 148 may calculate or otherwise determine set points of control devices. The control system 148 may be communicatively coupled to a remote computing system that performs calculations and provides direction including values for set points. In operation, the control system 148 may facilitate processes of the system 100 including to direct operation of the reactor 106 and the downstream system 108. Again, the control system 148 may receive user input or computer input that specifies the set points of control components in the system 100. The control system 148 may determine, calculate, and specify the set point of control devices. The determination can be based at least in part on the operating conditions of the system 100 including feedback information from sensors and instrument transmitters, and the like.
Some implementations may include a control room that can be a center of activity, facilitating monitoring and control of the process or facility. The control room may contain a human machine interface (HMI), which is a computer, for example, that runs specialized software to provide a user-interface for the control system. The HMI may vary by vendor and present the user with a graphical version of the remote process. There may be multiple HMI consoles or workstations, with varying degrees of access to data. The control system 148 can be a component of the control system based in the control room. The control system 148 may also or instead employ local control (e.g., distributed controllers, local control panels, etc.) distributed in the system 100. The control system 148 can include a control panel or control module disposed in the field.
The reactor 206 may be analogous to the reactor 106 of
The reactor 206 is a vessel having at least three parts or sections (zones): dry reformer 208, heat exchanger 210, and methanol synthesis reactor 212, which are in the same vessel and analogous to the dry reforming section 114, heat exchange section 118, and methanol synthesis section 128 of
The feedstock for the dry reforming may generally include CH4 (or natural that is primarily CH4) and CO2. The dry reforming may be a technique for conversion of CH4 and CO2 into syngas without the introduction of steam (water). Implementations are performed without introduction of oxygen. Thus, embodiments of the dry reforming are not steam reforming, not mixed-steam CO2 reforming (MSCR) (which may also be known as bi-reforming), and not autothermal reforming (ATR).
The feed 104 to the reactor 206 includes CO2 and CH4. Natural gas may be fed to provide the CH4. Natural gas includes primarily CH4, for example, at 70-90 mol %. Natural gas may include higher alkanes (e.g., ethane, propane, butane) and other components (e.g., nitrogen, hydrogen sulfide, etc.) at a combined concentration, for example, less than 30 mol %. In certain embodiments, the natural gas includes at least 80 mol % CH4 or at least 90 mol % CH4. The natural gas may be combined with a CO2 stream having primarily CO2 to give the feed 104. In embodiments, the natural gas may have no measurable O2 and/or measurable water (H2O), or have trace amounts of 02 and/or H2O. Natural gas generally has no more than 1 mol % of O2 and no more than 1 mol % of H2O. If natural gas is fed, the natural gas and the CO2 of the feed 104 may be fed in a combined stream or as separate streams to the dry reformer 208 of the reactor 206. The flow rate (e.g., volumetric rate, mass rate, or molar rate) of the feed 104 may be controlled via at least one flow control valve (disposed along a supply conduit) or by a mechanical compressor, or a combination thereof. The ratio (e.g., molar, volumetric, or mass ratio) in the feed 104 of the natural gas (or the CH4 in the natural gas) to the CO2 may be adjusted by modulating (e.g., via one or more control valves) at least one of the flow rates of the natural gas or CO2 streams. The supply pressure of the feed 104 may provide for or facilitate the operating pressures in the reactor 106. Moreover, in one implementation, the system 200 may include upstream equipment (e.g., desulfurizer, pre-reformer, etc.) to process or treat the feed 104.
The CH4 content (or natural gas content) in the feed 104 may be at a volume concentration, for example, in the ranges of 20% to 60%, 25% to 60%, or 25% to 50%, or less than 60 vol %, less than 50 vol %, or less than 30 vol %. The CO2 content in the feed 104 may be at a volume concentration in the ranges of 40% to 80%, 40% to 75%, or 50% to 75%, or at least 40 vol %, at least 50 vol %, or at least 75 vol %.
In certain embodiments, the dry reforming in the dry reformer 208 is a fixed-bed catalytic process. Thus, the dry reformer 208 may have a fixed bed of dry reformer catalyst (dry reforming catalyst). The dry reforming in the dry reformer 208 may be a catalytic reaction where, for instance, the catalyst has an oxide support with active metal or metal sites available for the reaction. The dry reformer catalyst may be, for example, a nickel-based catalyst. The dry reformer catalyst may be or include, for example, noble metals, nickel (Ni), or Ni alloys. In some embodiments, the catalyst is magnesium oxide (MgO) or MgO nanoparticles. The MgO or MgO nanoparticles may be promoted with Ni and/or molybdenum (Mo), for example. In one implementation, the catalyst is MgO nanoparticles promoted with Ni and Mo. Other dry reformer catalysts are applicable.
Again, the feed 104 to the reactor 206 and thus to the dry reformer 208 includes CH4 and CO2. While O2 is generally not fed to the dry reformer 208, O2 may be involved in the dry reforming via the dissociation of the CO2. With respect to the dry reforming mechanism, the dry reforming may disassociate CO2 into O2 and CO. A re-oxidation reaction may occur via the O2 at reduced oxide sites of the catalyst support in some implementations. The oxygen from the oxide site of the catalyst support can react with CH4 to produce CO and H2 as contribution to the syngas.
The dry reforming reaction is typically endothermic. Thus, in operation, heat is added to the dry reformer 208. In some implementations, the portion of the reactor 206 vessel having the dry reformer 208 may have a vessel jacket for flow of heat transfer fluid (e.g., steam, hot oil, hot synthetic fluid, etc.) to transfer heat from the heat transfer fluid from the jacket through the vessel wall to the dry reforming reaction mixture in the dry reformer 208. In addition or in lieu of a vessel jacket, electrical heaters may provide heat for the endothermic dry reforming reaction. The electrical heaters may be disposed in the reactor 206 vessel in the dry reformer 208 or on an external surface of reactor 206 vessel at the dry reformer 208. Other configurations of heat transfer and temperature control of the dry reformer 208 are applicable. The operating temperature in the dry reformer 208 may be, for example, at less than 850° C., less than 800° C., in the range of 700° C. to 900° C., in the range of 750° C. to 875° C., or in the range of 800° C. to 850° C. The operating pressure of (in) the dry reformer 208 may be, for example, in the range of 10 bars to 70 bars.
As discussed, hydrogen may be added to the reactor 206 to increase the molar ratio of H2 to CO of the syngas generated by the dry reformer 208. Hydrogen may be added to the reactor 206 vessel at an inlet nozzle of the reactor vessel into an internal discharge portion of the dry reformer 208 or at other parts of the reactor 206. The source of the H2 may be, for example, a H2 piping header or a H2 tube trailer, and the like. In some implementations, the source of the H2 is a water electrolysis unit. The H2 supplied by the water electrolysis unit may be labeled as renewable H2 in implementations in which the water electrolysis unit is driven by renewable energy sources, such as energy sources relying on wind or solar.
The syngas (including any added H2) is cooled in the heat exchanger 210. The heat exchanger 210 is generally disposed within the reactor 206 vessel. In operation, the heat exchanger 210 cools (removes heat from) the syngas discharged from the dry reformer 208 The cooling medium for the heat exchanger 210 may be, for example, cooling water. The cooling medium may flow through the heat exchanger 210 to absorb heat from the syngas. The heat exchanger 210 may be, for example, a shell-and-tube heat-exchanger type or configuration in which the tubes are situated in the reactor 206 vessel. The reactor 206 vessel wall may act as the shell of the heat exchanger 210 housing the tubes, or the shell of the heat exchanger 210 housing the tubes is disposed in the reactor 206 vessel. Other heat exchanger configurations are applicable.
The methanol synthesis reactor 212 in the reactor 206 vessel receives the cooled syngas that flows from (discharged from) the heat exchanger 210. The methanol synthesis reaction in the methanol synthesis reactor 212 that converts the syngas to methanol 102 is generally exothermic. Therefore, the reactor 206 vessel at the methanol synthesis reactor 212 may have a vessel jacket for a heat-transfer fluid that is a cooling medium (e.g., cooling water). In addition to (or in lieu of) a vessel jacket, the reactor 206 vessel may have cooling coils internally in the methanol synthesis reactor 212 that route a cooling medium. The operating temperature in the methanol synthesis reactor 212 may be, for example in the range of 175° C. to 325° C., or in a range of 200° C. to 300° C., or at least 175° C., at least 200° C., or less than 350° C. The operating pressure may be, for example, in a range of 10 bars to 70 bars or in a range of 10 bars to 50 bars.
The methanol synthesis reactor 212 has methanol synthesis catalyst to convert the syngas to methanol (e.g., methanol 102). The methanol synthesis catalyst may be, for example, a Cu-based catalyst, CuO-based catalyst CuO—ZnO based catalyst, etc. The methanol 102 generated via the methanol synthesis discharges in the reactor 206 effluent 110 from the methanol synthesis reactor 212 and thus from the reactor 206 vessel in the illustrated implementation.
The system 200 may include a separation system 214 that may be analogous to the downstream system 108 of
The separation system 214 may employ, for example, a multi-stage cooling separation. The separation system 214 may be or include a multi-stage cooling separation unit. The multi-stage cooling may include condensation and flash separation. The gas phase flow of a flash separation vessel after cooling and partial condensation may enter the next flash separation vessel. The separation system(s) may include a membrane separator vessel, a distillation column, a vessel having adsorbent, and so forth. In the illustrated embodiment, the product methanol 102 stream discharges from separation system 214.
The system 200 may include the control system 148, as discussed with respect to
Therefore, a reactor having a reactor vessel may perform both the dry reforming and methanol synthesis in the same reactor vessel. Accordingly, the reactor may perform two different types of reaction (dry reforming and methanol synthesis) in the same reactor vessel.
At block 302, the method includes providing feed including methane and carbon dioxide to the vessel. The method may provide the feed to a dry reformer (or dry reforming section) in the vessel. Again, the vessel may be a vessel of a reactor and thus be labeled as the reactor vessel. The vessel may have a feed inlet (e.g., inlet nozzle) to receive the feed. The feed inlet nozzle may be coupled (e.g., flanged connection, threaded connection, etc.) to a supply conduit conveying the feed to the vessel. The vessel may include more than one feed inlet nozzles to receive the feed. In certain implementations, a control valve is disposed along a conduit conveying the carbon dioxide for the feed. The control valve controls flow rate of the carbon dioxide to give a specified amount of carbon dioxide of the feed. Thus, the method may include controlling the flow rate of the carbon dioxide provided for the feed to the vessel to give a specified amount of carbon dioxide of the feed. The specified amount of carbon dioxide of the feed may be, for example, ratio (e.g., molar ratio) of the carbon dioxide to the methane of the feed or a concentration (e.g., vol % or mol %) of the carbon dioxide in the feed.
At block 304, the method includes converting the methane and the carbon dioxide by dry reforming (e.g., via dry reforming catalyst) in the vessel into syngas including hydrogen and carbon monoxide. The dry reforming may be performed via the dry reforming catalyst in a dry reformer (or dry reforming section) in the vessel. The dry reforming catalyst may be a fixed bed of catalyst in the dry reforming section (dry reformer) in the vessel.
At block 306, the method may include adding hydrogen to the vessel, such as to increase the ratio (e.g., molar ratio) in the syngas of hydrogen to carbon monoxide. The vessel may have a hydrogen inlet (e.g., inlet nozzle) coupled to a hydrogen supply conduit (external to the vessel) to receive the hydrogen to increase the molar ratio of hydrogen to carbon monoxide of the syngas in the vessel. In some implementations, a water electrolysis unit (including a water-electrolysis electrochemical cell) provides the hydrogen through the hydrogen supply conduit to the hydrogen inlet on the vessel. In certain implementations, a flow control valve is disposed along the supply conduit conveying the hydrogen to the hydrogen inlet on the vessel, wherein the control valve controls flow rate of the hydrogen from the hydrogen source (e.g., water electrolysis unit) to the vessel.
At block 308, the method includes cooling the syngas via a heat exchanger (heat exchange section) in the vessel. The method may include flowing the syngas from the dry reforming section through the heat exchange section in the vessel to cool the syngas with a cooling medium (e.g., cooling water) in the heat exchange section. The heat exchange section may include the heat exchanger that cools the syngas with the cooling medium, and wherein flowing the syngas from the dry reforming section through the heat exchange section includes flowing the syngas through the heat exchanger (e.g., shell-and-tube heat exchanger).
At block 310, the method includes synthesizing methanol (e.g., via methanol synthesis catalyst) from the syngas in the vessel. The method may include flowing the syngas as cooled from the heat exchange section (heat exchanger) to the methanol synthesis section in the vessel, and synthesizing methanol from the syngas via the methanol synthesis catalyst in the methanol synthesis section. The methanol synthesis catalyst may be a fixed bed of catalyst in the methanol synthesis section (methanol synthesis reactor) in the vessel to give the methanol as a component of the vessel effluent.
At block 312, the method includes discharging effluent (having the methanol) from the vessel. The vessel may have an outlet discharge nozzle to discharge the effluent from the vessel into an effluent discharge conduit. The discharging of the effluent from the vessel may be discharging the effluent from the methanol synthesis section (or methanol synthesis reactor) in the vessel. Again, the vessel may have an effluent outlet (outlet nozzle) coupled to an effluent discharge conduit external to the vessel for discharge of the effluent from the vessel (e.g., to a separation system, as discussed with respect to block 314).
At block 314, the method may include processing the effluent (as discharged) to remove components (e.g., H2, CO, CO2, H2O, any unreacted methane, etc.) from the effluent to give the methanol as product. In implementations, the combination of hydrogen, carbon monoxide, and carbon dioxide may be the majority of the components removed. The processing of the effluent to remove the components may be performed in a separation system (e.g., including at least one flash vessel). In implementations, the separation system may be a multi-stage cooling (including partial condensation) system. Other unit operations for the separation system may be implemented, such as membrane separation (membrane separator vessel), distillation (distillation column), and so on.
At block 316, the method may include providing (recycling, returning) at least one of the components removed from the effluent to the vessel. The vessel may include an inlet (e.g., an inlet nozzle) to receive at least one of the components removed from the effluent. The inlet nozzle may be coupled to a conduit conveying the component(s) from the separation system. The method may include providing (e.g., via a conduit) at least one of the hydrogen, the carbon monoxide, or the carbon dioxide removed from the effluent to the dry reforming section (dry reformer) in the vessel. The vessel may have an inlet nozzle at the dry reforming section to receive this return of component(s) to the vessel. The method may include providing (e.g., via a conduit) at least one of the hydrogen, the carbon monoxide, or the carbon dioxide removed from the effluent to the methanol synthesis section. The vessel have an inlet nozzle at the methanol synthesis section to receive this return of component(s) to the vessel. An embodiment a method of producing methanol via dry reforming and methanol synthesis, the method including providing feed including methane and carbon dioxide to a vessel, converting methane and carbon dioxide in the vessel into syngas including hydrogen and carbon monoxide via dry reforming in the vessel, cooling the syngas via a heat exchanger in the vessel, synthesizing methanol from the syngas in the vessel, and discharging effluent (including methanol) from the vessel. The method may include heating a dry reforming section of the vessel and cooling a methanol synthesis section of the vessel. The method may include processing the effluent as discharged to remove components from the effluent to give the methanol as product, the components including hydrogen, carbon monoxide, and carbon dioxide. If so, the method may include recycling the hydrogen, the carbon monoxide, and the carbon dioxide removed from the effluent to the vessel. The converting of the methane and the carbon dioxide in the vessel may involve converting the methane and the carbon dioxide via dry reforming catalyst in the vessel into the syngas. The synthesizing of the methanol may involve synthesizing the methanol from the syngas via methanol synthesis catalyst in the vessel. The method may include adding hydrogen to the vessel to increase a molar ratio of hydrogen to carbon monoxide of the syngas.
Another embodiment is a method of producing methanol, including converting (dry reforming) methane and carbon dioxide via a dry reforming catalyst in a dry reforming section in a reactor vessel into syngas including hydrogen and carbon monoxide, wherein the converting includes dry reforming. The method may include providing feed including the methane and the carbon dioxide to the dry reforming section in the reactor vessel. The method includes flowing the syngas from the dry reforming section through a heat exchange section in the reactor vessel to cool the syngas with a cooling medium in the heat exchange section. The heat exchange section may have a heat exchanger that cools the syngas with the cooling medium, wherein flowing the syngas from the dry reforming section through the heat exchange section includes flowing the syngas through the heat exchanger. The method includes flowing the syngas as cooled from the heat exchange section to a methanol synthesis section in the reactor vessel. The method includes synthesizing methanol from the syngas via a methanol synthesis catalyst in the methanol synthesis section. The method may include discharging effluent including the methanol from the reactor vessel. The method may include processing effluent including the methanol discharged from the reactor vessel to remove hydrogen, carbon monoxide, and carbon dioxide from the effluent to give the methanol as product. If so, the method may include providing at least one of the hydrogen, the carbon monoxide, or the carbon dioxide removed from the effluent to the dry reforming section. The method may include providing at least one of the hydrogen, the carbon monoxide, or the carbon dioxide removed from the effluent to the methanol synthesis section.
Yet another aspect relates to a methanol production system including a reactor vessel having a feed inlet to receive a feed including methane and carbon dioxide. A control valve may be disposed along a conduit conveying the carbon dioxide for the feed to control flow rate of the carbon dioxide to give a specified amount of carbon dioxide of the feed. The specified amount may be a ratio of the carbon dioxide to the methane of the feed or a concentration of the carbon dioxide in the feed. The reactor vessel includes a dry reforming section having a dry reforming catalyst in the reactor vessel to convert the methane and the carbon dioxide into syngas including hydrogen and carbon monoxide. The dry reforming catalyst may be a fixed bed of catalyst in the dry reforming section in the reactor vessel. The reactor vessel includes a heat exchange section having a heat exchanger in the reactor vessel to receive the syngas from the dry reforming section and cool the syngas with a cooling medium. The heat exchanger may be a shell-and-tube heat exchanger. The cooling medium may include cooling water. The reactor vessel includes a methanol synthesis section having a methanol synthesis catalyst in the reactor vessel to synthesize methanol from the syngas and discharge an effluent including the methanol from the reactor vessel. The methanol synthesis catalyst may be a fixed bed of catalyst in the methanol synthesis section in the reactor vessel. The methanol production system may include a separation system to remove components from the effluent as discharged to give the methanol as methanol product, the components removed including hydrogen, carbon monoxide, and carbon dioxide, wherein the separation system includes a flash vessel, and wherein the reactor vessel has an effluent outlet for discharge of the effluent from the reactor vessel. The reactor vessel may have an inlet to receive at least one of the components removed from the effluent. The reactor vessel may have a hydrogen inlet to receive hydrogen to increase a molar ratio of hydrogen to carbon monoxide of the syngas in the reactor vessel. A water electrolysis unit including a water-electrolysis electrochemical cell may provide the hydrogen received at the hydrogen inlet. A control valve disposed along a conduit conveying the hydrogen to the hydrogen inlet, wherein the control valve controls flow rate of the hydrogen from the water electrolysis unit to the reactor vessel.
The Examples are given only as examples and not meant to limit the present techniques. Examples 1-4 are presented.
Conditions of Examples 1 and 2 are given in Table 1. In Example 1, the feed (excluding nitrogen) was 50 mol % CO2 and 50 mol % CH4. In Example 2, the feed (excluding nitrogen) was 75 mol % CO2 and 25 mol % CH4. Nitrogen gas was fed along with the CH4 and CO2. Nitrogen is inert and does not react.
In Example 1, an evaluation of a dry reforming catalyst was performed in the laboratory with micro-reactor and online gas chromatography (GC). The micro-reactor was a stainless-steel tube with diameter of 9 millimeters (mm) mounted in a furnace. During the micro-scale testing, about 1 gram of catalyst was added to the tube, and the tube mounted in the furnace. Methane, carbon dioxide, and nitrogen were introduced to the furnace by a mass flow controller. The temperature of reactor was increased up to 800° C. with a ramp of 10° C./minute and kept at 800° C. during the reaction. Composition of effluent gas discharged from the reactor was analyzed from online GC in order to calculate conversions and H2/CO molar ratio. The time on stream for the reaction was 850 hours. The conversion of CH4 and the conversion of CO2 were both about 100% over the entire 850 hours.
In Example 2, an evaluation of the dry reforming catalyst (same catalyst as in Example 1) was performed in the laboratory with micro-reactor and online gas chromatography (GC). The micro-reactor was a stainless-steel tube with diameter of 9 millimeters (mm) mounted in a furnace. During the micro-scale testing, about 1 gram of catalyst was added to the tube, and the tube mounted in the furnace. Methane, carbon dioxide, and nitrogen were introduced to the furnace by a mass flow controller. The temperature of reactor was increased up to 800° C. with a ramp of 10° C./minute and kept at 800° C. during the reaction. Composition of effluent gas discharged from the reactor was analyzed from online GC in order to calculate conversions and H2/CO molar ratio. The time on stream for the reaction was 24 hours. The conversion of CH4 over the 24 hours was consistently about 95%. The conversion of CO2 over the 24 hours was consistently about 45%.
A reactor was simulated via Aspen Plus® software (version 10). Aspen Plus® software is available from Aspen Technology, Inc. having headquarters in Bedford, Mass., USA. The reactor simulated has a dry reforming part and methanol synthesis part (and heat exchanger disposed there between), such as the reactor 106, 206 discussed above with respect to
Based on the simulation results for Example 3, it was found that 31.6 kilogram per day (kg/day) of CO2 and 11.55 kg/day of CH4 and 5.81 kg/day of extra H2 enabled to ideally produce 46.14 kg/day of methanol. Based on the simulation results for Example 4, 11.55 kg/day of CH4, 95.06 kg/day of CO2 and 9.68 kg/day of extra H2 can ideally produce 61.52 kg/day of methanol.
A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the disclosure.
