EP4526280A2 - Systèmes, dispositifs et procédés d'intensification de reformeurs et de synthèse chimique en aval - Google Patents
Systèmes, dispositifs et procédés d'intensification de reformeurs et de synthèse chimique en avalInfo
- Publication number
- EP4526280A2 EP4526280A2 EP23808530.2A EP23808530A EP4526280A2 EP 4526280 A2 EP4526280 A2 EP 4526280A2 EP 23808530 A EP23808530 A EP 23808530A EP 4526280 A2 EP4526280 A2 EP 4526280A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- plant
- reactor
- reactor unit
- flare gas
- bpd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 313
- 238000000034 method Methods 0.000 claims description 148
- 238000000926 separation method Methods 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 230000008569 process Effects 0.000 claims description 69
- 239000003054 catalyst Substances 0.000 claims description 62
- 238000012545 processing Methods 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000012263 liquid product Substances 0.000 claims description 30
- 239000012530 fluid Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 21
- 238000004891 communication Methods 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 238000012856 packing Methods 0.000 claims description 11
- 238000000066 reactive distillation Methods 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006262 metallic foam Substances 0.000 claims description 3
- 239000003129 oil well Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 102
- 238000003786 synthesis reaction Methods 0.000 description 47
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- 230000015572 biosynthetic process Effects 0.000 description 34
- 239000000463 material Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 229910001868 water Inorganic materials 0.000 description 25
- 239000000203 mixture Substances 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 238000012546 transfer Methods 0.000 description 20
- 230000001965 increasing effect Effects 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- 239000002826 coolant Substances 0.000 description 13
- 238000004821 distillation Methods 0.000 description 13
- 239000002250 absorbent Substances 0.000 description 11
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- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
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- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000010146 3D printing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- -1 ethylene, propylene, 1 -butene Chemical class 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 210000003041 ligament Anatomy 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C29/15—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
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1893—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/068—Ammonia synthesis
Definitions
- the present inventions relate to methods and systems that provide for the development and utilization of smaller scale chemical synthesis systems.
- the present inventions relate to new and improved methods, devices and systems for recovering and converting waste gases, such as flare gas, into useful and economically viable materials.
- flare gas and similar such terms should be given their broadest possible meaning, and would include gas generated, created, associated or produced by, or from, oil and gas production, hydrocarbon wells (including shale, conventional and unconventional wells), petrochemical processing, refining, landfills, waste water treatment, livestock production, and other municipal, chemical and industrial processes.
- flare gas would include stranded gas, associated gas, landfill gas, vented gas, biogas, digester gas, small-pocket gas, and remote gas.
- the composition of flare gas is a mixture of different gases.
- the composition can depend upon the source of the flare gas.
- gases released during oil-gas production mainly contain natural gas.
- Natural gas is more than 90% methane (CH4) with ethane and smaller amounts of other hydrocarbons, water, N2 and CO2 may also be present.
- Flare gas from refineries and other chemical or manufacturing operations typically can be a mixture of hydrocarbons and in some cases H2.
- Landfill gas, biogas or digester gas typically can be a mixture of CH4 and CO2, as well as small amounts of other inert gases.
- flare gas can contain one or more of the following gases: methane, ethane, propane, n-butane, isobutane, n- pentane, isopentane, n-hexane, ethylene, propylene, 1 -butene, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen, oxygen, nitrogen, and water.
- flare gas is produced from smaller, individual point sources, such as a number of oil or gas wells in an oil field, a landfill, or a chemical plant.
- flare gas Prior to the present inventions flare gas, and in particular flare gas generated from hydrocarbon producing wells, and other smaller point sources, was burned to destroy it, and in some instances may have been vented directly into the atmosphere. This flare gas could not be economically recovered and used.
- gas and “synthesis gas” and similar such terms should be given their broadest possible meaning and would include gases having as their primary components a mixture of H2 and CO; and may also contain CO2, N2, and water, as well as, small amounts of other materials.
- product gas and similar such terms should be given their broadest possible meaning and would include gases having H2, CO and other hydrocarbons, and typically significant amounts of other hydrocarbons, such as methane.
- reprocessed gas includes “syngas”, “synthesis gas” and “product gas”.
- partial oxidation As used herein unless specified otherwise, the terms “partial oxidation”, “partially oxidizing” and similar such terms mean a chemical reaction where a sub- stoichiometric mixture of fuel and air (i.e., fuel rich mixture) is partially reacted (e.g., combusted) to produce a syngas.
- partial oxidation includes both thermal partial oxidation (TPOX), which typically occurs in a reformer, and catalytic partial oxidation (CPOX).
- TPOX thermal partial oxidation
- CPOX catalytic partial oxidation
- CC ⁇ e is used to define carbon dioxide equivalence of other, more potent greenhouse gases, to carbon dioxide (e.g., methane and nitrous oxide) on a global warming potential basis of 100 years, based on Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5) methodology.
- carbon intensity is taken to mean the lifecycle CO2e generated per unit mass of a product.
- % and mol % are used interchangeably and refer to the moles of a first component as a percentage of the moles of the total, e.g., formulation, mixture, material or product.
- cost is the expenditure required to create and sell products and services, or to acquire assets.
- Capital cost is the cost of the property, equipment and facilities that makes up a plant or facility, such as a chemical processing plant.
- sonoseparation i.e., separation processes and equipment, including chemical separations, using sound and, in particular ultrasound
- sonoseparation i.e., separation processes and equipment, including chemical separations, using sound and, in particular ultrasound
- fine droplets generated when water-alcohol mixtures are subjected to ultrasound- induced capillary waves, can be performed at ambient pressures and temperatures and are enriched in alcohol concentrations that exceed those in the bulk solution and those prescribed by vapor-liquid phase equilibria.
- Such processes may improve the production grade of the product stream without the costly requirements of installing and operating distillation columns (e.g., to purify crude methanol).
- structured materials are used to reduce the capital cost and operating costs of downstream conversion of syngas produced in an engine-reformer to liquid products such as methanol or ammonia.
- the structured materials have the effect of increasing thermal homogeneity in a reacting mixture and increasing heat transfer rates from the reacting mixture to the cooling medium.
- the structure materials can be micro-channel reactors, milli-channel reactors, structured catalyst (e.g., monoliths), high-thermal-conductivity catalyst packings, fractal devices and combinations and variations of these, among others devices.
- Micro- and milli-reactors can have small feature sizes and complex internal geometries (e.g., fractal devices) that lend themselves well to new additive manufacturing techniques (e.g., metal 3D printing).
- high thermal conductivity catalyst packings are used to replace traditional catalyst beds (e.g., catalyst deposited on alumina pellets).
- the high temperature packing material can be a metal mesh or the like that supports or sequesters the catalyst.
- the catalyst can be a powder that is physically sequestered in the fine metal mesh packing or deposited using one or more catalyst deposition techniques (e.g., wash coating, wet impregnation, etc.).
- a small-scale, low capital intensity (Cl) plant for converting a syngas into a higher-value product, the plant having: a reactor unit configured to receive a flow of a syngas; wherein the reactor unit is configured to convert the syngas into a liquid product; wherein the reactor unit is a small-scale processing unit; and, wherein the reactor unit has a low Cl.
- this plant may also have an air inlet for receiving a flow of air; a flare gas inlet for receiving a flow of a flare gas; a reformer in fluid communication with the air inlet and flare gas inlet; wherein the reformer is configured to receive the flows of the flare gas and air; and, the reformer configured to convert the air and flare gas into the syngas, and thereby provide the flow of the syngas to the reactor.
- the reactor unit is a two-stage unit; wherein the reactor unit has a means for reactive separation; wherein the reactor unit has a means for reactive separation, wherein the means for reactive separation has one or more of a reactive adsorption device, a reactive distillation device, and a reactive membrane device; wherein the reactor unit has a micro-channel reactor; wherein the reactor unit has a milli-channel reactor; wherein the reactor unit has a structured catalyst; wherein the reactor unit has a high-thermal-conductivity catalyst packing; wherein the reactor unit has a, fractal device; wherein the Cl is less than about $110,000/bpd; wherein the Cl is from about $110,000/bpd to $45,000/bpd; wherein the capacity is less than about 1 ,000 bpd; wherein the capacity is from about 2 bpd to 900 bpd; where in the liquid product has methanol; where in
- a small-scale, low capital intensity (Cl) plant for converting a flare gas into methanol, the plant having: an air inlet for receiving a flow of air; a flare gas inlet for receiving a flow of a flare gas; a reformer in fluid communication with the air inlet and the flare gas inlet; wherein the reformer is configured to receive the flows of the flare gas and air; the reformer in fluid communication with a reactor unit; wherein the reactor unit is configured to receive a flow of the syngas from the reformer; and wherein the reactor unit is configured to convert the syngas into methanol; the reactor unit having a reactive separation process; wherein the reactor unit is a small-scale processing unit.
- the reactive separation process has a sweep; wherein the sweep has a liquid sweep; wherein the sweep has a gaseous sweep; wherein the reactive separation process has a reactive adsorption; wherein the reactive separation process has a reactive distillation; wherein the reactive separation process has a reactive membrane separation; and, havinga methanol refining unit.
- a small-scale, low capital intensity (Cl) plant for converting a flare gas into methanol, the plant having: an air inlet for receiving a flow of air; a flare gas inlet for receiving a flow of a flare gas; a reformer in fluid communication with the air inlet and the flare gas inlet; wherein the reformer is configured to receive the flows of the flare gas and air; the reformer in fluid communication with a reactor unit; wherein the reactor unit is configured to receive a flow of the syngas from the reformer; and wherein the reactor unit is configured to convert the syngas into methanol; and, the reactor unit having a sonoseparator; wherein the reactor unit is a small-scale processing unit.
- a small-scale, low capital intensity (Cl) plant for converting a flare gas into methanol
- the plant having: an air inlet for receiving a flow of air; a flare gas inlet for receiving a flow of a flare gas; a reformer in fluid communication with the air inlet and the flare gas inlet; wherein the reformer is configured to receive the flows of the flare gas and air; the reformer in fluid communication with a reactor unit; wherein the reactor unit is configured to receive a flow of the syngas from the reformer; and wherein the reactor unit is configured to convert the syngas into methanol; and, the reactor unit having a microchannel reactor; wherein the reactor unit is a small-scale processing unit.
- microchannel reactor having a plurality of cooling plates and a plurality of reaction plates; and, wherein the microchannel reactor has a reaction plate with sweep.
- a small-scale, low capital intensity (Cl) plant for converting a flare gas into methanol
- the plant having: an air inlet for receiving a flow of air; a flare gas inlet for receiving a flow of a flare gas; a reformer in fluid communication with the air inlet and the flare gas inlet; wherein the reformer is configured to receive the flows of the flare gas and air; the reformer in fluid communication with a reactor unit; wherein the reactor unit is configured to receive a flow of the syngas from the reformer; and wherein the reactor unit is configured to convert the syngas into methanol; and, the reactor unit having a high thermal conductivity (HTC) catalyst bed; wherein the reactor unit is a small-scale processing unit.
- HTC high thermal conductivity
- these plants, systems and processes having one or more of the following features: having an HTC bed; wherein the HTC bed has catalyst aggregates loaded into a metal foam support; wherein the catalyst support is aluminum; wherein the relative density of the foam is less than 10%; wherein the methanol is refined grade methanol; wherein the Cl is less than about $110,000/bpd; wherein the Cl is from about $45,000/bpd to $110,000/bpd; wherein the capacity is less than about 1 ,000 bpd; wherein the capacity is from about 2 bpd to 900 bdp; wherein the plant is an onsite plant and located adjacent to a source of flare gas; wherein the source of flare gas is an oil well; and, wherein the reactor unit has a catalytic bed reactor having a high thermal conductivity support.
- a method of onsite conversion of a flare gas to a liquid product using a small-scale, low capital intensity (Cl) plant having: receiving a flow of a flare gas from a flare gas source; providing the flare gas flow to a reformer engine; converting the flare gas flow in the reformer engine into a syngas, thereby providing a syngas flow; providing the syngas flow to a reactor unit; processing the syngas into a liquid product in the reactor unit, wherein the processing has a reactive separation process.
- the reactor unit has a first reactor and a second reactor, and the processing is a two-stage process using the first reactor and the second reactor, and wherein the reactive separation process takes place in the second reactor; wherein the reactive separation process has a reactive adsorption; wherein the reactive separation process has a reactive distillation; wherein the reactive separation process has a reactive membrane separation; wherein the processing has using a catalytic bed reactor having a high thermal conductivity support; wherein the processing has using a microchannel reactor; further having a sonoseperation process to purify the liquid product; wherein the source of the flare gas is an oil field and the method is carried out at the oil field; wherein the Cl is less than about $110,000/bpd; wherein the Cl is from about $45,000/bpd to $110,000/bpd; wherein less than about 1 ,000 bpd of liquid product is produced; wherein from about 2 bpd to 900
- a method of designing a small-scale, low capital intensity (Cl) plant for converting a flare gas into methanol including: selecting components of a reactor unit to conduct a syngas to methanol process; wherein the components of the reactor unit include components to conduct a reactive separation process; optimizing the syngas to methanol process, the reactive separation process, or both, to provide a design for reactor unit having a small-scale and a low Cl.
- the reactor unit has a Cl of less than about $110,000/bpd; wherein the reactor unit has a Cl from about $45,000/bpd to $110,000/bpd; wherein the reactor unit has a capacity of less than about 1 ,000 bpd; wherein the reactor unit has a capacity from about 2 bpd to 900 bdp; and, wherein the plant is configured to provide a refined grade methanol.
- FIG. 1 is a chart showing an embodiment of the variation in capital intensity of gas-to-liquids (GTL) plants with plant scale in accordance with the present inventions.
- GTL gas-to-liquids
- FIG. 2 is a schematic diagram of an embodiment of a system and method showing basic gas-to-methanol process configuration with no process intensification.
- FIG. 3 is a schematic diagram of an embodiment of a system and method showing gas-to-methanol process configuration with reactive separation of products in accordance with the present inventions.
- FIG. 6 is a schematic prospective view of an embodiment of a microchannel reactor showing cooling plates and two options for reaction plates (with and without a sweep stream for reactive separation) in accordance with the present inventions.
- embodiments of the present inventions relate to new systems and devices for chemical synthesis that reduce the capital intensity (e.g., capital cost per unit of throughput in, for example, units of Untied States Dollars (USD) per barrels per day (bpd) of capacity) of smaller chemical production facilities.
- the cost of capital equipment tends to scale sub-linearly with capacity at approximately six-tenths power.
- larger processing equipment e.g., bigger reactors, bigger chambers, bigger separators, etc.
- had much better capital intensity i.e., lower values
- Cl In general capital intensity (Cl), is the ratio of the cost of a particular piece of equipment, or the cost of all of the pieces of equipment needed to conduct a particular manufacturing process, e.g., a chemical process, vs. the production or output capacity of that piece of equipment or pieces of equipment.
- Cl as used herein, unless expressly stated otherwise, is the cost in US dollars for a particle piece of equipment or particular pieces of equipment (i.e., a production unit), vs the capacity or output of a product (e.g., rated capacity, projected capacity or actual operating capacity) in bpd from that particular piece of equipment or production unit.
- the units for Cl are US dollars/bpd.
- Embodiments of the present inventions provide the ability to greatly reduce the Cl for smaller pieces of equipment (e.g., smaller capacity) and smaller production units (e.g., smaller capacity). This, among other things, provides for much greater cost effectiveness, for the use and placement of small onsite equipment and processing units. For example, by having a small processing unit, having a low Cl, at a remotely located low value source material supply, the low value source material can be cost effectively processed into a high value material, greatly reducing shipping costs from the remote location.
- embodiments of the present invention provide the ability to reduce the Cl of small-scale equipment and production units by 50% or more, 60% or more, 70% or more, and 90% or more, and be from 30% to 90%, from 40% to 80%, from 60% to 80%, and from 50% to 90%.
- a percentage reduction is the amount of decrees divided by the original value times 100.
- these small-scale equipment and production units have a capacity of 2 bpd to 5,000 bpd, 5 bpd to 1 ,000 bpd, from 5 bpd to 700 bpd, from 10 bpd to 200 bpd, less than 1 ,000 bpd, less than 700 bpd, less than 500 bpd, less than 100, bpd, and less than 10 bpd.
- these small-scale equipment and processing units can have Cis that are the same as the Cis for larger scale (i.e., higher capacity) versions of such equipment and processing units.
- a 1 ,000 bpd processing unit can have the same Cl as a 100,000 bpd processing unit.
- embodiments of the present inventions can have the same Cl as pieces of equipment and processing units that have capacities that are from 2x to 1 ,000x larger, from 2x to 10x larger, from 10x to 100x larger, from 5x to 50x larger, at least 2x larger, at least 10x larger, and at least 100x larger.
- small-scale equipment and processing units refers to capacities that are smaller than 5,000 bpd, smaller than 2,000 bpd, smaller than 1 ,000 bpd, smaller than 500 bpd, smaller than 100 bpd, smaller than 50 bpd, smaller than 10, bdp, and smaller than 5 bpd, and from 2 bpd to 5,000 bpd, from 2 bpd to 1 ,000 bpd, from 5 bpd to 700 bpd, from 10 bpd to 200 bpd.
- low Cl refers to Cis that are less than 250,000 $/bpd, less than 200,000 $/bpd, less than 100,000 $/bpd, less than 50,000 $/bpd, and from 40,000 $/bpd to 200,000 $/bpd, from 50,000 $/bpd to 150,000 $/bpd, and from 50,000 $/bpd to 110,000 $/bpd.
- embodiments of the present inventions include embodiments of these small-scale equipment and processing units having these low Cis.
- embodiments of the present inventions break, or overcome, the long standing scaling paradigm, by providing equipment and processing units that have both small-scale and low Cl.
- embodiments of the present invention process intensification (PI), as set forth in this specification to reduce capital costs for small-scale equipment and production units.
- PI process intensification
- an embodiment of an approach to reduce the capital intensity is to leverage the principles of PI to reduce the capital costs for chemical production, shifting off the traditional line 101 in FIG. 1 and into the region shown approximately by the oval 102.
- embodiments off the present inventions can provide improved operating costs and improved efficiencies.
- Other potential advantages of these embodiments can include improving process safety, thereby reducing energy intensity and minimizing carbon footprint.
- present specification generally addresses improvements to systems, devices and methods to recover in an economical fashion usable fuels from flare gas, and in particular, in an embodiment, to achieve such recovery at smaller, isolated or remote locations or point sources for the flare gas
- embodiments of the present inventions find application and benefits in any industrial (e.g., chemical, hydrocarbon, waste management, etc.) or agricultural (e.g., livestock, food processing, etc.) processes setting, and in particular, where onsite small-scale systems are advantageous.
- preferred embodiments of the present inventions take uneconomic hydrocarbon-based fuels at a wellhead and remote locations that are primarily gaseous hydrocarbons and convert them to a more valuable, easily condensable or liquid compounds, such as methanol.
- source fuel e.g., waste gases
- Another source could be biogas from landfill or anaerobic digesters.
- embodiments of the present inventions are directed to one or more of three methods and device providing process intensification that can be used together or separately, or with other methods and devices: (1 ) Maximizing synergistic effects from partial processes, such as, Functional PI for Reduction of Costs; (2) Optimize the driving forces at every scale, in particular by harnessing non-thermal driving forces, such as Thermodynamic PI for Reduction of Costs; and (3) Giving each molecule the same processing experience, such as Spatial PI for Reduction of Costs.
- the first method and devices relate to the functional domain of PI and generally seeks to integrate process steps in new or different ways to leverage synergies, increase product yield, increase energy efficiency, reduce the physical footprint of a process, and combinations and variations of these.
- Examples include heat-exchanger (HEX) reactors, hybrid distillation, and especially reactive separations.
- HEX heat-exchanger
- reactive separations can be used to combine the reaction and separation steps to overcome the equilibrium limitation and increase the single-pass yield.
- methods and devices to selectively remove the product from the reactor in situ or in a close coupled fashion are used.
- This approach is generally referred to as reactive separations.
- Removing the products from an equilibrium limited reaction has the net effect of inducing additional conversion of reactants according to Chatelier’s principle.
- the separation can be done using various separation technologies such as adsorption, absorption, distillation, and membranes yielding hybrid processes called reactive adsorption, reactive distillation, and membrane reactors.
- Reactive separations can be used to increase conversion at a fixed pressure or to achieve the same conversion as a traditional reactor at lower pressure.
- the second method and devices relate to the thermodynamic domain of PI and generally seeks to optimize driving forces.
- the principle applies to switching from thermal, equilibrium separations of the products to a non-thermal, nonequilibrium alternative.
- separations in chemical manufacturing typically constitute the majority of the equipment cost and operating costs in a chemical plant. These separation processes account for 10-15% of the world's energy consumption.
- distillation the chemical process industry is dominated by distillation, which is very energy intensive.
- the driving force is heat and the separation depends on differences in the volatility of the components within a mixture.
- the third methods and devices relate to the spatial domain of PI and generally seeks to give each molecule the same processing experience (e.g., well- defined and homogeneous temperature-pressure-time histories for packets of fluid passing through the process).
- Other advantages include inducing high heat and mass transfer rates and increasing the surface area for heat and mass transfer.
- process equipment for PI in the spatial domain for reactions include micro-channel reactors, milli-channel reactors, structured catalyst (e.g., monoliths), high-thermal- conductivity catalyst packings, and fractal devices. Because of the complex internal geometries of micro-channel and other devices, these approaches often lend themselves to additive manufacturing (i.e., 3D printing) because they are more difficult to produce with traditional subtractive manufacturing techniques (e.g., require increased parts count).
- Micro-channel reactors use compact micro-channel geometries to increase the heat transfer area between the catalyst bed and the cooling water; these micro-channels also decrease the characteristic distance for heat transfer inside the tubes (i.e., the tube inner diameter), which increases the thermal homogeneity within the catalyst beds.
- the heat transfer rates are measured to be up to 10X higher for microchannel devices.
- the improved heat transfer allows for a compact and precisely controlled process that can handle the highly exothermic nature of the methanol and ammonia synthesis reactions. While these two chemistries are discussed in detail, this approach also applies to other chemistries with no loss of generality.
- Micro-channel devices are also well suited for high pressure applications because the hoop stress (and thus the required wall thickness) scales linearly with channel diameter (or hydraulic diameter).
- micro-channel devices increase heat transfer rates and heat transfer area compared to conventional geometries such as BWRs.
- FIG. 2 there is shown a schematic production flow diagram of a gas-to-liquids process and system that converts flare gas into a syngas intermediate and then to a methanol product via high pressure, catalytic reaction.
- the synthesis unit is a two-stage unit 209 with a first reactor unit 209a and a second reactor unit 209b.
- the system 200 has an inlet air compressor 201 , a mixer 206 for mixing the incoming flow of air and the incoming flow of flare gas.
- the system 200 has an engine reformer 202 for converting the flare gas-air mixture into a syngas.
- the system 200 also has a particulate filter 204, guard beds 203, deoxo reactor 205.
- the portion of the system, directed to converting the syngas to methanol has a water knockout 207, a compressor 210, a two-stage reactor unit 209, having a first reactor 209a and a second reactor 209, a compressor 211 , a hydrogen separation unit 213 and a condensing unit 212.
- product streams are expanded through valves (or backpressure regulators) in a Joule-Thompson (i.e., isenthalpic) process prior to product condensation and collection of crude methanol.
- Joule-Thompson i.e., isenthalpic
- Low single-pass conversions have a recycle loop for unreacted molecules and consequent compression of this gas phase effluent stream back to the inlet of the reactor, which must be sized to accommodate this additional recycle volume.
- This recycle loop thus leads to costs associated with installing and operating a compressor and with increased sizing of the reactor vessel.
- FIG. 3 there is shown a schematic production flow diagram of a gas-to-liquids process and system that converts flare gas into a syngas intermediate and then to a methanol product via high pressure, catalytic reaction.
- the synthesis unit is a two-stage unit 309, with a first reactor unit 309a and a second reactor unit 309b and a reactive separation loop 350.
- the system 300 has an inlet air compressor 301 , a mixer 306 for mixing the incoming flow of air and the incoming flow of flare gas.
- the system 300 has an engine reformer 302 for converting the flare gas-air mixture into a syngas.
- the system 300 also has a particulate filter 304, guard beds 303, deoxo reactor 305.
- the portion of the system, directed to converting the syngas to methanol has a water knockout 307, a compressor 310, a two-stage reactor unit 309, having a first reactor 309a and a second reactor 309, a compressor 311 , a hydrogen separation unit 313 and a condensing unit 312.
- the system 300 has a reactive separation loop 350 (e.g., a methanol separation loop) that has desorber 311 .
- the process uses a two-stage methanol synthesis reactor 309 with reactive separation in the second stage (Rxtr 2) 309b only.
- the first stage (Rxtr 1 ) 309a generally does not approach equilibrium and thus does not warrant reactive separation.
- the embodiment shown in this FIG. 3 is reactive absorption or membrane separation with a liquid sweep.
- the reactor 309b could be a trickle bed or a membrane reactor with the liquid absorbent (sweep) on the permeate side of the membrane.
- Methanol is selectively removed from the reactor in situ resulting in a methanol-depleted gaseous stream consisting primarily of unreacted syngas and a methanol-rich absorbent stream.
- the depletion of methanol in the gaseous stream leads to increased methanol yield as reaction equilibrium limitations are removed.
- the primary recycle loop e.g. FIG. 2
- the methanol-rich absorbent stream is depressurized as it passes through a valve, after which, methanol desorbs and then condenses in subsequent steps in the desorber 311 .
- the absorbent now in a regenerated state, is pumped back to reaction pressure and recirculated to the reactor inlet.
- embodiments of the type shown in FIG. 3, and in particular the syntheses unit 309 with the reactive separation loop 350 can have a low Cl, can be a small-scale processing unit, and can be both small-scale and have a low Cl.
- Embodiments of the type shown in FIG. 3, and in particular the syntheses unit 309 with the reactive separation loop 350 can have the percentage reductions in Cl ass set forth above in this Specification.
- these small-scale equipment and processing units, of the type shown in the embodiment of FIG. 3 can have Cis that are the same as the Cis for larger scale (i.e., higher capacity) versions of such equipment and processing units as set forth above in this Specification.
- FIG. 4 there is shown a schematic production flow diagram of a gas-to-liquids process and system that converts flare gas into a syngas intermediate and then to a methanol product via high pressure, catalytic reaction.
- the synthesis unit is a two-stage unit 409, with a first reactor unit 409a and a second reactor unit 409b and a reactive separation of byproducts.
- the system 400 has an inlet air compressor 401 , a mixer 406 for mixing the incoming flow of air and the incoming flow of flare gas.
- the system 400 has an engine reformer 402 for converting the flare gas-air mixture into a syngas.
- the system 400 also has a particulate filter 404, guard beds 403, deoxo reactor 405.
- the portion of the system, directed to converting the syngas to methanol has a water knockout 407, a compressor 410, a two-stage reactor unit 409, having a first reactor 409a and a second reactor 409, a hydrogen separation unit 413 and a condensing unit 412.
- the process uses a two-stage methanol synthesis reactor 409 with reactive separation in the second stage (Rxtr 2) 409b only.
- the first stage (Rxtr 1 ) 409a generally does not approach equilibrium and thus does not warrant reactive separation.
- the embodiment shown in this FIG. 4 is membrane separation with a gaseous sweep.
- the membrane reactor could use a polymeric or ceramic membrane material that is perm-selective to water and a sweep gas (e.g., air) on the permeate side of the membrane.
- embodiments of the type shown in FIG. 4, and in particular the syntheses unit 409 with the reactive separation sweep can have a low Cl, can be a small-scale processing unit, and can be both small-scale and have a low Cl.
- Embodiments of the type shown in FIG. 4, and in particular the syntheses unit 409 with the reactive separation sweep can have the percentage reductions in Cl ass set forth above in this Specification.
- these small-scale equipment and processing units, of the type shown in the embodiment of FIG. 4 can have Cis that are the same as the Cis for larger scale (i.e., higher capacity) versions of such equipment and processing units as set forth above in this Specification.
- FIG. 5 there is shown a schematic production flow diagram of a gas-to-liquids process and system that converts flare gas into a syngas intermediate and then to a methanol product via high pressure, catalytic reaction.
- the synthesis unit is a two-stage unit 509, with a first reactor unit 509a and a second reactor unit 509b and the sonoseparation of the condensate stream, consisting of crude methanol.
- the system 500 has an inlet air compressor 501 , a mixer 506 for mixing the incoming flow of air and the incoming flow of flare gas.
- the system 500 has an engine reformer 502 for converting the flare gas-air mixture into a syngas.
- the system 500 also has a particulate filter 504, guard beds 503, deoxo reactor 505.
- the portion of the system, directed to converting the syngas to methanol has a water knockout 507, a compressor 510, a two-stage reactor unit 509, having a first reactor 509a and a second reactor 509, a compressor 511 , a hydrogen separation unit 513 and a condensing unit 512.
- the system 500 also a system to refine the methanol produced from the synthesis unit (e.g. methanol refining unit).
- the methanol refining unit has a sonoseparator 552, a mist collector 551 and a generator 550.
- the sonoseparation step proceeds by exposing this liquid stream, which can contain up to 10 vol% water, to ultrasound waves, in the sonoseparator 552, generating a mist composed of micron-sized droplets, enriched in methanol, that are entrained in inert gas flow (e.g., nitrogen).
- the embodiment shown in this FIG. 5 includes a collection set-up (e.g., mist collector 551 ) that facilitates the nucleation of a liquid phase from the flowing effluent mist.
- the recovered liquid in these mist collectors can be composed of highly pure, refined grade methanol (99.85% methanol), achieved without the need for cost-intensive installation and operation of thermal, equilibriumlimited separation processes, such as distillation columns.
- Power for the ultrasound actuator in the sonoseparator 552 can be supplied by a generator 550 coupled to the shaft of the upstream engine reformer 502 (as shown in FIG. 5), or by expansion of the tail gas in a turbo-expander coupled to a generator, by renewable sources (e.g., wind, solar), or by other sources.
- the water-rich stream exiting the sonoseparator 552 that is depleted in methanol can be used elsewhere in the process, stored, used to stimulate a well, further purified on-site, disposed on-site, transported and processed remotely, used for irrigation, or the like.
- embodiments of the type shown in FIG. 5, and in particular the syntheses unit 509 with the sonoseparation system can have a low Cl, can be a small- scale processing unit, and can be both small-scale and have a low Cl.
- Embodiments of the type shown in FIG. 5, and in particular the syntheses unit 509 with the sonoseparation system can have the percentage reductions in Cl ass set forth above in this Specification.
- these small-scale equipment and processing units, of the type shown in the embodiment of FIG. 5 can have Cis that are the same as the Cis for larger scale (i.e. , higher capacity) versions of such equipment and processing units as set forth above in this Specification.
- FIG. 6 there is shown an exploded perspective schematic view of an embodiment of a micro-channel reactor geometry with cooling.
- This microchannel reactor can be used in any gas-to-liquid systems and processes, in particular flare gas to methanol systems and processes. Further, this micro-channel reactor can be used as the reactor in any of the embodiments of the types of systems and processes shown in FIGS. 2 to 5. Preferably, this type of micro-channel reactor would be the second reactor in the system, or could be a third or additional reactor.
- the micro-channel device 600 has two reaction units or plates 602, 604 that have cooling units or plates 601 , 603, 605 on either side of the reaction units. It being understood that the figure is an exploded view, and thus, in actuality the surfaces of the units are in physical and thermal contact with the adjacent units. While 5 units are shown it is understood that there could be 3 units (one reaction and two cooling), 7 units, 9 units, 11 units, etc. While it is preferred that each reaction unit has a cooling unit on both sides (as shown in FIG. 6), embodiments may have configurations where the outer most reaction unit has only a single cooling unit adjacent to it.
- the flow of reactants is shown by arrows 602b, 604b.
- the flow of the reactants 602b, 604b is in a serpentine path in each of the respective reaction units 602, 604.
- the flow of the coolant is shown by arrows 601a, 603a, 605a.
- the flow of the coolants 601a, 603a, 605a in in a parallel path in each of the respective cooling units 601, 603, 605.
- heat is transferred from reactants to the coolant through the walls of the micro-channel device 600.
- characteristic heat transfer lengths are kept short, and heat transfer area per unit of overall volume is larger than in traditional reactor designs.
- the advantaged heat transfer helps to ensure uniformity of the catalyst bed temperature and mitigates hot-spot formation, which is a primary mechanism for catalyst sintering and deactivation.
- the coolant could be a single-phase heat transfer fluid or a boiling fluid such as water.
- the coolant and reactant flows are countercurrent so that, in the case of an exothermic equilibrium-limited reaction, the heat (generated from reaction) from the reactor effluent stream can be transferred to the inlet coolant fluid (exhibiting the lowest temperature) at the reaction-plate outlet, encouraging higher equilibrium conversions, although other configurations (concurrent, crossflow) are envisioned.
- a reaction unit (one, more, than one or all) can have a second reactant, promoter, quench, or sweep stream that can be introduced into the flow of the reactant in the reactor unit or plate.
- the reaction unit 602 is a “reaction plate with sweep”.
- the flow of the sweep stream is shown by arrow 602c.
- the second stream, e.g., sweep stream 602c can be an absorbent that selectively removes the products or byproducts in situ in a microchannel, reactive separation configuration. This would be viewed as a reactive separation.
- a microchannel mixer can be used near the entrance of the reaction unit to create alternating slugs or bubbles of sweep fluid and reactant fluid to provide increased interfacial surface area for mass transfer.
- the microchannel mixer can be, for example, a static mixer.
- a microchannel 24isengage can be used to disengage the sweep fluid and the reactant fluid near the exit of the reaction unit.
- the two fluids are disengaged based on wettability or capillary forces using microchannel features (e.g., an array of posts) in the flow path.
- the thickness of the channel walls required for high-pressure applications is smaller for these microchannel devices compared to larger, conventional equipment designs because of the linear scaling between hoop stress (and hence wall thickness) and channel hydraulic diameter.
- the thinner walls reduce the amount of material required for fabrication and hence reduces the manufacturing cost.
- Manufacturing cost can further be lowered by use of additive manufacturing (e.g., 3-D printing) to form the microchannel plates.
- Additive manufacturing also reduces the part count by allowing channels to be printed in place as a single part without the need for a parting line as would otherwise be required for casting or conventional machining. Avoiding the parting line reduces cost (fewer parts) and reduces the likelihood of leaks at the seal (e.g., o-ring, gasket, brazed connection) joining the two halves of the microchannel plate.
- the additive manufacturing may be paused to allow for manual or automated loading of catalyst in the channels and later resumed to complete the channels and encasing of the catalyst.
- the 3D printer can have multiple print heads for printing both the microchannel walls and catalyst/support in the same program/operation.
- the 3D printer may use various types of additive manufacturing including selective laser sintering (SLS), binder jetting, fused filament fabrication (FFF), and the like.
- the catalyst can be printed as an ink that is deposited on the channel walls or another high-surface-area textured support that may also be 3D printed.
- each reaction plate can include a serpentine path to optimize residence time for the chemistry to proceed to the desired conversion.
- the cooling plates can preferably be configured to distribute the coolant among a collection of parallel paths to provide uniform cooling to the reaction plate.
- a coolant header that is located within the reaction plate, as shown in FIG. 6 can be used to distribute the flow of the incoming coolant between the parallel channels within the plate, and then a return or collection header can also be used to combine the parallel channels into a single exist channel for the coolant to then leave the plate.
- the coolant headers, and in particular the distribution header can be designed to minimize flow distribution between the parallel channels.
- FIG. 7 there is shown a schematic diagram, with callout, showing the use of a high-thermal-conductivity catalyst support such as a fine, microfibrous nonwoven mat 701 , embedded within reactor tubes 702 in a boiling water reactor (tube/shell configuration).
- the thermal conductivity of the support e.g., copper, nickel, or other metals or alloys
- the microfibrous catalyst supports 701 improve bed temperature uniformity, allow the use of fine catalyst particles thereby eliminating intra-pellet mass transfer limitations, and improve bed-to-wall heat transfer.
- the microfibrous supports are used with a sweep stream that selectively removes the products or byproducts in a reactive separation configuration that also incorporates microfibrous structured material internal packing.
- This embodiment contains elements of both PI in the functional and spatial domains.
- the sweep stream could be a liquid absorbent or the like.
- FIG. 1 there is shown a graph plotting how capital intensity varies with process scale for prior art gas-to-liquids (GTL) plants.
- GTL gas-to-liquids
- line 101 capital intensity is highest for small-scale processes and follows a power-law scaling.
- embodiments of the present inventions provide gas-to-liquid flare gas processing systems that have Cis in the area 102, which is similar to the Cis for a world scale plant.
- Process intensification either functional, thermodynamic, or spatial, can be used to reduce the capital intensity, especially at smaller scales, rather than simply scaling down the same technology used at the world scale plants.
- a downstream synthesis reactor and process that selectively removes the product or byproduct of the synthesis reaction from unreacted synthesis gas (syngas) from the reformer to shift the equilibrium to achieve higher conversion at the same reaction conditions.
- the reactor and process have the following features:
- a means of separation of the products from the reactants in the reactor which may include one of adsorption, absorption, membrane separation, distillation, or the like.
- a downstream synthesis reactor and process that selectively removes the product or byproduct of the synthesis reaction from unreacted synthesis gas (syngas) from the reformer to shift the equilibrium to achieve higher conversion at the same reaction conditions.
- the reactor and process have the following features:
- a means of separation of the products from the reactants in the reactor which may include one of adsorption, absorption, membrane separation, distillation, or the like.
- a sonoseparation method and device that upgrades crude methanol to refined methanol using a non-thermal method, as an alternative to conventional distillation.
- the method and device have one or more of the following features:
- the electric power for the ultrasonic actuators being produced by a generator coupled to the shaft of the engine reformer.
- a means of also accepting other electric power for the sonoseparation such as renewable power produced by turbo-expander, solar, wind or other source.
- the structured material being one of a micro-channel reactor, a millichannel reactor, a monolith, a high-thermal-conductivity catalyst packing, a fractal device, or the like.
- the structured material being one of a micro-channel reactor, a millichannel reactor, a monolith, a high-thermal-conductivity catalyst packing, a fractal device, or the like.
- the device and method having one or more of the following features:
- HTC high thermal conductivity
- These supports are composed of open cell structures that allow fluid to permeate through their void space, such as foams used in other applications, ranging from heat exchangers, air/oil separators, filters, and scrubbers.
- foam structures can be composed of solid ligaments and be made with materials that exhibit high thermal conductivity values, leading to high rates of heat transfer and more uniform heating or cooling of flowing gases. These heat transfer rates may depend on the material of the foam (e.g., alloy, oxide, ceramic, etc.) as well as physical parameters such as the void space, the number of pores per inch (PPI, i.e., pore density), ligament thickness, and the intimacy of contact between the foam and wall surfaces.
- PPI pores per inch
- ligament thickness the intimately contact between the foam and wall surfaces.
- thermally conductive, supporting foams can be exploited in reaction environments, among others, where non-uniform heating within a packed-bed reactor often leads to localized heat variations that could degrade or deactivate catalytic materials, leading to higher risk of runaway reactions, or to limitations in attainable conversions, because of the constraints imposed by chemical equilibria.
- Implementing open-cell structures within modular reactors for the conversion of syngas to methanol can potentially lead to lower catalyst requirements, less frequent catalyst replacements, smaller reactor vessel sizes, and lower pressure operation and compression work and thus translate to smaller overall system footprints and to process designs that are inherently simpler and ultimately less expensive to build and operate.
- Metal foams are preferred to alternative HTC structures, such as fine nonwoven metal meshes, because the foams are easier to pack and more practical for commercial reactors.
- catalysts for industrial methanol synthesis typically composed of CuO, ZnO, and AfeOsJ are sold in the form of cylindrical pellets (approximately 6 mm diameter x 4 mm). These catalyst materials can be crushed and sieved to retain aggregates exhibiting a narrow particle size range (e.g., 0.25 to 1.0 mm), suitable for loading into the pores of the HTC foam support.
- the reactor can use the HTC of Example 7.
- the aluminum 6101 HTC foam consists of pores exhibiting an average diameter (1 .27 mm; 20 ppi) sufficient for accommodating these aggregates foam, and a relative density of 8-10%. A 1/16” O.D.
- stainless steel thermowell was positioned at the centerline of the catalyst bed and extended along the length of the reactor, in order to measure the temperature, using a K-type thermocouple (0.02-in. diameter), at different axial positions (x) along the total length (L) of the bed.
- Methanol synthesis reactions were performed at given pressures (up to 50 bar) and temperatures (200 to 250°C) by flowing syngas mixtures over freely-loaded catalyst aggregates or aggregates packed in the HTC-support, at variable gas hourly space velocities (GHSV, units of (L/h)inietgas/Lcataiystbed).
- GHSV gas hourly space velocities
- the reactor was enclosed within a heated oven furnace, the temperature of which (Toven) was kept constant; at all bed positions, Toven was lower than the reactor temperature ( rx tr), reflecting the heat generated from the exothermic methanol formation from CO and CO2 hydrogenation. Temperatures were measured at varying axial positions within and upstream of the catalyst bed.
- the greater temperature uniformity garnered from the use of HTC-supports thus provides each molecule with a more similar processing experience, leading to the higher H2 and carbon conversions observed at all GHSV and an intrinsically more active catalyst bed for the HTC-support system, as shown in Table 1 .
- HTC high thermal conductivity
- the methanol reactor being a multi-tubular boiling water reactor with HTC supports and catalyst in the tubes and boiling water on the shell side.
- the methanol reactor being a quench reactor with HTC supports and catalyst in one or more substantially adiabatic sections of the reactor vessel with quench gas introduced between the sections.
- the HTC supports being made of materials with high thermal conductivity such as copper, aluminum, graphite, or zinc.
- the reformer reactor being an engine reformer.
- HTC high thermal conductivity
- HTC high thermal conductivity
- Reactive separation e.g., reactive distillation, reactive adsorption, reactive absorption, reactive membrane separation
- Non-thermal separation e.g., sonoseparation, membrane separation
- present inventions may lead to new, and heretofore unknown theories to explain the conductivities, fractures, drainages, resource production, chemistries, and function-features of embodiments of the methods, articles, materials, devices and system of the present inventions; and such later developed theories shall not limit the scope of protection afforded the present inventions.
- the various embodiments of devices, systems, activities, methods and operations set forth in this specification may be used with, in or by, various processes, industries and operations, in addition to those embodiments of the Figures and disclosed in this specification.
- the various embodiments of devices, systems, methods, activities, and operations set forth in this specification may be used with: other processes industries and operations that may be developed in the future; with existing processes industries and operations, which may be modified, in-part, based on the teachings of this specification; and with other types of gas recovery and valorization systems and methods.
- the various embodiments of devices, systems, activities, methods and operations set forth in this specification may be used with each other in different and various combinations.
- the configurations provided in the various embodiments of this specification may be used with each other.
- the components of an embodiment having A, A’ and B and the components of an embodiment having A”, C and D can be used with each other in various combination, e.g., A, C, D, and A, A”, C and D, etc., in accordance with the teaching of this specification.
- the scope of protection afforded to the present inventions should not be limited to a particular embodiment, configuration or arrangement that is set forth in a particular embodiment, example, or in an embodiment in a particular Figure.
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Abstract
L'invention concerne des installations intensifiées comprenant des reformeurs chimiques et un équipement de synthèse chimique en aval. L'invention concerne également des systèmes, des procédés et des dispositifs permettant une intensification de processus (PI) qui conduit à la réduction du nombre de pièces, à une fonctionnalité de fusion, à l'élimination de goulots d'étranglement, à la réduction des coûts et à la modularisation de sous-systèmes pour une facilité d'assemblage et d'entretien en vue d'atteindre la simplification globale nécessaire pour obtenir un coût de produit compétitif à de petites échelles. Dans un mode de réalisation, les installations améliorées utilisent des reformeurs de moteur pour produire un gaz de synthèse, qui est en outre converti en produits finaux à l'aide de réacteurs en aval intensifiés.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2022/029707 WO2022245879A2 (fr) | 2021-05-18 | 2022-05-17 | Systèmes et procédés de conversion de gaz de torche modulaires autonomes |
US202263343087P | 2022-05-18 | 2022-05-18 | |
PCT/US2022/044724 WO2023049450A1 (fr) | 2021-09-26 | 2022-09-26 | Procédés et systèmes associés à un moyeu de valorisation de méthanol modulaire |
PCT/US2023/067087 WO2023225532A2 (fr) | 2022-05-17 | 2023-05-16 | Systèmes, dispositifs et procédés d'intensification de reformeurs et de synthèse chimique en aval |
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EP (1) | EP4526280A2 (fr) |
AU (1) | AU2023273035A1 (fr) |
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US20070151451A1 (en) * | 2005-12-22 | 2007-07-05 | Rekers Dominicus M | Process for the cooling, concentration or purification of ethylene oxide |
CN102597173A (zh) * | 2009-09-08 | 2012-07-18 | 俄亥俄州立大学研究基金会 | 具有原位co2捕集的合成燃料和化学品生产 |
US9169773B2 (en) * | 2012-04-18 | 2015-10-27 | Massachusetts Institute Of Technology | Engine reformer systems for lower cost, smaller scale manufacturing of liquid fuels |
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- 2023-05-16 AU AU2023273035A patent/AU2023273035A1/en active Pending
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