US20230416179A1 - Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel - Google Patents
Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel Download PDFInfo
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- US20230416179A1 US20230416179A1 US18/463,093 US202318463093A US2023416179A1 US 20230416179 A1 US20230416179 A1 US 20230416179A1 US 202318463093 A US202318463093 A US 202318463093A US 2023416179 A1 US2023416179 A1 US 2023416179A1
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- dme
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 415
- 238000002407 reforming Methods 0.000 title claims abstract description 119
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 105
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 240
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 181
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 152
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 151
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000001257 hydrogen Substances 0.000 claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 82
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims description 79
- 239000002826 coolant Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 27
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 abstract description 17
- 230000002194 synthesizing effect Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000003345 natural gas Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000006057 reforming reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 241000183024 Populus tremula Species 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000005431 greenhouse gas Substances 0.000 description 5
- 239000013529 heat transfer fluid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 230000004044 response Effects 0.000 description 3
- 238000010977 unit operation Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000002453 autothermal reforming Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000005204 segregation Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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Definitions
- This disclosure relates to dry reforming of methane and dimethyl ether (DME) synthesis.
- Methane which may be labeled as the simplest hydrocarbon, may be subjected to steam reforming to generate synthetic gas (syngas) that includes hydrogen (H 2 ) and carbon monoxide (CO).
- syngas may be distributed including 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 method of producing dimethyl ether (DME) via dry reforming and DME 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 DME from the syngas in the vessel, and discharging effluent (having DME) from the vessel.
- DME dimethyl ether
- the method includes 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.
- 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 DME synthesis section in the reactor vessel.
- the method includes synthesizing DME from the syngas via a DME synthesis catalyst in the DME synthesis section.
- a DME production system including a reactor vessel having a feed inlet to receive a feed comprising 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 DME synthesis section having a DME synthesis catalyst in the reactor vessel to synthesize DME from the syngas and discharge an effluent including the DME from the reactor vessel.
- FIG. 1 is a diagram of a system that produces dimethyl ether (DME).
- DME dimethyl ether
- FIG. 2 is a diagram of a system that produces DME, and which may be analogous to FIG. 1 .
- FIG. 3 is a block flow diagram of a method of producing DME via dry reforming and DME synthesis in the same vessel
- FIG. 4 is an Aspen Plus® simulation diagram.
- DME dimethyl ether
- methoxymethane may generally be a colorless gas at ambient conditions.
- DME has the formula CH 3 OCH 3 and may be thought of as the simplest ether.
- DME may also be expressed as the formula (CH 3 ) 2 O or the simplified formula expression C 2 H 6 O.
- Some aspects of the present disclosure are directed DME generation from carbon dioxide and methane in a vessel (a reactor vessel). Carbon dioxide and methane may be fed to the vessel.
- the DME generated in the vessel may discharge from the vessel.
- the DME synthesis may be via dry reforming of the methane in the vessel.
- the DME may be synthesized from the synthetic gas (syngas) generated by the dry reforming. Again, the dry reforming and the DME synthesis may occur in the same vessel.
- Dry reforming may be beneficial for consuming the two-greenhouse gases methane (CH 4 ) and carbon dioxide (CO 2 ). Dry reforming is a process that may react CH 4 with CO 2 to produce syngas with the aid of catalyst.
- the syngas may include hydrogen (H 2 ) and carbon monoxide (CO).
- the dry reforming reaction may be characterized as CH 4 +CO 2 ⁇ 2H 2 +2CO.
- aspects may include DME production by performing both dry reforming and DME synthesis in the same vessel.
- embodiments of the present techniques include a reactor for DME synthesis via dry reforming, and in which both the dry reforming reaction and the DME synthesis reaction occur in the same reactor vessel.
- the reactor (reactor vessel) may have at least three sections including a dry reforming section, a heat exchanger section, and a DME synthesis section. The reactor converts carbon dioxide and methane into DME in the vessel of the reactor.
- CO 2 conversion technologies have attracted attention at least because of difficulties associated with geological storage of CO 2 .
- An aim of CO 2 conversion may be to utilize concentrated CO 2 (e.g. from CO 2 capture) as a feedstock to produce valuable chemicals via various conversion processes.
- dry reforming of CH 4 is a CO 2 conversion technology for mitigating CO 2 emissions.
- the dry reforming of CH 4 may also reduce emissions of CH 4 , which like CO 2 , is a greenhouse gas.
- Embodiments herein utilize CO 2 as feedstock via DRM to produce DME.
- the syngas produced from DRM is utilized directly in DME production.
- the syngas produced from DRM may be primarily H 2 and CO at a molar ratio of 1:1 based on the ideal thermodynamic equilibrium.
- FIG. 1 is a system 100 that produces DME 102 .
- the feed 104 includes CO 2 and CH 4 .
- CO 2 the CO 2 footprint
- CH 4 may be fed in a methane-rich stream, such as natural gas. Utilization of CH 4 as feed can reduce CH 4 emissions at a facility.
- the system 100 includes a reactor 106 , as well as a downstream system 108 that processes effluent 110 from the reactor 106 to give the DME 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.
- 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 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) might be structurally separate in the vessel via, for example, divider plate or divider meshes. 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.
- 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 .
- the reactor 106 is configured to perform two different reactions of dry reforming and DME synthesis contemporaneously in two respective sections, as discussed below. While the DME 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 CH 4 +CO 2 ⁇ 2H 2 +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 CH 4 and CO 2 of the feed 104 into synthetic gas (syngas).
- the generated syngas includes H 2 and CO.
- the dry reforming catalyst 116 may be a fixed bed of catalyst in the dry reforming section 114 .
- 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 CO 2 and CH 4 in the feed 104 to the dry reforming section 114 can vary, for example, in the range of 1:1 to 3:1.
- the molar ratio of H 2 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 produced syngas is generally H 2 and CO, and the molar ratio of H 2 to CO in the syngas is ideally 1 but in practice can be, for example, in the range of 0.4 to 1.
- heat may be added to the dry reforming section 114 .
- 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 DME synthesis.
- the heat exchange section 118 cools the syngas 120 discharged from the dry reforming section 114 .
- the syngas 120 can include additional H 2 added to increase the molar ratio of H 2 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 .
- the cooling medium supply 124 enters the heat exchange section 116 .
- 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 116 .
- the reactor vessel 112 may have a cooling-medium outlet (e.g., outlet nozzle) coupled to a return conduit (external to the vessel 112 ) conveying the cooling medium return 126 to the cooling medium system.
- 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.
- 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.
- 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 DME synthesis section 128 that may be labeled as a DME synthesis zone, DME synthesis portion, DME synthesis reactor, DME reactor, etc.
- the DME synthesis section 128 may be enclosed within the reactor vessel 112 of the reactor 106 .
- the DME synthesis section 128 receives the cooled syngas 120 discharged from the heat exchange section 118 .
- the DME synthesis section 128 has a DME synthesis catalyst 130 to convert the syngas 120 to DME (e.g., DME 102 ).
- the DME synthesis catalyst 130 may be, for example, a copper-based catalyst.
- the catalyst 130 may be a copper oxide (CuO) based catalyst or a zinc oxide (ZnO) based catalyst.
- the catalyst 130 includes a mixture of copper oxide and zinc oxide, supported on alumina. Other catalysts are applicable.
- the reactions may involve these three reactions (1) methanol synthesis from CO and H 2 , (2) methanol dehydration to give DME, and (3) water gas shift to give (4) the overall reaction.
- the DME synthesis can be conducted at a temperature in the range of 175° C. to 350° C., or in the range of 200° C. to 300° C., or at least 175° C., at least 200° C., or less than 350° C., and at a pressure, for example, in the range of 10 bars to 70 bars.
- the unit bar as used herein is bar absolute (bara).
- the H 2 :CO feed molar ratio for DME synthesis can be varied in the range of 1:1 to 2:1. In some instances, to optimize (increase) the feed H 2 /CO ratio, extra H 2 produced by water (H 2 O) electrolysis utilizing renewable power sources can be injected.
- the residence time in the dry reforming section 114 (dry reforming reaction) and in the DME synthesis section 128 (DME synthesis reactions) may be similar.
- the residence time in the DME 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 DME 102 synthesized may discharge from the DME synthesis section 128 in effluent 110 from the reactor vessel 112 .
- an online analytical instrument 131 e.g., an online gas chromatograph instrument
- 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 below), (2) flow rate of the hydrogen 122 (see below), or (3) other operating conditions of the reactor 106 .
- the reactor vessel 112 may include a discharge portion 133 to facilitate discharge of the effluent 110 of the reactor 106 .
- there is no independent discharge portion 133 and the effluent 110 of the reactor 106 instead discharges generally directly from the DME synthesis section 128 .
- the DME synthesis reaction in the DME synthesis section 128 that converts the syngas 120 to DME 102 is generally exothermic. Therefore, the reactor vessel 112 at the DME 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 DME synthesis section 128 ) that route a cooling medium. To cool the reaction mixture and control temperature of the DME synthesis section 128 , heat transfer may occur from the reaction mixture in the DME synthesis section 128 to the cooling medium in the reactor vessel jacket or in the cooling coils.
- 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 CO 2 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 % CH 4 ), such as natural gas, or a process stream or waste stream having CH 4 .
- 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 CO 2 in the feed 104 or a specified molar ratio of CO 2 to CH 4 in the feed 104 .
- the molar ratio of CO 2 to CH 4 in the feed 104 may be specified in the range of 1:1 to 3:1.
- the amount of CO 2 in the feed 104 is in the range of 30 vol % to 70 vol %, or at least 40 vol %.
- 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 CO 2 in the feed 104 or the specified molar ratio (e.g., at least 1) of CO 2 to CH 4 in the feed 104 .
- the volume percent or molar percent of each of CO 2 and CH 4 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.
- 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 CO 2 and CH 4 in the feed 104 .
- 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 CO 2 in the feed 104 , such as for the specified concentration of CO 2 in the feed or for the specified molar ratio of CO 2 to CH 4 in the feed 104 .
- the master controller may direct the flow controller (FC) of the flow control valve 136 as a slave controller.
- the master controller may specify a slave set point (e.g., volume flow rate of CO 2 132 stream or mass flow rate of CO 2 132 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 .
- 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 .
- 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 .
- the molar ratio of H 2 to CO in the syngas 120 as generated by the dry reforming section 114 may generally be approximated at the ideal ratio of 1 for the ideal thermodynamic equilibrium or stoichiometric relationship for the dry reforming reaction in the dry reforming section 114 .
- the molar ratio of H 2 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.
- the molar ratio of H 2 to CO in the syngas 120 may be estimated based on, for example, the relative amounts of CO 2 and CH 4 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 H 2 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 H 2
- an online analytical instrument e.g., online gas chromatograph instrument
- sample the syngas 120 e.g., as cooled in the heat exchange section 118
- measure the composition of the syngas 120 with or without the addition of the hydrogen 122
- a source 142 of hydrogen provides the hydrogen 122 that is added to the reactor vessel 112 to increase the molar ratio of H 2 to CO in the syngas 120 .
- the DME synthesis in the DME synthesis section 128 may benefit, for example, with the syngas 120 having a molar ratio of H 2 to CO of at least 1, or at least 1.1.
- the hydrogen 122 may be injected not only to adjust the molar ratio of the H 2 /CO, but also to reduce the temperature of the syngas 120 .
- the injected hydrogen 122 may cool the syngas 120 .
- 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 H 2 to CO in the syngas 120 .
- a control valve 142 e.g., flow control valve
- the addition point of the hydrogen 122 is depicted at the discharge portion of the dry reforming section 114 .
- 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 DME synthesis section 128 .
- 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.
- 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.
- 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.
- the electrochemical cell of the water electrolysis unit reduction of the water at the cathode generates H 2 .
- Oxidation of water at the anode generates oxygen gas (O 2 ).
- the H 2 and O 2 may be collected separately.
- the overall equation of the decomposition of the water in the electrolytic cell can be: 2H 2 O ⁇ 2H 2 +O 2 . 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 H 2 and O 2 at a H 2 /O 2 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.
- hydrogen 122 produced from the water electrolysis unit can be added to the syngas 120 to adjust the molar ratio of H 2 to CO in the syngas 120 .
- 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 H 2 to CO in the syngas 120 .
- the desired molar ratio may be specified based on the desired molar ratio of H 2 to CO for the DME synthesis.
- the addition of the hydrogen 122 may increase the H 2 :CO molar ratio, for example, to between 1 to 2.
- 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 .
- 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 H 2 to CO in the syngas 120 .
- the master controller may direct the flow controller (FC) of the flow control valve 142 as a slave controller.
- 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 DME 102 generated in the DME synthesis section 128 .
- the effluent 110 may include H 2 , CO, and CO 2 .
- the amount, e.g., mole percent (mol %), of CO 2 in the effluent 110 may be correlative with (e.g., directly proportional with) the amount of CO 2 in the feed 104 , or correlative with (e.g., directly proportional with) with the molar ratio or volume ratio of CO 2 to CH 4 in the feed 104 .
- the effluent 110 can include unreacted CH 4 , such as when the conversion of the CH 4 of the feed 104 less than 100% in the reactor 106 (including in the dry reforming section 114 ).
- the effluent 110 includes less than 5 mol % of CH 4 , less than 1 mol % of CH 4 , less than 0.5 mol % CH 4 , or less than 0.1 mol % of CH 4 .
- 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 DME 102 .
- the components 144 may include, for example, H 2 , CO, CO 2 , and any unreacted CH 4 .
- the components 144 may be recycled to the reactor 106 or sent to other users.
- the downstream system 106 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.
- 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.
- 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 DME 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.
- PLC programmable logic controller
- DSC distributed computing system
- 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 .
- 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 .
- 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.
- HMI human machine interface
- the HMI may vary by vendor and present the user with a graphical version of the remote process.
- 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.
- FIG. 2 is a system 200 that produces DME 102 .
- the system 200 includes a reactor 206 that performs dry reforming of CH 4 .
- the feed 104 to the reactor 206 includes CO 2 and CH 4 .
- the dry reforming of CH 4 with CO 2 as the oxidant is a technique that beneficially converts the greenhouse-gases CO 2 and CH 4 into syngas that is primarily H 2 and CO.
- the molar ratio H 2 to CO in the syngas may deviate from ideal thermodynamic equilibrium of 1 to in the range of 0.4 to 1, for example.
- Hydrogen may be added to the syngas in the reactor 206 to increase the molar ratio of H 2 to CO if desired.
- the reactor 206 may be analogous to the reactor 106 of FIG. 1 .
- the reactor 206 may include two reactors in the same reactor vessel: a reactor for dry reforming CH 4 to generate syngas and a reactor for DME synthesis from the syngas.
- the reactor 206 is a vessel having at least three parts or sections (zones): dry reformer 208 , heat exchanger 210 , and DME synthesis reactor 212 , which are in the same vessel and analogous to the dry reforming section 114 , heat exchange section 118 , and DME synthesis section 128 of FIG. 1 , respectively.
- the dry reformer 208 reactor and the DME synthesis reactor 212 are in the same reactor vessel.
- the heat exchanger is also disposed in the same reactor vessel between the dry reformer 208 reactor and the DME synthesis reactor 212 .
- the feedstock for the dry reforming may generally include CH 4 (or natural that is primarily CH 4 ) and CO 2 .
- the dry reforming may be a technique for conversion of CH 4 and CO 2 into syngas without the introduction of steam (water). Implementations are performed without introduction of oxygen.
- embodiments of the dry reforming are not steam reforming, not mixed-steam CO 2 reforming (MSCR) (which may also be known as bi-reforming), and not autothermal reforming (ATR).
- the feed 104 to the reactor 206 includes CO 2 and CH 4 .
- Natural gas may be fed to provide the CH 4 .
- Natural gas includes primarily CH 4 , 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 %.
- the natural gas includes at least 80 mol % CH 4 or at least 90 mol % CH 4 .
- the natural gas may be combined with a CO 2 stream having primarily CO 2 to give the feed 104 .
- the natural gas may have no measurable O 2 and/or measurable water (H 2 O), or have trace amounts of O 2 and/or H 2 O.
- Natural gas generally has no more than 1 mol % of O 2 and no more than 1 mol % of H 2 O. If natural gas is fed, the natural gas and the CO 2 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 CH 4 in the natural gas) to the CO 2 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 CO 2 streams.
- the supply pressure of the feed 104 may provide for or facilitate the operating pressures in the reactor 106 .
- the system 200 may include upstream equipment (e.g., desulfurizer, pre-reformer, etc.) to process or treat the feed 104 .
- the CH 4 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 CO 2 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 %.
- the dry reforming in the dry reformer 208 is a fixed-bed catalytic process.
- 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.
- 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.
- the catalyst is MgO nanoparticles promoted with Ni and Mo.
- Other dry reformer catalysts are applicable.
- the feed 104 to the reactor 206 and thus to the dry reformer 208 includes CH 4 and CO 2 .
- O 2 may be involved in the dry reforming via the dissociation of the CO 2 .
- the dry reforming may disassociate CO 2 into O 2 and CO.
- a re-oxidation reaction may occur via the O 2 at reduced oxide sites of the catalyst support in some implementations.
- the oxygen from the oxide site of the catalyst support can react with CH 4 to produce CO and H 2 as contribution to the syngas.
- the dry reforming reaction is typically endothermic.
- heat is added to the dry reformer 208 .
- 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 .
- heat transfer fluid e.g., steam, hot oil, hot synthetic fluid, etc.
- 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 .
- 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.
- hydrogen may be added to the reactor 206 to increase the molar ratio of H 2 to CO of the syngas generated by the dry reformer 208 .
- Hydrogen may be added to the reactor 206 vessel at a discharge portion of the dry reformer 208 or at other parts of the reactor 206 .
- the source of the H 2 may be, for example, a H 2 piping header or a H 2 tube trailer, and the like.
- the source of the H 2 is a water electrolysis unit.
- the H 2 supplied by the water electrolysis unit may be labeled as renewable H 2 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 H 2 ) 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 DME synthesis reactor 212 in the reactor 206 vessel receives the cooled syngas discharged from the heat exchanger 210 .
- the DME synthesis reaction in the DME synthesis reactor 212 that converts the syngas to DME 102 is generally exothermic. Therefore, the reactor 206 vessel at the DME 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 DME synthesis reactor 212 that route a cooling medium.
- the operating temperature in the DME synthesis reactor 212 may be, for example in the range of 175° C. to 350° 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.
- the DME synthesis reactor 212 has DME synthesis catalyst to convert the syngas to DME (e.g., DME 102 ).
- the DME synthesis catalyst may be, for example, a Cu-based catalyst, CuO—ZnO based catalyst, etc.
- the DME 102 generated via the DME synthesis discharges in the reactor 206 effluent 110 from the DME 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 FIG. 1 .
- the effluent 110 may be processed in the separation system 214 to give the DME 102 product.
- Components e.g., H 2 , CO, CO 2 , etc.
- These removed components may be recycled to the reactor 206 .
- two recycle streams 216 , 218 having at least some of these removed components are depicted.
- the recycle stream 216 is fed to the dry reformer 208 .
- the recycle stream 218 is fed to the DME synthesis reactor 212 .
- the recycle streams 216 , 218 may each be primarily the combination of H 2 , CO, and CO 2 . In implementations, at least 50 mol % (or at least 80 mol %) of each of the recycle streams 216 , 218 is the combination of H 2 , CO, and CO 2 .
- the recycle stream 216 and the recycle stream 218 may have the same composition.
- the recycle stream 216 may have a composition different than the composition of the recycle stream 218 . For instance, the concentration of CO 2 in the recycle stream 216 may be greater than the concentration of CO 2 than the recycle stream 218 .
- 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.
- the product DME 102 stream discharges from separation system 214 .
- the system 200 may include the control system 148 , as discussed with respect to FIG. 1 .
- the control system 146 may direct or facilitate operations of the system 200 .
- FIG. 3 is a method 300 of producing DME via dry reforming and DME synthesis in the same vessel.
- the vessel may be a vessel of a reactor.
- the vessel may be a reactor vessel.
- a reactor having a reactor vessel may perform both the dry reforming and DME synthesis in the same reactor vessel. Accordingly, the reactor may perform two different types of reaction (dry reforming and DME synthesis) in the same reactor vessel.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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).
- the method includes synthesizing DME (e.g., via DME 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 DME synthesis section in the vessel, and synthesizing DME from the syngas via the DME synthesis catalyst in the DME synthesis section.
- the DME synthesis catalyst may be a fixed bed of catalyst in the DME synthesis section (DME synthesis reactor) in the vessel to give the DME as a component of the vessel effluent.
- the method includes discharging effluent (having the DME) 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 DME synthesis section (or DME synthesis reactor) in the vessel.
- 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 ).
- the method may include processing the effluent (as discharged) to remove components (e.g., hydrogen, carbon monoxide, carbon dioxide, any unreacted methane, etc.) from the effluent to give the DME as product.
- components e.g., hydrogen, carbon monoxide, carbon dioxide, any unreacted methane, etc.
- 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).
- 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.
- 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 DME synthesis section.
- the vessel have an inlet nozzle at the DME synthesis section to receive this return of component(s) to the vessel.
- the present techniques uniquely recognize the feasibility and benefits of combining dry reforming with olefin synthesis (in the same vessel), as describe herein.
- An embodiment is a method of producing DME via dry reforming and DME 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 DME from the syngas in the vessel, and discharging effluent (having DME) from the vessel.
- the synthesizing of the DME may involve forming methanol from the syngas and forming DME by dehydrating the methanol.
- the method may include processing the effluent as discharged from the vessel to remove components from the effluent to give the DME as product, the components removed 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 include converting the methane and the carbon dioxide via dry reforming catalyst in the vessel into the syngas.
- the synthesizing of the DME may include synthesizing the DME from the syngas via DME 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 DME.
- the method includes 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.
- 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 DME synthesis section in the reactor vessel.
- the method includes synthesizing DME from the syngas via a DME synthesis catalyst in the DME synthesis section.
- the method may include providing feed including the methane and the carbon dioxide to the dry reforming section in the reactor vessel, wherein synthesizing DME from the syngas includes forming methanol from the syngas via the DME synthesis catalyst and dehydrating the methanol via the DME synthesis catalyst to give the DME.
- the method may include discharging effluent having the DME from the reactor vessel.
- the heat exchange section may include a 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.
- the method may include processing effluent having the DME discharged from the reactor vessel to remove hydrogen, carbon monoxide, and carbon dioxide from the effluent to give the DME as product.
- 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 DME synthesis section.
- a DME production system including a reactor vessel having a feed inlet to receive a feed comprising 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, wherein the cooling medium includes cooling water.
- the reactor vessel includes a DME synthesis section having a DME synthesis catalyst in the reactor vessel to synthesize DME from the syngas and discharge an effluent including the DME from the reactor vessel.
- the DME synthesis catalyst may be a fixed bed of catalyst in the DME synthesis section in the reactor vessel.
- the DME production system may include a separation system to remove components from the effluent as discharged to give the DME as DME product, wherein the components removed include hydrogen, carbon monoxide, and carbon dioxide.
- the separation system may include a flash vessel.
- the reactor vessel may have 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 by the separation system.
- 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.
- the DME production system may have a water electrolysis unit comprising a water-electrolysis electrochemical cell to 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.
- Example 1 the feed (excluding nitrogen) was 50 mol % CO 2 and 50 mol % CH 4 .
- the feed (excluding nitrogen) was 75 mol % CO 2 and 25 mol % CH 4 .
- Nitrogen gas was fed along with the CH 4 and CO 2 . Nitrogen is inert and does not react.
- 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.
- mm millimeters
- 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 H 2 /CO molar ratio.
- the time on stream for the reaction was 850 hours.
- the conversion of CH 4 and the conversion of CO 2 were both about 100% over the entire 850 hours.
- 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.
- 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 CO 2 over the 24 hours was consistently about 45%.
- Example 2 Catalyst Nickel-based catalyst Nickel-based catalyst CO2 Feed 50% 75% CH4 Feed 50% 25% Temperature 800° C. 800° C. Pressure 1 bar 14 bars Conversions CH4: 100%, CO2: 100% CH4: ⁇ 95%, CO2: ⁇ 45% H2/CO molar ratio ⁇ 1 ⁇ 0.5 Time on stream (hours) 850 24
- a reactor was simulated via Aspen Plus ⁇ software (version 10). Aspen Plus ⁇ software is available from Aspen Technology, Inc. having headquarters in Bedford, Massachusetts, USA. The reactor simulated has a dry reforming part and DME synthesis part (and heat exchanger disposed there between), such as the reactor 106 , 206 discussed above with respect to FIGS. 1 - 2 .
- FIG. 4 is the Aspen simulation diagram for the two simulations performed in Example 3 and Example 4, respectively.
- the stream temperatures depicted in FIG. 4 is in ° C.
- the stream information for the stream labels in FIG. 4 is in Table 4 (Example 3) and Table 7 (Example 4) below.
- the Aspen stoichiometric reactor was utilized for simulating the dry reforming part and the DME synthesis part, respectively.
- the Aspen heat exchanger was applied to mimic the heat exchanger part.
- the aforementioned catalyst experimental results (as seen in Table 1) were applied.
- DME synthesis conditions are typical conditions.
- the values for DME selectivity and CO conversion are input.
- Example 3 Based on the simulation results for Example 3, it was found that 31.6 kilogram per day (kg/day) of CO 2 and 11.55 kg/day of CH 4 and 2.9 kg/day of extra H 2 enabled to ideally produce 11.60 kg/day of DME. Based on the simulation results for Example 4, 11.55 kg/day of CH 4 , 95.06 kg/day of CO 2 and 1.94 kg/day of extra H 2 can ideally produce 15.46 kg/day of DME.
- the OTHR-HC is ethane, butane, etc.
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Abstract
A system and method for producing dimethyl ether (DME) via dry reforming and DME synthesis in the same vessel, including 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, and synthesizing DME from the syngas in the vessel.
Description
- This application is a divisional of and claims priority to U.S. patent application Ser. No. 17/401,029, filed Aug. 12, 2021, the entire contents of which are hereby incorporated by reference.
- This disclosure relates to dry reforming of methane and dimethyl ether (DME) synthesis.
- Methane, which may be labeled as the simplest hydrocarbon, may be subjected to steam reforming to generate synthetic gas (syngas) that includes hydrogen (H2) and carbon monoxide (CO). The syngas may be distributed including 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 method of producing dimethyl ether (DME) via dry reforming and DME 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 DME from the syngas in the vessel, and discharging effluent (having DME) from the vessel.
- Another aspect is a method of producing DME. The method includes 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. 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 DME synthesis section in the reactor vessel. The method includes synthesizing DME from the syngas via a DME synthesis catalyst in the DME synthesis section.
- Yet another aspect is a DME production system including a reactor vessel having a feed inlet to receive a feed comprising 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 DME synthesis section having a DME synthesis catalyst in the reactor vessel to synthesize DME from the syngas and discharge an effluent including the DME from the reactor vessel.
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FIG. 1 is a diagram of a system that produces dimethyl ether (DME). -
FIG. 2 is a diagram of a system that produces DME, and which may be analogous toFIG. 1 . -
FIG. 3 is a block flow diagram of a method of producing DME via dry reforming and DME synthesis in the same vessel -
FIG. 4 is an Aspen Plus® simulation diagram. - Some aspects of the present disclosure are directed to dry reforming and dimethyl ether (DME) synthesis in the same vessel to generate DME. DME, also known as methoxymethane, may generally be a colorless gas at ambient conditions. DME has the formula CH3OCH3 and may be thought of as the simplest ether. DME may also be expressed as the formula (CH3)2O or the simplified formula expression C2H6O.
- Some aspects of the present disclosure are directed DME generation from carbon dioxide and methane in a vessel (a reactor vessel). Carbon dioxide and methane may be fed to the vessel. The DME generated in the vessel may discharge from the vessel. The DME synthesis may be via dry reforming of the methane in the vessel. In particular, the DME may be synthesized from the synthetic gas (syngas) generated by the dry reforming. Again, the dry reforming and the DME synthesis may occur 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.
- Aspects may include DME production by performing both dry reforming and DME synthesis in the same vessel. Thus, embodiments of the present techniques include a reactor for DME synthesis via dry reforming, and in which both the dry reforming reaction and the DME 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 DME synthesis section. The reactor converts carbon dioxide and methane into DME 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 DME. As presented herein in embodiments, the syngas produced from DRM is utilized directly in DME 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.
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FIG. 1 is asystem 100 that producesDME 102. Thefeed 104 includes CO2 and CH4. Advantageously, utilization of CO2 as feed can reduce CO2 emissions (the CO2 footprint) at a facility. In implementations, the CH4 may be fed in a methane-rich stream, such as natural gas. Utilization of CH4 as feed can reduce CH4 emissions at a facility. - The
system 100 includes areactor 106, as well as adownstream system 108 that processeseffluent 110 from thereactor 106 to give theDME 102 product. Thereactor 106 may generally be a continuous reactor. Thesystem 100 may generally be a continuous system. - The
reactor 106 includes areactor 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 thevessel 112 to the inside of thevessel 112 wall. Thereactor vessel 112 may be metal, such as stainless steel. Thereactor vessel 112 may have a vertical orientation as depicted, or may have a horizontal orientation. In implementations, thevessel 112 may have elliptical heads. Thereactor vessel 112 may have nozzles (e.g., flanged, threaded, etc.) at inlets and outlets for coupling to inlet supply conduits and outlet discharge conduits. Thereactor 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 thevessel 112 into multiple sections. Thereactor 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 thevessel 112 into multiple sections. The three sections (parts) might be structurally separate in the vessel via, for example, divider plate or divider meshes. 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. These and other vessel internals may be, for example, a stainless steel, a Hastelloy®, or an Inconel®, and the like. Thereactor 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 thesame vessel 112. - In the illustrated embodiment, the
reactor 106 is configured to perform two different reactions of dry reforming and DME synthesis contemporaneously in two respective sections, as discussed below. While the DME synthesis within thevessel 112 may be in sequence downstream of the dry reforming within thevessel 112, the two reactions may occur as the same time in the continuous operation of thereactor 106. - The
reactor 106 includes a dry reformingsection 114 to perform (via reforming catalyst 116) the dry reforming reaction represented by CH4+CO2→2H2+2CO. The dry reformingsection 114 may be labeled as a dry reforming zone, dry reforming part, dry reformer, etc. The dry reformingsection 114 may be enclosed within thereactor vessel 112 of thereactor 106. The dry reformingsection 114 has dry reformingcatalyst 116 to convert CH4 and CO2 of thefeed 104 into synthetic gas (syngas). The generated syngas includes H2 and CO. The dry reformingcatalyst 116 may be a fixed bed of catalyst in the dry reformingsection 114. In certain implementations, the dry reformingcatalyst 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 thefeed 104 to the dry reformingsection 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 produced syngas is generally H2 and CO, and the molar ratio of H2 to CO in the syngas is ideally 1 but in practice 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 reformingsection 114, or thereactor vessel 112 may have a vessel jacket at the dry reformingsection 114 for a heat transfer fluid (as a heating medium). - The
reactor 106 includes aheat 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 thevessel 112. Theheat exchange section 118 may be enclosed within thereactor vessel 112 of thereactor 106. A purpose of theheat exchange section 118 may be to cool thesyngas 120 to a desired temperature for feed to the DME synthesis. - In operation, the
heat exchange section 118 cools thesyngas 120 discharged from the dry reformingsection 114. In some implementations, thesyngas 120 can include additional H2 added to increase the molar ratio of H2 to CO in thesyngas 120. Theheat exchange section 116 utilizes a cooling medium to cool thesyngas 120. The cooling medium may be, for example, water such as cooling tower water. The cooling medium may flow through theheat exchange section 116 without change in composition and absorb heat from thesyngas 120. - In operation, the cooling
medium supply 124 enters theheat exchange section 116. Thereactor vessel 112 may have a cooling-medium inlet (e.g., inlet nozzle) coupled to a supply conduit (external to the vessel 112) conveying the coolingmedium supply 124 to thereactor vessel 112. The coolingmedium return 126 discharges from theheat exchange section 116. Thereactor vessel 112 may have a cooling-medium outlet (e.g., outlet nozzle) coupled to a return conduit (external to the vessel 112) conveying the coolingmedium return 126 to the cooling medium system. - With the cooling medium cooling (absorbing heat from) the
syngas 120, the coolingmedium return 126 has a greater temperature than the coolingmedium supply 124. Heat transfer occurs from thesyngas 120 to the cooling medium. The coolingmedium supply 124 may be, for example, less than 25° C. The coolingmedium return 126 may be, for example, at least 100° C. Theheat exchange section 118 may be, for example, a shell-and-tube heat-exchanger type or configuration in which tubes are situated in theheat exchange section 118. Theheat exchange section 118 can be configured to flow the cooling medium through the tubes, and flow thesyngas 120 external to the tubes. On the other hand, theheat exchange section 118 can be configured to flow thesyngas 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 aDME synthesis section 128 that may be labeled as a DME synthesis zone, DME synthesis portion, DME synthesis reactor, DME reactor, etc. TheDME synthesis section 128 may be enclosed within thereactor vessel 112 of thereactor 106. TheDME synthesis section 128 receives the cooledsyngas 120 discharged from theheat exchange section 118. TheDME synthesis section 128 has aDME synthesis catalyst 130 to convert thesyngas 120 to DME (e.g., DME 102). TheDME synthesis catalyst 130 may be, for example, a copper-based catalyst. Thecatalyst 130 may be a copper oxide (CuO) based catalyst or a zinc oxide (ZnO) based catalyst. In certain implementations, thecatalyst 130 includes a mixture of copper oxide and zinc oxide, supported on alumina. Other catalysts are applicable. For DME synthesis from syngas, the reactions may involve these three reactions (1) methanol synthesis from CO and H2, (2) methanol dehydration to give DME, and (3) water gas shift to give (4) the overall reaction. - Methanol Formation
-
- Water Gas Shift
- Overall Reaction
- The DME synthesis can be conducted at a temperature in the range of 175° C. to 350° C., or in the range of 200° C. to 300° C., or at least 175° C., at least 200° C., or less than 350° C., and at a pressure, for example, in the range of 10 bars to 70 bars. The unit bar as used herein is bar absolute (bara). The H2:CO feed molar ratio for DME synthesis can be varied in the range of 1:1 to 2:1. In some instances, to optimize (increase) the feed H2/CO ratio, extra H2 produced by water (H2O) electrolysis utilizing renewable power sources can be injected.
- In general, the residence time in the dry reforming section 114 (dry reforming reaction) and in the DME synthesis section 128 (DME synthesis reactions) may be similar. However, the residence time in the
DME synthesis section 128 may be adjusted, for example, by injecting hydrogen after the dry reformingsection 114, by changing thecatalyst 130 volume (amount), and the like. - The
DME 102 synthesized may discharge from theDME synthesis section 128 ineffluent 110 from thereactor 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 thereactor vessel 112 to measure composition of theeffluent 110. In some implementations, thecontrol system 148 in response to theeffluent 110 composition as measured by the onlineanalytical instrument 131, may automatically adjust: (1) flow rate of thecarbon dioxide 132 stream (see below), (2) flow rate of the hydrogen 122 (see below), or (3) other operating conditions of thereactor 106. - In some implementations, the
reactor vessel 112 may include adischarge portion 133 to facilitate discharge of theeffluent 110 of thereactor 106. In other implementations, there is noindependent discharge portion 133, and theeffluent 110 of thereactor 106 instead discharges generally directly from theDME synthesis section 128. - The DME synthesis reaction in the
DME synthesis section 128 that converts thesyngas 120 toDME 102 is generally exothermic. Therefore, thereactor vessel 112 at theDME synthesis section 128 may have a vessel jacket for a heat-transfer fluid that is a cooling medium (e.g., cooling water). Thereactor vessel 112 may have cooling coils (internally in thereactor vessel 112 at the DME synthesis section 128) that route a cooling medium. To cool the reaction mixture and control temperature of theDME synthesis section 128, heat transfer may occur from the reaction mixture in theDME 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 tomethane 134 to give thefeed 104 for introduction to thereactor vessel 112. Thecarbon dioxide 132 stream may be, for example, at least 90 percent (%) of CO2 by volume (vol %) or on a molar basis (mol %). Themethane 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 thecarbon dioxide 132 stream and/or themethane 134 stream may be controlled to give a desired or specified percent concentration (e.g., vol % or mol %) of CO2 in thefeed 104 or a specified molar ratio of CO2 to CH4 in thefeed 104. For example, the molar ratio of CO2 to CH4 in thefeed 104 may be specified in the range of 1:1 to 3:1. In implementations, the amount of CO2 in thefeed 104 is in the range of 30 vol % to 70 vol %, or at least 40 vol %. In the illustrated implementation, thesystem 100 includes a control valve 136 (e.g., flow control valve) to control (including adjusting) the flow rate of thecarbon dioxide 132 stream to give the specified percent (e.g., at least 40 vol %) of CO2 in thefeed 104 or the specified molar ratio (e.g., at least 1) of CO2 to CH4 in thefeed 104. In implementations, the volume percent or molar percent of each of CO2 and CH4 in thefeed 104 can be calculated based on the known flow rates and compositions of thecarbon dioxide 132 steam andmethane 134 stream. In one embodiment, an online analyzer instrument 136 (e.g., online gas chromatograph instrument) disposed along the conduit conveying thefeed 104 measures the amounts (e.g., in vol %) of each of CO2 and CH4 in thefeed 104. - In some implementations, the
control system 148 may automatically adjust the set point of thecontrol valve 136 in response to the composition of thefeed 104 as calculated by thecontrol system 148 or as measured by theonline 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 thefeed 104, such as for the specified concentration of CO2 in the feed or for the specified molar ratio of CO2 to CH4 in thefeed 104. To maintain this entered set point (of the master controller), the master controller may direct the flow controller (FC) of theflow control valve 136 as a slave controller. In particular, the master controller may specify a slave set point (e.g., volume flow rate ofCO 2 132 stream or mass flow rate ofCO 2 132 stream) of the FC for thecontrol valve 136 to give the desired set point of the master controller. - The
feed 104 may be introduced to aninlet portion 140 of thereactor vessel 112 to facilitate introduction of thefeed 104 into the dry reformingsection 114. In other implementations, thefeed 104 thereactor vessel 112 does not include anindependent inlet portion 140, and thefeed 104 is instead introduced generally directly into the dry reformingsection 114. In some embodiments, thecarbon dioxide 132 andmethane 134 may be added in two respective separate streams to thereactor vessel 112 via two respective inlets of thereactor vessel 112. - In implementations, as mentioned, the molar ratio of H2 to CO in the
syngas 120 as generated by the dry reformingsection 114 may generally be approximated at the ideal ratio of 1 for the ideal thermodynamic equilibrium or stoichiometric relationship for the dry reforming reaction in the dry reformingsection 114. In practice, the molar ratio of H2 to CO in thesyngas 120 as generated by the dry reformingsection 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 thesyngas 120 may be estimated based on, for example, the relative amounts of CO2 and CH4 in thefeed 104, the operating conditions (e.g., pressure, temperature, etc.) of the dry reformingsection 114, the condition of the dry reformingcatalyst 116, and so forth. Again, in certain embodiments, the molar ratio of H2 to CO in thesyngas 120 as generated by the dry reformingsection 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 range of 1 to 2 or 1.1 to 2, or at least 1.1 or at least 1.2. In certain implementations, an online analytical instrument (e.g., online gas chromatograph instrument) is disposed along thereactor 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 thesyngas 120. - A
source 142 of hydrogen provides thehydrogen 122 that is added to thereactor vessel 112 to increase the molar ratio of H2 to CO in thesyngas 120. The DME synthesis in theDME synthesis section 128 may benefit, for example, with thesyngas 120 having a molar ratio of H2 to CO of at least 1, or at least 1.1. Thehydrogen 122 may be injected not only to adjust the molar ratio of the H2/CO, but also to reduce the temperature of thesyngas 120. The injectedhydrogen 122 may cool thesyngas 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 thesyngas 120. In the illustrated embodiment, the addition point of thehydrogen 122 is depicted at the discharge portion of the dry reformingsection 114. However, thehydrogen 122 may also be added to theheat exchange section 118 or at the introduction of the syngas 120 (as cooled in the heat exchange section 118) to theDME synthesis section 128. - In certain implementations, the
source 142 ofhydrogen 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: 2H2O→2H2+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 thesyngas 120 to adjust the molar ratio of H2 to CO in thesyngas 120. As mentioned for some implementations, aflow control valve 142 disposed along the conduit conveying thehydrogen 122 modulates the amount ofhydrogen 122 added to give the desired or specified molar ratio of H2 to CO in thesyngas 120. Again, the desired molar ratio may be specified based on the desired molar ratio of H2 to CO for the DME synthesis. The addition of thehydrogen 122 may increase the H2:CO molar ratio, for example, to between 1 to 2. - 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 thehydrogen 122 into thereactor vessel 112. - In some implementations, the
control system 148 may automatically adjust the set point of thecontrol valve 142 in response to the composition of thesyngas 120 as calculated by thecontrol 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 thesyngas 120. To maintain this entered set point (of the master controller), the master controller may direct the flow controller (FC) of theflow control valve 142 as a slave controller. In particular, the master controller may specify a slave set point (e.g., volume flow rate ofhydrogen 122 or mass flow rate of hydrogen 122) of the FC for thecontrol valve 142 to give the desired set point of the master controller. - The
effluent 110 discharged from thereactor 106 includes theDME 102 generated in theDME synthesis section 128. In addition to theDME 102, theeffluent 110 may include H2, CO, and CO2. The amount, e.g., mole percent (mol %), of CO2 in theeffluent 110 may be correlative with (e.g., directly proportional with) the amount of CO2 in thefeed 104, or correlative with (e.g., directly proportional with) with the molar ratio or volume ratio of CO2 to CH4 in thefeed 104. In implementations, theeffluent 110 can include unreacted CH4, such as when the conversion of the CH4 of thefeed 104 less than 100% in the reactor 106 (including in the dry reforming section 114). In certain implementations, theeffluent 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 thereactor 106 may discharge from thereactor vessel 112 to adownstream system 108 for processing theeffluent 110. Thedownstream system 108 may be a separation system to removecomponents 144 from theeffluent 110 to give theproduct DME 102. Thecomponents 144 may include, for example, H2, CO, CO2, and any unreacted CH4. Thecomponents 144 may be recycled to thereactor 106 or sent to other users. - To separate the
components 144 from theeffluent 110, thedownstream 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 thecomponents 144 from theeffluent 110 in thedownstream 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 DME may include acontrol system 148 that may facilitate or direct operation of thesystem 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. Thecontrol system 148 may receive data from sensors (e.g., temperature, pressure, etc.) and online analytical instruments in thesystem 100. Thecontrol system 148 may perform calculations. Thecontrol system 148 may specify set points for control devices in thesystem 100. Thecontrol system 148 may be disposed in the field or remotely in a control room. Thecontrol system 148 may include control modules and apparatuses distributed in the field. - The
control system 148 may include aprocessor 150 andmemory 152 storing code (e.g., logic, instructions, etc.) executed by theprocessor 150 to perform calculations and direct operations of thesystem 100. Thecontrol 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. Thememory 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. Thecontrol 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 thesystem 100. Thecontrol system 148 typically includes a user interface for a human to enter set points and other targets or constraints to thecontrol system 148. In some implementations, thecontrol system 148 may calculate or otherwise determine set points of control devices. Thecontrol system 148 may be communicatively coupled to a remote computing system that performs calculations and provides direction including values for set points. In operation, thecontrol system 148 may facilitate processes of thesystem 100 including to direct operation of thereactor 106 and thedownstream system 108. Again, thecontrol system 148 may receive user input or computer input that specifies the set points of control components in thesystem 100. Thecontrol 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 thesystem 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. Thecontrol system 148 may also or instead employ local control (e.g., distributed controllers, local control panels, etc.) distributed in thesystem 100. Thecontrol system 148 can include a control panel or control module disposed in the field. -
FIG. 2 is asystem 200 that producesDME 102. Thesystem 200 includes areactor 206 that performs dry reforming of CH4. Thefeed 104 to thereactor 206 includes CO2 and CH4. The dry reforming of CH4 with CO2 as the oxidant is a technique that beneficially converts the greenhouse-gases CO2 and CH4 into syngas that is primarily H2 and CO. The molar ratio H2 to CO in the syngas may deviate from ideal thermodynamic equilibrium of 1 to in the range of 0.4 to 1, for example. Hydrogen may be added to the syngas in thereactor 206 to increase the molar ratio of H2 to CO if desired. - The
reactor 206 may be analogous to thereactor 106 ofFIG. 1 . Thereactor 206 may include two reactors in the same reactor vessel: a reactor for dry reforming CH4 to generate syngas and a reactor for DME synthesis from the syngas. - The
reactor 206 is a vessel having at least three parts or sections (zones):dry reformer 208,heat exchanger 210, andDME synthesis reactor 212, which are in the same vessel and analogous to the dry reformingsection 114,heat exchange section 118, andDME synthesis section 128 ofFIG. 1 , respectively. Thus, thedry reformer 208 reactor and theDME synthesis reactor 212 are in the same reactor vessel. In this implementation, the heat exchanger is also disposed in the same reactor vessel between thedry reformer 208 reactor and theDME synthesis reactor 212. - 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 thereactor 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 thefeed 104. In embodiments, the natural gas may have no measurable O2 and/or measurable water (H2O), or have trace amounts of O2 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 thefeed 104 may be fed in a combined stream or as separate streams to thedry reformer 208 of thereactor 206. The flow rate (e.g., volumetric rate, mass rate, or molar rate) of thefeed 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 thefeed 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 thefeed 104 may provide for or facilitate the operating pressures in thereactor 106. Moreover, in one implementation, thesystem 200 may include upstream equipment (e.g., desulfurizer, pre-reformer, etc.) to process or treat thefeed 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 thefeed 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, thedry reformer 208 may have a fixed bed of dry reformer catalyst (dry reforming catalyst). The dry reforming in thedry 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 thereactor 206 and thus to thedry reformer 208 includes CH4 and CO2. While O2 is generally not fed to thedry 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 thereactor 206 vessel having thedry 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 thedry 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 thereactor 206 vessel in thedry reformer 208 or on an external surface ofreactor 206 vessel at thedry reformer 208. Other configurations of heat transfer and temperature control of thedry reformer 208 are applicable. The operating temperature in thedry 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) thedry 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 thedry reformer 208. Hydrogen may be added to thereactor 206 vessel at a discharge portion of thedry reformer 208 or at other parts of thereactor 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. Theheat exchanger 210 is generally disposed within thereactor 206 vessel. In operation, theheat exchanger 210 cools (removes heat from) the syngas discharged from thedry reformer 208 The cooling medium for theheat exchanger 210 may be, for example, cooling water. The cooling medium may flow through theheat exchanger 210 to absorb heat from the syngas. Theheat exchanger 210 may be, for example, a shell-and-tube heat-exchanger type or configuration in which the tubes are situated in thereactor 206 vessel. Thereactor 206 vessel wall may act as the shell of theheat exchanger 210 housing the tubes, or the shell of theheat exchanger 210 housing the tubes is disposed in thereactor 206 vessel. Other heat exchanger configurations are applicable. - The
DME synthesis reactor 212 in thereactor 206 vessel receives the cooled syngas discharged from theheat exchanger 210. The DME synthesis reaction in theDME synthesis reactor 212 that converts the syngas toDME 102 is generally exothermic. Therefore, thereactor 206 vessel at theDME 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, thereactor 206 vessel may have cooling coils internally in theDME synthesis reactor 212 that route a cooling medium. The operating temperature in theDME synthesis reactor 212 may be, for example in the range of 175° C. to 350° 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. - The
DME synthesis reactor 212 has DME synthesis catalyst to convert the syngas to DME (e.g., DME 102). The DME synthesis catalyst may be, for example, a Cu-based catalyst, CuO—ZnO based catalyst, etc. TheDME 102 generated via the DME synthesis discharges in thereactor 206effluent 110 from theDME synthesis reactor 212 and thus from thereactor 206 vessel in the illustrated implementation. - The
system 200 may include aseparation system 214 that may be analogous to thedownstream system 108 ofFIG. 1 . InFIG. 2 , theeffluent 110 may be processed in theseparation system 214 to give theDME 102 product. Components (e.g., H2, CO, CO2, etc.) may be removed from theeffluent 110 to give theproduct DME 102. These removed components may be recycled to thereactor 206. In the illustrated embodiment, two recyclestreams recycle stream 216 is fed to thedry reformer 208. Therecycle stream 218 is fed to theDME synthesis reactor 212. In implementations, the recycle streams 216, 218 may each be primarily the combination of H2, CO, and CO2. In implementations, at least 50 mol % (or at least 80 mol %) of each of the recycle streams 216, 218 is the combination of H2, CO, and CO2. Therecycle stream 216 and therecycle stream 218 may have the same composition. On the other hand, therecycle stream 216 may have a composition different than the composition of therecycle stream 218. For instance, the concentration of CO2 in therecycle stream 216 may be greater than the concentration of CO2 than therecycle stream 218. - The
separation system 214 may employ, for example, a multi-stage cooling separation. Theseparation 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, theproduct DME 102 stream discharges fromseparation system 214. - The
system 200 may include thecontrol system 148, as discussed with respect toFIG. 1 . The control system 146 may direct or facilitate operations of thesystem 200. -
FIG. 3 is amethod 300 of producing DME via dry reforming and DME synthesis in the same vessel. The vessel may be a vessel of a reactor. Thus, the vessel may be a reactor vessel. - Therefore, a reactor having a reactor vessel may perform both the dry reforming and DME synthesis in the same reactor vessel. Accordingly, the reactor may perform two different types of reaction (dry reforming and DME 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 DME (e.g., via DME 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 DME synthesis section in the vessel, and synthesizing DME from the syngas via the DME synthesis catalyst in the DME synthesis section. The DME synthesis catalyst may be a fixed bed of catalyst in the DME synthesis section (DME synthesis reactor) in the vessel to give the DME as a component of the vessel effluent. - At
block 312, the method includes discharging effluent (having the DME) 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 DME synthesis section (or DME 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., hydrogen, carbon monoxide, carbon dioxide, any unreacted methane, etc.) from the effluent to give the DME 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 DME synthesis section. The vessel have an inlet nozzle at the DME synthesis section to receive this return of component(s) to the vessel. - The present techniques uniquely recognize the feasibility and benefits of combining dry reforming with olefin synthesis (in the same vessel), as describe herein.
- An embodiment is a method of producing DME via dry reforming and DME 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 DME from the syngas in the vessel, and discharging effluent (having DME) from the vessel. The synthesizing of the DME may involve forming methanol from the syngas and forming DME by dehydrating the methanol. The method may include processing the effluent as discharged from the vessel to remove components from the effluent to give the DME as product, the components removed 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 include converting the methane and the carbon dioxide via dry reforming catalyst in the vessel into the syngas. The synthesizing of the DME may include synthesizing the DME from the syngas via DME 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 DME. The method includes 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. 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 DME synthesis section in the reactor vessel. The method includes synthesizing DME from the syngas via a DME synthesis catalyst in the DME synthesis section. The method may include providing feed including the methane and the carbon dioxide to the dry reforming section in the reactor vessel, wherein synthesizing DME from the syngas includes forming methanol from the syngas via the DME synthesis catalyst and dehydrating the methanol via the DME synthesis catalyst to give the DME. The method may include discharging effluent having the DME from the reactor vessel. The heat exchange section may include a 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. The method may include processing effluent having the DME discharged from the reactor vessel to remove hydrogen, carbon monoxide, and carbon dioxide from the effluent to give the DME 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 DME synthesis section.
- Yet another embodiment is a DME production system including a reactor vessel having a feed inlet to receive a feed comprising 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, wherein the cooling medium includes cooling water. The reactor vessel includes a DME synthesis section having a DME synthesis catalyst in the reactor vessel to synthesize DME from the syngas and discharge an effluent including the DME from the reactor vessel. The DME synthesis catalyst may be a fixed bed of catalyst in the DME synthesis section in the reactor vessel. The DME production system may include a separation system to remove components from the effluent as discharged to give the DME as DME product, wherein the components removed include hydrogen, carbon monoxide, and carbon dioxide. The separation system may include a flash vessel. The reactor vessel may have 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 by the separation system. 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. The DME production system may have a water electrolysis unit comprising a water-electrolysis electrochemical cell to 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 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.
- 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%.
-
TABLE 1 Evaluation of dry reforming catalyst-Example 1 and Example 2 Example 1 Example 2 Catalyst Nickel-based catalyst Nickel-based catalyst CO2 Feed 50% 75% CH4 Feed 50% 25% Temperature 800° C. 800° C. Pressure 1 bar 14 bars Conversions CH4: 100%, CO2: 100% CH4: ~95%, CO2: ~45% H2/CO molar ratio ~1 ~0.5 Time on stream (hours) 850 24 - A reactor was simulated via Aspen Plus© software (version 10). Aspen Plus© software is available from Aspen Technology, Inc. having headquarters in Bedford, Massachusetts, USA. The reactor simulated has a dry reforming part and DME synthesis part (and heat exchanger disposed there between), such as the
reactor FIGS. 1-2 . -
FIG. 4 is the Aspen simulation diagram for the two simulations performed in Example 3 and Example 4, respectively. The stream temperatures depicted inFIG. 4 is in ° C. The stream information for the stream labels inFIG. 4 is in Table 4 (Example 3) and Table 7 (Example 4) below. In the simulations, the Aspen stoichiometric reactor was utilized for simulating the dry reforming part and the DME synthesis part, respectively. The Aspen heat exchanger was applied to mimic the heat exchanger part. For dry reforming conditions and conversions, the aforementioned catalyst experimental results (as seen in Table 1) were applied. DME synthesis conditions are typical conditions. The values for DME selectivity and CO conversion are input. - 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 2.9 kg/day of extra H2 enabled to ideally produce 11.60 kg/day of DME. Based on the simulation results for Example 4, 11.55 kg/day of CH4, 95.06 kg/day of CO2 and 1.94 kg/day of extra H2 can ideally produce 15.46 kg/day of DME. In the tabulated simulation results below, the OTHR-HC is ethane, butane, etc.
-
TABLE 2 Dry Reforming Conditions for Example 3 Dry reforming condition 1 Feed 50 mol % CH4, 50 mol % CO2 Catalyst Ni-based catalyst Temperature 850° C. Pressure 40 bars Conversion 100% CH4, 100% CO2 Products H2:CO = 1:1 -
TABLE 3 DME Synthesis Conditions for Example 3 DME synthesis condition Feed H2:CO = 1:1 molar ratio Catalyst Cu-based catalyst Temperature 260° C. Pressure 40 bars Conversion 52.9% CO Products 66.1% DME selectivity -
TABLE 4 Stream Information for Example 3 Stream CH4 CO2 1ST-PROD AFT-MXR AFT-HEX FIN-PROD Phase Vapor Vapor Vapor Vapor Vapor Vapor Temp (° C.) 25 25 850 850 260 260 Press (bar) 40 40 40 40 40 40 Mole Fractions (mol %) CH4 100.0% 0.0% 0.0% 0.0% 0.0% 0.5% CO2 0.0% 100.0% 0.0% 0.0% 0.0% 13.2% H2O 0.0% 0.0% 0.0% 0.0% 0.0% 1.2% H2 0.0% 0.0% 50.0% 50.0% 50.0% 34.5% CO 0.0% 0.0% 50.0% 50.0% 50.0% 36.8% DME 0.0% 0.0% 0.0% 0.0% 0.0% 13.7% OTHR-HC 0.0% 0.0% 0.0% 0.0% 0.0% 0.1% Mass Flows (kg/day) CH4 11.55 0.00 0.00 0.00 0.00 0.16 CO2 0.00 31.69 0.00 0.00 0.00 10.73 H2O 0.00 0.00 0.00 0.00 0.00 0.40 H2 0.00 0.00 2.90 2.90 2.90 1.28 CO 0.00 0.00 40.33 40.33 40.33 19.00 DME 0.00 0.00 0.00 0.00 0.00 11.60 OTHR-HC 0.00 0.00 0.00 0.00 0.00 0.07 -
TABLE 5 Dry Reforming Conditions for Example 4 Dry reforming condition 2 Feed 25 mol % CH4, 75 mol % CO2 Catalyst Ni based catalyst Temperature 850° C. Pressure 40 bars Conversion 100% CH4, 55% CO2 Products H2:CO = 1:2 molar ratio -
TABLE 6 DME Synthesis Conditions for Example 4 DME synthesis condition Feed H2:CO = 1:1 molar ratio Catalyst Cu based catalyst Temperature 260° C. Pressure 40 bars Conversion 52.9% CO Products 66.1% DME selectivity -
TABLE 7 Stream Information for Example 4 Stream CH4 CO2 1ST-PROD H2 AFT-MXR AFT-HEX FIN-PROD Phase Vapor Vapor Vapor Vapor Vapor Vapor Vapor Phase Phase Phase Phase Phase Phase Phase Temp (° C.) 25 25 850 25 730.25 260 260 Press (bar) 40 40 40 40 40 40 40 Mole Fractions (mol %) CH4 100% 0% 0% 0% 0% 0% 0% CO2 0% 100% 22% 0% 18% 18% 33% H2O 0% 0% 11% 0% 9% 9% 13% H2 0% 0% 22% 100% 36% 36% 22% CO 0% 0% 44% 0% 36% 36% 23% DME 0% 0% 0% 0% 0% 0% 9% OTHR-HC 0% 0% 0% 0% 0% 0% 0% Mass Flows (kg/day) CH4 11.55 0.00 0.00 0.00 0.00 0.00 0.21 CO2 0.00 95.06 42.25 0.00 42.25 42.25 56.55 H2O 0.00 0.00 8.65 0.00 8.65 8.65 9.19 H2 0.00 0.00 1.94 1.94 3.87 3.87 1.71 CO 0.00 0.00 53.78 0.00 53.78 53.78 25.33 DME 0.00 0.00 0.00 0.00 0.00 0.00 15.46 OTHR-HC 0.00 0.00 0.00 0.00 0.00 0.00 0.09 - 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.
Claims (10)
1. A dimethyl ether (DME) production system comprising:
a reactor vessel comprising:
a feed inlet to receive a feed comprising methane and carbon dioxide;
a dry reforming section comprising a dry reforming catalyst in the reactor vessel to convert the methane and the carbon dioxide into syngas comprising hydrogen and carbon monoxide;
a heat exchange section comprising a heat exchanger in the reactor vessel to receive the syngas from the dry reforming section and cool the syngas with a cooling medium; and
a DME synthesis section comprising a DME synthesis catalyst in the reactor vessel to synthesize DME from the syngas and discharge an effluent comprising the DME from the reactor vessel.
2. The DME production system of claim 1 , comprising a separation system to remove components from the effluent as discharged to give the DME as DME product, the components comprising hydrogen, carbon monoxide, and carbon dioxide, wherein the separation system comprises a flash vessel, and wherein the reactor vessel comprises an effluent outlet for discharge of the effluent from the reactor vessel.
3. The DME production system of claim 2 , wherein the reactor vessel comprises an inlet to receive at least one of the components removed from the effluent.
4. The DME production system of claim 1 , wherein the dry reforming catalyst is a fixed bed of catalyst in the dry reforming section in the reactor vessel, and wherein the DME synthesis catalyst is a fixed bed of catalyst in the DME synthesis section in the reactor vessel.
5. The DME production system of claim 1 , wherein the reactor vessel comprises a hydrogen inlet to receive hydrogen to increase a molar ratio of hydrogen to carbon monoxide of the syngas in the reactor vessel.
6. The DME production system of claim 5 , comprising a water electrolysis unit comprising a water-electrolysis electrochemical cell to provide the hydrogen received at the hydrogen inlet.
7. The DME production system of claim 6 , comprising 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.
8. The DME production system of claim 1 , comprising a control valve 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.
9. The DME production system of claim 8 , wherein the specified amount comprises a ratio of the carbon dioxide to the methane of the feed or a concentration of the carbon dioxide in the feed.
10. The DME production system of claim 1 , wherein the heat exchanger comprises a shell-and-tube heat exchanger, and wherein the cooling medium comprises cooling water.
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