4nn209, 718 cre_povember. 2023 [20 2a Cover Story Hydrogen Production via Methane Pyrolysis: An Overview of ‘Turquoise’ H» “Turquoise’ hydrogen processes generate H, without releasing CO». Presented here are the opportunities and challenges for producing hydrogen by methane pyrolysis Carl Fromm. Green Star BCS, LLC yyorogen-producing pro cesses are classiied using f color scheme according to ther carbon footprint (Table 4; [7-3). So-called “turquoise hydrogen” is produced by methane decomposition, which encompasses the folowing: thermal breakdown cof molecular bonds (pyrolysis), non: thermal breakdown using non-ther- ‘mal plasma (plasmalyss), radiation (photovsis; and chemical spiting (hemolysis) through —halogenation OF NiCi, redox reactions [4,5]. Ad- jacent Ho-producing processes in volve pyrolysis of plastic waste, paper and biomass, methane couping into acetylene, cry methane reforming, hydrogen sulfide spitting and others. ‘This article discusses the thermo- dynamics, process. configurations and technical challenges associated with turquoise hydrogen production. A companion piece to this article (608 pp. 12-16) covers the commer. ial development of turquoise Hp, along with the progress of compa- nies and research organizations that {are pushing the technology ahead. At the present time, turquoise y- drogen is a competitor to incumbent atey hydrogen, produced by steam methane reforming (SMR), and 10 blue hycrogen, produced by SMR. with added carbon capture and storage (SMR-CCS). Compared to SMR, methane. pyrolysis consumes. twice as much feed fo produce the same quantity of hydrogen. How- ever, it does not produce direct COp emissions, and offers energy sav- ings, as well as potential revenues {rom the sale of carbon co-product. Methane pyrolysis Methane can be viewed as a hydro- gen carrie, ike ammonia, rather than as.a tual. The methane pyrolysis (MP) reaction (Equation (1)), also called methane cracking, spitting or ther- molysis, breaks methane molecules rectly into elemental hydrogen and carbon at elevated temperatures, typically at 600-1,200°C: CH(g) —> 2H-4g) + C's) gH® = 74.85 ku/mol CH, AGH OOO = 91,7 KON CH, (1) The MP reaction is endothermic and requires 37.4 kJimol H at standard conditions, in contrast to th286 kJ/mol Hz needed to produce green H, by water splitting through electrolysis or thermolysis. It_ also compares favorably to the 63 ki/ mol Hp required by the SMR reac- tion combined with the water-gas shift reaction and steam generation for the reformer, If all H, produced is combusted, the overall cycie can be viewed as burning off hydrogen only while leav- ing carbon intact. Combustion of produced Hp yields 484 kl/mol CH, which provides 60% of the low heal- ing value of methane (802 kJ/mol CH,), where carbon is fully oxidized t0.CO,, ‘The MP process can thermally sus tain itseif since only 15-25% of avai- able H, combustion heat is needed 10 provide the required heat for the reaction. The remaining 75-85% of Hy produced can be exported or used onsite. ‘Methane conversion yield is ro- moted by low pressures and higher temperatures, in accordance with La Chateiers principle. MP reactors are maintained above atmospheric pres- ‘sure to prevent in-leakage of air any- ‘where in the process, to minimize ro- actor size and to speed the reaction. ‘As for kinetics, the reaction be- ‘comes spontaneous at approx- mately 550°C and attains chemical Ec calor clasication Hy manufacturing process MM ‘0, emissions from pan oper ‘ots ig 0, per ko prediced ‘Bock ‘Btuninus cal gestion 18-20(11 Bom mn coal foe) pasteaton 7-142) Gey Ro rate 2 ening au ‘Sm with cs oassing, Tue Natura gs decompostion on Goon eyes of wat sng renewable eroy CHEVICALENGINEERNG WWNICHEVENGONLINECOM NOVEMBER 2023 al https wunxtbook comfaccessinsligence/ChemicalEngineeringiche_november-2023index shoti/20 184in209, 718 yr cre_povember. 2023 [20 rover Rey es reaured er ong hon bre! 2a i i iN nat pre ta alee ‘equilibrium at higher temperatures (1,300°C+) and higher pressures (61 atm). Reaction rates at lower temperatures are relatively slow, so the overall conversion is kinetically limited. For this reason, consider- able research efforts have been in- vested into developing catalysts ca- ppable of speeding up the reaction at lower temperatures. For inital reactor sizing and deter- mining the overall CH, conversion, the MP reaction rate, 7, can be ex: pressed through simple first-order kinetic equation: ~OICH Yat = K(CH,] @ ‘where the reaction rate constant, k, is given by the Arrhenius equation. ‘A oxp -E/RM«ICHa) ® ‘The pre-exponential factor A and the activation energy E, are determined experimentaly and can be found in Iterature for specific reactor configu- rations. For example, Becker and oth- 3 [6] present a compilation of A and , values for various reactor types. Equation (1) does not account for reactive species, such as acetylene, ethylene, ethane and higher hycro- carbons, along with CO, HzO and FIGURE 1. Tis low clagram shows the element of ene metane- pros process used in manutcturigturuosehysogen mercaptans that may be present in natural gas. To account for these species, schemes invoking simul- taneous reactions were develoned {600 the onine version ofthis article at www chemengoniine. com) Natural gas (NG), themain source of methane, is widely available through the existing S-milion-mile long pipe- fine infrastructure in the U.S., which is a significant plus for wide-ranging MP deployment. By contrast, transport ing Ho ftom centralized ‘production facies to potential users will require huge and challenging expansion of tho existing 1,700 mile-long Hp pipe- Ine infrastructure. The greenhouse gas emissions (GHGE) that originate within the MP Plants include fugitive NG leaks and ‘combustion of tal gas fom He pu- rifcation operations. Offsite GHGE orginate in upstream NG produc tion, transport and. storage opera tions, and involve NG leaks, flaring and combustion to generate heat for NG purification, power for prpeine compressors and associated fossil- fuel power plants. Operating plant ‘missions can be easily exceeded by offsite emissions, which stresses, the importance of eliminating NG leaks everywhere in the supply chain, using power from renewable energy ‘Sources, or generating plant power onsite using Hp. In the context of offsite impacts, it is worth noting that MP can remove (CO, from the atmosphere if the feed is biomethane obtained by anaerobic decomposition of biomass, such as landfil gas, anaerobic digestor off- {gas from green waste decomposi- tion or from municipal and industrial, wastewater treatment Reaction products ‘As stated above, the main products ff the MP reaction are Hp and solid cearbon. The main uses of Hp include: * A reactant for production of basic chemicals (such as. among), pe- troleum refning, reduction of metal ‘oxide ores, hydrogenation of fats and other processes * A clean (no carbon emission) fuel for processes requiring figh-tem- perature heat, such as ore smelting, calcination, manufacture of cement, lass, ceramic materials and others * A clean fuel for electric power gen- eration and for propulsion of ships, locomotives. and aircraft using ei ther direct combustion or fuel calls. ‘Automotive use is limited by lack of large-scale He distribution inftestruc- (CHEMICAL ENGINEERING WWWVCHEMENGONLNECOM NOVEMEER 2023 https wunxtbook comfaccessineligence/ChemicalEngineeringiche_november-2023index shotii20 284nn209, 718 ture, although this can be changed by distributed modular MP systems Produced elemental carbon can be used commercially as a filer for tire rubber and plastics, @ pigment for ink and coatings, an adsorbent, reducing reactant for pyrometal lurgical applications, for electrodes manufacturing, and more recently, asa flament for production of struc: tural polymers using carbon fibers, ‘nanotubes (Figure 2) or graphene, If the MD process is deployed on large scale commensurate with the current Hy world-wide demand (around 97 milion metric tons Ha! yt), the solid cartvon produced (284 milion m.t/yr of C) would far ex- ceed current combined demand for carbon black, graphite, metal lurgical coke, and anode coke (50 milion m.tiyr_ of ©). Unless. new high-volume commercial uses are ‘established, this huge excess of 244 milion m./yr of C would have to be land:-disposed (for example, in aban doned mines). This problem would be exacerbated if future demand for Hy is increased — for example, re placing coke with Hg in steel manu facture can increase Hp demand by 90 milion m.t./yr alone. Perpetual storage of solid carbon does not pose the risk of CO, re- leases associated with CCS, which involves transporting and storing of liquefied or supercritical CO. under pressure in geological formations. in stead, the risks include carbon dust explosions and potential toxicity due to presence of residual carcinogenic polycyclic aromatic hydrocarbons (PAH). Fortunately, both of these risks can be mitigated, Unlike CO2 pipelines required for CCS, transpor- tation infrastructure for buk solids is firmly in place. Also, filing empty mines with carbon could preserve some coal-mining jobs. Process configuration The block flow diagram shown in Figure 1 shows a generic MD pro: ‘cess and outines various technology alternatives. Brief descriptions of the process steps folow, Feed purification. Pipeline-qualty natural gas feed may be treated wth zinc oxide (2n0) to remove odorant mercapiens and any residual HS ‘che_november- 2023 [20-21 por to reaction to avord metal cata- Iyst posoning. For thornal or carbon- catalyzed reactors, the desuturzaton stop is not necessary, since minor amounts of HS and mercaptans in the feed actualy promote methane decomposition in the presence of carbon [7], in genera, smal concen- trations of Cp to Cs. hycrocarbons, Cp, Np and HO should not sig- nian affect the methane pyroy- sis process, although their process fate, such as methane-water rac: tions leading to CO or COs foeration, needs to be considered in the overall iprocess design. One concern arises if Gp, hydrocarbons are present in NG at higher concentrations, which could lead to excesswve carbon deposition. Mtigaton measures may include pre- pyrolysis reactors (6 Methane pyrolysis reactors. Met ane pyrolysis reactors can be grouped into three categories: plasma, thermal and cataytc. Table 2 contains de- sctipions of each reactor ype. Entrained carbon separation. Car- bbon particles entrained inthe reactor ext gas can be soparated using oy- clones, sintered-metal fiters or high- temperature baghouses equipped with ceramic fiter elements He purification. In this step, Hp is separated from unreacted CH, Co. hydrocarbons and other species present in the ftered and cooled re- actor offgas. The separated hycro- carborich steam is recycled back to the reacter. Separation processes include pressure-swing adsorption (PSA), membrane separation and lean 0 absorptior”/desorption. These pro- cesses Can also be used to remove on-hycrocarbon species (euch as Np, Op, HeS and HO) fom the re- actor ofgas. To prevent thor buldup, the hycrocarbon-rich recycle stream must be purged, or a separate stream containing these compounds. would have to be generated (for example, through staged PSA depressurization and purge sequence) A portion of the purified Hp may bo recycled back to the process for plasma-gas generation andor Pauses ta ra ice carver aoe needed to minimize carbon depos- its on feed-gas injection nozzles or reactor wall Taligas treatment. Since the purge CHEMICALENGNEERING WWW.CHEMENGONLINECOM NOVEMBER 2028 WSS aie dine lNE O, INCREASE BEANS ANS) | \ AUMA CORALINK Discover our digital ecosystem auma coralink.auma.com https wunxtbook comfaccessineligence/ChemicalEngineeringiche_november-2023index shotii20 a84in209, 718 yr che_november- 2028 [20-21 (OEE Reactor Descrinon| ‘ype Pasra rer ssa reacts cons of oh hema (in plasma nt non-heme, plasma react. eps sea gh oes 20000) yan elt ae {sie alsa torch ether reco ty mong the (<6. 0000 pata gas ener by passing Uregha plas rch Meare cma ans are toen yh br ta and extn, Pasa gas smite wth part fe nening et and routed oe reac- tn cares here tis met in sps wih theremin fed gs. The esto chamber Brvdesesece tine fx ecarbtio oflomed ree aca an nso fr eazton ‘roasts non hralpana eac, Be fee assay healed 1 700-S00C by ‘sing recy taupe “wa pls (600-6000) ners by merous ‘ty Gran adr, "col asa geet ochre dae: {tn team pled decharge roa dichage In a theral plasma reals CH bond ‘res ey nkractons wth Nih-neay Pat-tperte) aecns Methane con ersn and eacton raat cangton pan on plasra gona pe “Themal eats ype cpr at 1003200 a poie aoe fatal ant manly roncatate Ci ecomooston sg the flog cntguraons. Tubular racers, wit ing gas miss ead by rece wal that ar hap! by xa eters rt eas ram H cambston Fuca tes actors whore racSvs ecu bah inthe racing gas mite ae nthe ‘face of ude pares. Ty eontquatins employ butbing beds where stot he ‘3 conte nthe tubing tau depersed pati ers pase, The het ‘Severed by het ecto val by aso Sream of sol partls crete tough an extra ete “Ercne bed ests ato kno as ft, spout be rs react) emp it {ube ter sige wih te reacting ges motu and enraned parce ie ete and ‘at ia sparain camber e-entand pares escent ine amas roaring {elt ib lot renoot lh acer Soom Sons acon bes reed bak ‘Die lit ube tere emer “Moving bed reactors wee 2 domvar-noving dese ba of parts sn ret cent ‘ah an wparemonng es. Bara naan cls at eestor wal andthe ea {i 2, aough er eating meted canals be used “Maten-ecia sacs wie ecing gs miei bubbes heugh pol of mote ‘nal or a orb eed ay eect parson Peat ty ot ec wal By a tral al ckaston este. Curation cud) bbble column ets where ‘aon foodie tering ga utlsaecumuates on rp of be lta removed ‘hrogh an orion) wet inc eats where te descending rng met fe ‘emoves carbon fm eres, a6 (9) eapliysg-ow rescore Cty atic rac se a cataystoanwerate MP reactions pote Ch, conversa over eects temperatures (1,000 andimgrve selectvtyfover Hy rr twa te deed tr fearben, Cay reechons canbe concn nour acts fed bod eats or Inioten moda acs or the talgas may include small ‘amounts of hydrocarbons, CO, or HS, diect atmospheric discharge may not be acceptable without treat- mont using either regenerative or recuperativeyeatalytc. oxidizers. To minimize carbon footprint, high en- ‘ergy eficiency is required, and pro ‘duced Hy should be considered for auniiay foe Carbon processing and purifica- tion, Separated carbon that exits the reactor, cyclone, or iter as a dense particulate stieam may requite coo! ing prior to subsequent steps. This ‘can be performed in bulk solids coo) ers employing vertical plate or tube ‘col exchangers, rotary coolers or jacketed augers. Size reduction using high-velocity 985 ets, miropulverizers, or contin- tous bal, rod or pebble mis, along with the particle siz classifier and re- cycle may be necessary to produce particles suitable for recirculation back to a fluid-bed or to a moving- bed reactor after reheating, Carton co-product may have to be stripped of adsorbed Hp, H2S, CHs land larger hydrocarbons to alleviate safety conoems in downstream han- dling. Stripping may be performed using steam-biown or ai-biown 1o- tary drums oF fluid beds. If reduc ing residual PAH concentrations is desired, carbon can be heated to high temperatures to volatlize anc/or pyrolyze PAH while stripping lighter species. Alternatively, PAH may be removed using solvent extraction [9] ‘and possibly recycled back to the MP reactor. Stripper off-gas should be routed to the taigas treatment before atmospheric venting, Carbon particles removed from ‘molten media reactors may be con- taminated with salts or metals, which ‘can be removed by evaporation in a rotary kiln or in a tunnel furnace. Water-soluble salts may be removed ‘by a water washing cascade with an evaporator/erystallizer to recover the salts, and a dryer to dty washed car- bon ‘product. Metal contamination ‘may also be removed by particle-size Classification, magnetic separation or acid washing Carbon aggregation. in this step, fine carbon particles are aggregated to mitigate dusting from subsequent soids-handing operations and the associated safety and environmen tel concerns. Parte size can be in- ‘creased through briquetting, extrusion, {granulation or pelletizing after accion Of sulabie binders. Other steps may >be required for carbon nanomaterials. ‘Molt processing. This step iS needed for molten-media reactors, to remove any carbon and impuri- ties present in the melt to prevent their accumulation to unacceptable leve's. While carbon can be removed bby met fitration, cissolved contami nants may require purging, which necessitates makeup or periodic replacement. Purged molten metal ccan be soldiied and recycied offsite. Purged salt may have ta be disposed of 8 process waste. A melt circula- tion loop ‘with a reheater and elec ‘tromagnetic pump can be used as ‘a heat carrier, although heating cols, laced inside the reactor can also ‘provide this function, Catalyst processing. Catalyst mixed with carbon is withdrawn from fluid leed- or moving-bed reactors as. a dense particle stream. Processing may ental rillng followed by separa- tion of carbon and catalyst through sieves or particle-size classifiers. It ‘also can include catalyst regeneration, \whereby carbon deposits are burned off or gasfied using steam, and cata lyst reheating prior to recycling back to the reactor. Catalyst purge and makeup are also parlormed at ths step. Molten-meda catalysts require puriication, purge and makeup (see ‘melt processing). The recirculating calalyst stream can be reheated be- fore returning to the reactor to serve 1s reaction heat carter. (CHEMICAL ENGINEERING WWWVCHEMENGONLNECOM NOVEMEER 2023 https wunxtbook comfaccessineligence/ChemicalEngineeringiche_november-2023index shotii20 484nn209, 718 ere_povember-2028 [20-21] ferocene Fe(CsH)2 developed by Pactic Northwest Na- ‘and sulfur adjuvants tional Laboratory (PNNL; Richland, have been used to pro- Wash.; wwwpnni.gov) that uses fu mote carbon nanotube ized iron-based catalyst [16] formation without ca Altemativly, uidized catalyst part ‘bon wall deposits ina cles can undergo attrition and phase ddownflow tubular reac transformation inside the bed, rela. tortested by Huntsman ing aocumulated carbon in the form, (The Woodlands, Tex: of fine particles that are entrained |www.huntsman.com) into reactor gas and then elutiated for production of Mi- outof reactor, as is done inthe Hazer ralon, a carbon neno- Group Lid. (Perth, Australia: www. tube material [14, 15]. hazergroup.com.au) process. that, —= Prevention of carbon uses iron ore catalyst in multistage FIGURE 2 Metiane pois pocests can produce soverlfoms of uldup led to the de- fuidized-bed reactors [77]. arbor, such as carbon rote, he those shown here velopment of fuidzed- In the moving-bed reactor being Technical challenges bed reactors, moving- developed _by BASF SE (Ludwig The MP process poses technical bed reactors and bubble-column shafen, Germany; wnvw.basf.d) challenges. Four ofthe main ones — reactors, all of which are being ac- [18], a dense phase of cerbon per- ‘carbon depostion, stow reaction, dé- tively pursued by commercial fms. ticles moves downward countercur- lvering heat to the reactor and heat In the ficized-bed reactors, carbon _ rent to the gas flow inside a cyindor recovery — are discussed below. preferentially forms on the surface of equipped with the hot wall reaction Carbon deposition. Carbon depo- fluidized paricies which grow in size section heated by external induc sition on internal surfaces of tubular and are continuously removed from tion-coil. Hot sobd carbon particles reactors leads to reactor plugging the bed by gravity-setting below exchenge the heat directly with the and unstable operation. Fouled reac- the gas distributor or using an inter- reacting gas moving upward. Car tors must be periodicaly shut down nal overfiow weir near the top of the bon particles grow due to depos to remove carbon deposits from the bubbling fuid bed, as in the process tion of formed carbon on their sur walls and feed-gas injectors, and replacing or regenerating the fixed bed of catalyst. This necessitates the use of multiple parallel reactors to maintain. production continuty, which adds cost and considerable complexity to the process. Mitigation approaches include the Use of a wet-wal reactor, where the internal reactor surface is wetted by rotating or fling fm of iquid metal Or salt [10], a porous-wall reactor (in the context of methane chlorination leading to hydrogen and cartoon) [4}, Oorusing less adherent surfaces, such ‘as calcium-oxide wall coating to fa- citate mechanical carbon-deposit removal [77] or ceramics, including alumina, MgO-C, or SiC [8 Carbon buidup in plasma torches was addressed by the company Hi- ROG (Hull, UK; wwhiroc.com) by Using Ho-purged porous anodes in combination with vortex flow inside the torch chamber [72 kona Powor Inc. (Burnaby, 8.C.; wwwekonapower.com) developed ‘a pulsed intermittent-fow reactor where carbon deposition is mitigated by strong turbuience associated with rapid depressurizatn and high-ve- locty ges fow [13}, Nonecoverable For dott val adhns-cnemengont CHEMICALENGNEERING WWW.CHEMENGONLINECOM NOVEMBER 2028 https wunxtbook comfaccessinsligence/ChemicalEngineeringiche_november-2023index shoti/204in209, 718 yr face which, along with the wall shear forces, prevents carbon deposit on the reactor walls, Bubbile-column reactors. mitigate carbon deposition, as the reactons take place inside gas bubbles rising through a poo! of moten media, such ‘as metals (Sn, Pb, Ga, Te, NE, Cu- Bi, Ga-in-Sh) or sat (KBr, NAB, NaBr/ KBr, NaF, KG, NaCi, MnCig, acting as heat transfer fids at 900-1 400°C ‘and often as cataysts. Molten media is contained inside a oyincrical re- factor that may be provided with a submerged packed bed of ceramic tings or sprays in the vapor space to increase lquid-gas interface. Carbon ‘wall deposits are mitigated by carton formation at the bubble-fquid inter- face, which keeps it contaned inside the bubble. Vwhen rising gas bubbles burst upon reaching liquid surface, ‘carbon is released and floats on the met surface, from where it can be ‘continuously removed using an over- flow weir or gas flushing, ‘Slow reaction. As ciscussed above, the methane pyrolysis reaction is relatively slow. While raising the re- action temperature helps, when temperatures exceed 1,900°C, the ‘equilrium yiold of Hy starts to de- ‘crease due to the formation of acety- lene, ethylene and ethane. Moreover, higher temperatures result in higher net energy consumotion. To lessen the residence time and the reactor volume, it is possible to increase re- actor pressure, but at the expense of Hp yield. For these reasons, reactor design must carefuly examine Hp Yields and exit gas compositions asa function of reaction temperature and pressure along wth staged feed-gas injection and staged ditstion/cooting with Hp. Mutiple competing reactor configurations need to be analyzed using kinetic modeling to optimize the reactor design, Various catalysts have been devel- ‘oped to accelerate MP reactions at lower temperatures (<1,000°C) and to improve selectivity toward He and desred_allotropic. form of carbon; thase include the folowing * Sold catalysts, such as metals Co, Fe, Ni, Si, metals/alloys with pro- motersidopants (NECu, Ni-P, Ni Mo, Ni-La, Ni-Cu-Co, Ni-Sn, Fe-Co, Fe-Mo, Zn-Cu) supported on stica, che_november- 2028 [20-21 alumina or carbonaceous materials, metal oxides (FOO/Fo,0p, LaNiO,), metal carbides (FaxC, ‘NicC), and ‘metal-carbon nanostructures (N-C) + Motten-meda catalysis, such as liquid metals (Te, N-Bi, Ga, Pb), ia- vid sats (NaCl, KCI, MnCl, Nici, NaBy, KBr, NazCO3, K,C0., LisOs, cor their mixtures), Quid salts with ds persed sold catalyst particles in the form of finely divided elemental met- als (N, Mo, Mn, Co, Fe, Zn, Tl, Cu), their oxides, carbides or their mix. tures, and carbon catalysts (activated carbon, carbon black, graphite and formed carbon]. A recent compre- hensive review of MP catalysts was ‘conducted by McConachie [6]. Relative to soli catalysts, motten- media catalysts are not prone to ‘carbon buldup. However, their sta- bilty is affected by high temperature, Metal catalysts’ aotivty depends on the metal (NisCo>Fe) and exceeds that of carbon catalysts [7]. Rapid sdlid catalyst deactivation caused by carbon buildup, poisoning and sinter- 9 isthe key concern, Susceptibilty 10 deactivation is higher for N-based catalysts than for Fe-based and car- bbon-based catalysts Conventional reactivation of soid metalic catalysts. removes. carbon deposits using ovation or steam gasification, and resuits in CO, emis sions. This is avoided in the process developed by PNNL, where bimetalic Ni-Cu catalyst on a carbon nanotube support is used to pyrolyee methane at 600°C inside a ficized bubbling- bed reactor [16]. Formed carbon accumuiates on catalyst parties, wich are withdrawn ftom the bed, cooled and acid-washed to separate formed carbon from metalic catalyst precursors. Catalyst precursors are then used to resynthesize the cata- lyst for recycie back to the reactor. ‘The catalyst can be formulated to in- crease selectivity toward formation of carbon nanotubes. lron-based sold catalysts are more stable and deactivate at slower rates: than Ni-based catalysts. The process developed by Hazer Group uses flu- icized ion ore (Fe0yFeO) catalyst particles 17). Carbon forms as graph ite on the surface of catalyst parties, ‘which undergo. continuous. attrtion through intergranular breakup, re- leasing small graphite particles into the reactor offgas. Catalyst surtace is thus continuously regenerated, pre- venting deactivation due to carbon buildup. Separation of elurated solid catalyst from carbon is one of the challenges in such systems. ‘As previously mentioned, special conce-through non-recoverabie “cat- alysis” have been used fo promote carbon nanotube formation in tubu- lar MP reactors. These include ferto- cone Fo(C3Hs), and sulfur additives Use of ferrocene and iron pentacar- bony Fe(COs was investigated for the production of hydrogen in sola heated reactors [28] ‘Carbon catalysts are considerably less expensive, but also are less ac- tive than metalic catalysts, leading to higher operating temperatures (800 1,000°C) and longer residence times to acheve equivalent conversion Amorphous carbons (caroon black, activated carbon) are more active than ordered forns, such as graphite ‘Advantages for carbon catalysts over metalic catalysts include negigibie toxicity, high stably, longer ifeimes and no susceptbiliy to sutur poison- ing, which makes desuttrzation of the natural gas feed unnecessary. Regeneration of carbon catalysts may be performed through gasfica- ‘ion with steam, which generates CO, and H>, However, this is not needed for the once-through use of imported carbon catalyst with higher actity, such as activated carbon, Also, tay be preferable to rely on autocatalytic properties of formed carbon product instead of a once-through use of im- ported catalytic carbon, as practiced by Mader Hycrogen Inc. (Bothel, ‘Wash; wurw.modernhycrogen com). Low catalytic activity of fomed carbon can be compensated for by increasing the circulation rate of carbon product though the reactor, which increases the exposed particle surface area within the reactor. Methane decompostion can also bbe achieved through photolysis using heterogenous. photocatalysts inside fxed-bed tubular reactors with transparent walls iluminated by ex- ternal ight Delivery of heat to the reactor. n addtion to the enthalpy required by the endothermic MP reaction, sen- (CHEMICAL ENGINEERING WWWVCHEMENGONLNECOM NOVEMEER 2023 https wunxtbook comfaccessineligence/ChemicalEngineeringiche_november-2023index shotii20 es4nn209, 715 sible heat Is needed to get the re- actants to the desired temperature. The overall reaction heat requirement depends on the size of the recycle streams, and can amaunt to 1.21.5 times the reaction endotherm. In plasma reactors, the heat re- quirement is provided by electricity powering a plasma generator. Hy: drogen or staged feed-gas_injec- tion can be used to control the tem- perature profila. No additional heat ‘source is aquired, In non-plasma small-scale ex- perimental reactors, heat is typically delivered to the reacting mixture through a hot reactor wall, whereby the reactor is placed inside an elec: tric furnace or heated using external resistors or induction cols, Such a scheme does not scale up well with ‘growing reactor diameter, because the radial temperature gradient be- ‘comes very steep and efficient heat transfer becomes more difcut. ‘To circumvent scaleup issues as sociated with externally heated reac tors, pilot- and demonstration-scale plant design should considera circu lating side-stream of molten metal or Salt, carbon particles or catalyst pat= ticles, as a heat carer. Circulating stream(s) would be withdrawn from the reactor, processed as necessary, reheated and recycled back. Exter: nal reheaters can utlize resistive, induction and microwave heating, electric arc furnace, Ho-burring fired heaters, concentrated solar heating or immersed plasma torch (molten media oni) Using combustion heat to provide MP endotherm was explored by Mu radov [27], whereby a small amount of oxygen is added to a fidkzed:-bed catalytic reactor employing carbon and iron-based catalyst. Emissions of CO, would stil be 3-5 times smaller ‘compared to the conventional SMR process. A simiar approach is used by C-Zero, whereby His combusted to heat a Crculating molten media in- side a bubble column reactor. ‘Other schemes of delivering heat to reactors are being researched, One Of them under develooment by Palo ‘Ato Research Cenier {79} involves ‘condensation of zinc vapor to supply the reaction heat inside a molten zinc cyclone reactor. A scheme proposed che_november- 2028 [20-21 by Munera-Parra [26] uses chemical tenergy obtained through excthermic recombination of molecular hydrogen from plasma-generated atomic hy- drogen. A novel method utizes com- pression heating of methane to pyral- ysis temperature using a supersonic shock wave generated by wave rotor feformer technology [27]. Microwave heating of fluidized bed was patented by H-Quest (22) Heat recovery. The overall heat requirement can be significantly re duced by using heat recovery from reactor outlet streams, or by utilizing waste heat from adjacent processes (for example, from cooling of steel and slag in steel production served by dedicated MP installations) 2} Heat can be recovered by pre- heating the feed stream (natural gas mixed with methane recycle) and recycle stream against the reactor ‘ext streams. Caution must be ex- ercised to avoid coking inside heat exchanger tubes due to overheating Of the feed stream. ‘Owing to the high heat capacity Recut eae prev ienr ra sd CHEMICALENGNEERING WWW.CHEMENGONLINECOM NOVEMBER 2028 of He, most of the heat leaving the MP reactor (-80%) is carried by the gas with the remaining 20% car- ried by carbon. The entire reactor cfigas stream can be sent through fa shelland-tube heat exchanger prior to the solids separation step, {8s practiced in some carbon black plants. Alternatively, hot carbon is Separated ina cyclone or inside the reactor, prior to heat recovery from the solids-free gas through steam supetheating, followed by ‘steam generation, and followed by ‘an economizer. Heat can be recov- ‘ered from carbon using a buk solids ‘cooler equipped with a vertical plate ooil-tube exchanger. Supetheated steam can be utiized in @ combined-cycle cogeneration system employing Hp-fusled gas tur- bine to generate power for the plant, ‘as well as for export, Such a system ‘would also provide operational fex- ibility to accommodate swings in ex- texnal H demand, For more information, see pp. 12-46 of this issue, nits sn.natbook.comiaccessintsligence/ChemicalEngineeringiche_november-202S/index.phptn/20 7184in209, 718 yr MP process economics Publications deaing with techno- ‘economic analysis of MP technolo- gies use a wide-ranging set of as- sumptions, methodologies, plant ‘capacities and unit pricing of natural ‘928, carbon, electricity, water, con- sumables, labor, carbon-offset cred- its and other parameters. Because of this variabilty, the pubished data do not alow for equitable comparison of projected economic performance of ‘competing technologies. Neverthe- less, reviewed articles provide valu- able insights into expected economic performance of methane pyrolysis technology and are summarized as folows for uniformity, all costs are ‘expressed in 30 2028 doles): * Hycrogen production costs’ using 'SMR-CCS technology varied ‘fom '$1.401kg to $2.50/Kg of H,, depend ing on natural gas cost and other fac- tors used in analysis (23, 24, 16] * For motten salt (KC-NInCi,) bubble ‘column reactors, projected Hp pro- duction cost is $1.80/kg of Hp based ‘on natural gas at $2.90/G and zero revenue for produced carbon [24] + Hydrogen from molten media (N-Bi metal and sal) reactors costs $1,70/ ig of Hp to produce, which is much less than water electrolysis based on polymer electrode membrane (PEM) technology (§3.00/kg Hp for electric- ity cost alone). A earbon-offset credit ‘of $26/ton CO, is required to actieve ‘cost parity with SMR. Altemativey, carbon co-product revenues would have to exceed $200/t0n carbon for the same effect 25) ‘For fuidzec-bed reactors using solid Fe-based catalysts, projected Hy production cost was $3.20-3.50/ kg He based on natural gas at $7.50/ GU, with zero revenue for produced ‘carbon, and no catalyst recycle or ‘carbon purfication, all against $2.50/ ig Ho for SMR-CCS benchmark. For Hp to become compettve with SMR- ‘GCS, 20% of produced carbon would have to sell at $1.20-1.50kg. The ‘economics and thermal efciency are highly sensitive to catalyst actity and resulting Hy yield [75} * Carbon co-product revenue in the '8600-900/ten range wil completely Offset He production cost 26] * The H production cost from a flu: idized-bed MP reactor vill match that che_november- 2028 [20-21 of an SMR process (without CCS) if carbon sels for $300-B00/ton [27] ‘Production cost of Hp from the (MP process based on a hot cyclone reactor wetted by quid Zn metal is $2.50/kg of crude (04%) Ho, and $3.40/kg pure (80%+) Hp with zero carbon revenues for both cases [19] Overall, turquoise Hp can be pro- duced at $1.80-4.00/kg without carbon sales or ofsets, which is nat yet cost-compettve with grey Hp ($0.90-3.001kg to produce). How- ever, turquoise Hy may compete fa -vorably with blue hydrogen produced at $1.40-2.50/kg by SMIR-CCS, The economic feasibiity of tur uoise hydrogen can be vastly im- proved by seling carbon co-product and generating revenue from car bon-offset orecits or from avoided carbon tax for example, obtained by replacing SMR or ol-derived carbon black plants with an MP process). Economic fessibity can also be improved through technical innova- tion. For example, the ETCH process [5] that employs Ni-based redox re- actions is projected to produce Hp at $1.00-1.50/Kg of Hp without car- boon sales or carbon offsets revenue, which compares favorably to SMR. Current growing demend for carbon black and graphite creates significant market opportunites for MP-produced carbon. However, new markets for carbon are needed to strenathen the ddving force required for broad adon- tion of MP technology. Large-scale grassroots MP plants will have to compete with fully amor tized existing Hy plants. For this rea son, it may be worthwhile to consider the feasiity of retrofitting the exist- inginstalations with MP reactors and sdlids handling subsystems. For more information on MP, view the online version of this article at www.chemengonline.com. Edited by Scott Jenkins References Solna eaters ‘sas eect ee coe SRNR comataaae «fae mo oat oes oe © Siete ces amie ieee sete ete tach seers te Oa ty Se peranra ary" Reee Fat Bo Reecle ae Suse yest Esnavon eaoraet wl ae Le es panera "a teers tt eee : sa er a ere nan Sua Sie ane a ee Seo eee wh at Serer a _— Beeler eacnara sah ‘Stage eye a etnias ice Nagel aren Pram even a0 {aw Get fyonm fog, ara waza acer ee eee eersea tere “rata eae te Seer cen keel 24 rs kare Gro earn Gy agen ht toon ea See Fagen Ereme 43 0) 2540-2485, - ” Satie ates ats sce fener ik Ne be eee eae setahee riers a er et Sea ieetinatmncee Author CcatFemm eagroeso- eee pee rae Dy | Sars tn oe So SEU Fey Sate 260, Houston, rae: Ema caren {ahoo com He Pas ooo to 50 yeas of eroerence in process dewtosment ord Bart oeagn Oovorng a wile tangs of dustries,inchdng petteum rer rg. chomical. phamacrsteas metaluie, Utes end eworenenta protection. CHEMICAL ENGINEERING WWWVCHEMENGONLNECOM NOVEMaER 2023 https wunxtbook comfaccessinsligence/ChemicalEngineeringiche_november-2023index shoti/20 a8