2) United States Patent oy ow 2 Cy (60) oy Briggs, jr. et al. INTERNAL COMBUSTION ENGINE HAVING CARBON DIOXIDE CAPTURE AND FUEL ADDITIVE SYNTHESIS SYSTEM. Applicant: Southwest Research Institute, San Antonio, TX (US) Inventors: Thomas E. Briggs, J, Helos, TX (US); Graham Conway, San Antoni, TX US) Assignee: SOUTHWEST RESEARCH INSTITUTE, San Antonio, TX (US) Notice: Subject to any disclaimer, the teem ofthis pateat is extended of adjusted under 35 USC. 15446) by 18 days. Appl. Nos 17/446,837 Pilea: 3, 2021 Prior Publication Data US 202210074358 A1 Mar. 10, 2022 Related US. Application Data Provisional application No, 62/706,745, fled on Sep. 8, 2020, Im. cl, FOIN 01 (2006.01) 2p 192 (2008.01) (Continued us.cL CPC. Fu2d 19/0689 2013.01); BOLD 53228 013.01); BOLD $229 (2013.01), BOID 53/265 (2013.01), BOID 69/147 (2013.01) CUTE 17041 (2015.01); €U7C 1/12 (2013.01) CU7C 29/54 (2013.01); COPE 29/1518 (2013.01); €10L 1023 (2013.01); C10L. 706 (2013.01); CxOL 10/02 (2013.01); C1oL 1010 (2013.01); C25B 1/04 (2013.01); C25B 9/00 (2013.01); FOUN 3/005 (2013.01): FOIN 3/01 10 a | | engine emma co, | Fontan igh Separator a | nan | Gosoune Sani 20 Reformote_ | Tank 01 1608787B2 US 11,608,787 B2 Mar. 21, 2023 USt (10) Patent No.: (4s) Date of Patent: (2013.01), FOIN 40892 (2013.01); FORD 19/0649 (2013.01): FO2D 19/0655 (2013.01) Fond 19/12 (2013.01); FO2D 38027 (2013.01); F020 41/38 (2013.01); FORM 25/12 (2013.01) Continved) (58) Fleld of Classification Search CPC ne CORE VO; COTE 1/12; CONC 29/154: OUD 58228; ROID 53/229: BOLD 58/265; POIN 3/005; FOIN 3/01; FOIN 70802; FO2D 19/0685; FO2D 19/12; FO2M 25/12; FO2M 25/14; C101 220010492; C1OL 2290142 spc 123, 406.31, DIG. 12 See application file for complete search histor. 66) References Cited US. PATENT DOCUMENTS. 2513 8454732 B2 62013 Hang ot a (Comtinved) (OTHER PUBLICATIONS “Aramco Debuts Low CO2 Demonstzation Truck at SAE Inova tions in Mobility Event in Dei, ps: ww snaarameo com snines-neia neu 2019 sac-innovations-mnobility-event eet Primary Examiner —Exick 8 Solis (74) Attornes, Agent, or Firm Perreault & Pfleger, PLLC Grossman, Tucker, on ABSTRACT ‘Separation of earbon dioxide from the exhaust ofan intemal ‘combustion engine, the production of hydrogen from water, And reformation of earbon dioxide and hydrogen into rela tively high-octane fuel components 14 Claims, 1 Drawing Sheet “ fi ayo ft condensor tint, ‘nat esata ewwenoncsonUS 11,608,787 B2 Trae? sh met © usc. rere 2 ee TL, pan 2904 corsony, rea ssaezss eis 2 cen corsnsrapar songs nin cree fee = 2 eoeen muss eons Cal nats faniee ——Gocat aig ota asaya Pa nee = = noe “ne GoD Fawiew ——ocal fence © lewean «6 Referees ied feo (aust) Cen BOID o9/t4 (2006.01) 9.334.204 BL $2016 Radaclli BOL 8/001 finn ze (so) aaa ae a ere ates pie nay Pa gov 2 ey Herons a ; a care y1s1 aon) DM6O01 AL? 2016 Singin nnn CE CIOL 102 (2006.01) 20220136119 AL* Flanders Cio meas eo Giot twee ‘apoea ee funiue —‘Saveat maureen ——— = rap ise, Gea SEMUE A 2 GR sia ere mise amo) tegen ae eee come eta feawiere (onc) * ita by examinerUS 11,608,787 B2 Mar, 21, 2023 U.S. Patent AyOHROAII on mor Aronnefox ‘09 ‘mo7 Aennejey ysneyg » 4024039913 dosuapuod ob HOSHPOIHO*HOPHO 4 hn J | 09 | mo7 ABAneIoN 4ojyesedag isneuxg 709 a yuel ayeuusojoy cy | rayshs lonuoa aubuz "09 YBIH Aroane jou ft sreUxXy yuey euyjoseyUS 11,608,787 B2 1 INTERNAL COMBUSTION ENGINE HAVING CARBON DIOXIDE CAPTURE AND FUEL ADDITIVE SYNTHESIS SYSTEM FIELD ‘The present invention provides for separation of carbon «dioxide from the exhanst ofan internal combustion engine, the production of hydrogen from water, and reformation of ‘carbon dioxide and hydrogen into relatively high-octane fvel ‘eomponcas. BACKGROUND Internal combustion engines continue to be the most ‘economical and practical means of powering road transpor- tation for personal and commercial use. However, societal and regulatory demands are pushing for low- or 7em0-CO ‘emission transportation, which presently means battery elee= tric vehicles. These vehicles are not yet economical for certain applications, ean have relatively limited range and uty, and present certain material resource limitation. “There has been some interest and development in making the intemal combustion engine a zerCO,, technology. One pa is to use a non-carbon containing fuel suchas hydrogen. ‘This can work, but introduces challenges with a lack of fuel availability in the market, packaging of tanks for low= ‘density Tue, snd technical difiulties with hydrogen/mte- Fial interactions. Others have considered onlboard carbon dioxide capture ad stonge systems (example: Sati Aram 0s CO, capture and storage demonstration truck hap! ‘ww wsandiaramco.com/enaews-medianews/2010/sae-in- novations-mobility-eventdetit) This approach can yield relatively low CO, emissions, but requires relatively high ‘enoray demand systems forthe CO, separation and slorage, ‘and at present cannot capture allof the CO, emissions. There js also the challenge of what happens to the CO, a it must be removed fom the veiele and Used in a way that does 201 release it back to the atmosphor. ‘To satisly fuel economy and ureenhouse gas relations, ‘engines net inerease i thet eflicieney but are limited by ‘enu-gas knock —the compression ratio of the engine canaot be firther increased with existing market fuels due to the ‘octane number of those fuels. I higher octane fuels were available, the engines could be made to be more efficent There is also ongoing development of what are termed “advanced combustion engines” that use various methods of conttolling the auioignition of the fuel to allow for a kinetcally-controlled compression ignition process. These ‘engines offer high potential efficiencies, but are asin wen- ‘erally limited in function by the properties of market Fels “Accordingly, need remains for an on-board vehicle system that could generate fuel components that would afer relatively higher efficiency potential for intemal combustion ‘engine powered vehicles SUMMARY, An internal combustion engine comprising an engine ‘control system in communication with the engine that ‘deects and evaluates the presence of engine knock. carbon. dioxide separator is provided to separate carbon dioxide from intemal combustion engine exhaust along with @ ‘condenser and electrolyzer o separate water from the engine ‘exhaust to provide hydrogen. A reformer is present that ‘converts said separated carbon dioxide and hydrogen into ‘one or more high octane fel components. The engine 0 o 2 control system is configured to introduce the one or more high octane fuel components into te engine upon determi- ation that the engine requires said one or more components to mitigate andor prevent engine knock. ‘The present invention also relates to @ method of operat ‘ng an internal combustion engine comprising injecting fvel into a combustion chamber to form an afl mixture and combusting tho mixture and forming exhaust gas. One provides @ carbon dioxide separator and separates carbon Sioxide from the exhaust gas and also separates water from the exhaust gas and converts the water into a supply of hhydrogen. The separated carbon dioxide and hydrogen are combined to form one or more high otane fel componeats ‘One then provides an engine control system that detects and evaluates the presence of engine knock and) mitigates or prevents engine knoek by introdueing the one or more high fctane fuel Components into the intemal combustion engine. BRIEF DESCRIPTION OF THE DRAWING Embodiments of the present invention are described in etal below with reference to the attached drawing FIGURE wherein: FIG. 1 ie block diagram ofthe veicle-integrated carbon ioxide capture and fuel additive synthesis system. DETAILED DESCRIPTION OF THE DRAWING ‘The present invention provides for separation of earbon dioxide (CO,) from the exhaust of an internal combustion feng, the production of hydrogen frm water via use of an eleciriyzer, and the reformation of carbon dioxide and bydlogea into one or more relatively high-octane fel com- poneats. The one or more relatively high octane fuel com: poneats may then be fed to the engine as required. via use ‘of an engine control system (ECS) that evaluates engine performance. The FCS preferably evaluates, among other things, the knocking behavior of the engine which then responds by intaducing the one oF more relatively high ‘etane el component into the engine fuel to, among other things, mitigate or reduce the identified knocking (combos: ‘ion ofthe aiefuel mixture that does not result from propa- gation of the fame fron) ‘Attention is directed 10 FIG, 1 which illustrates a pre: emd embodiment of the present invention. The intemal combustion engine 10 output exhaust as illustrated is re tively high in CO, content. Such exhaust is then preferably assed through a CO, separator 12 where the COs removed from the exhaust can be pumped into a reformer 18. The (CO, separator 12 preferably relies upon a membrane separ ration of CO, from the mixture of exhaust gases. Such memibrane may preferably be in tubular form and include a substrate layer comprising inoruanic oxides. a barrier layer of in-situ formed L710, 2 Li,Zr0, sorbent layer and an inorganic oxide cup layer The substrate layer cof inorganie oxides are preferably of average pore size 3.0 um to 10.0 um whieh is 20-80% porous with a thickness of {60 mm to 15.0 mm, One may then deposit on the substrate layer precursors fr the Tommation of LigZ2O, and react the precursors for the formation of a L240, barter layer ‘wherein the barie layer is formed at thickness of 10 jun 10 100 um with a porosity of 0% to 30%. One may then deposit on the barrier layer a sorbent layer comprising 1,210, at a thickness of 100 jam to 500 pm followed by deposition of a cap layer on the sorbent layer comprising Snorganic oxides. The cap layer has a thickness of 50 jm to 250 jum. One may then expose such membrane (0 carbonUS 11,608,787 B2 3 dioxide a elevated temperatures (400° C. to 700° C.) and, separate carbon dioxide from the exist gns-mixture Reference is made to U.S, Pat, No. 8454,732 whose teach- ings are incorporated by reference. ‘Continuing, the exhavst that emerges from the CO. sepa rator 12 is relatively low in CO, content and is thea introduced to a condenser 14 which remaves water where the waters introduced into electalyzer 16. The electrolyzer 16 receives electricity, which may’ preferably be electricity from the vehicle battery system. The eletrolyzer 16 there- ore initiates electolysis of water and provides for the decomposition of water into oxygen and hydrogen. The hhyerogen gas so produced is then introduced to reformer 18, which as noted above, also receives CO, from the CO; separator 12 ‘Reformer 18 therefore provides forthe reaction of earbo «dioxide with hydrogen to form one of more relatively high ‘octane fuel components. The high octane fuel components are understood herein to be any components that when added 10 engine fuel (eg. gasoline), serve 10 increase the 2 ‘octane rating. Such components preferably include methane (CHL), methanol (CHOW) and/or ethanol (C;H,O1). Accordingly, the relormer 18 combines CO, and Il in the presence of a catalyst, and under elevated femperatire and pressure, fo generate iydocarbon products that increase, as noted, the octane rating oF aay avaiable ue, Multiple ‘catalyst fomnulations are prefered for such purpose. The preferred catalysts ean be CwZn0/AL,0, or Ni,Gay. With these prefered catalysts, the reformation reactions will ‘occurat prefered temperatures from 200° C.t0 300° C. and under prefered pressures ranging from 0.1 0 & MPa. Depending on the specific details of the catalyst and refor- mation conditions, a last 5% of the CO, and [will be preferably converted into CH, CH,OH, and C,t1,081. The ‘mehane, methanol and/or ethanol so produced may then be ‘conveniently stored in reformate tank 20. “The engine control system (ECS) preferably utilizes 3 processor along with a map-based contol strategy with eedhack to detect, evaluate and then determine when and ia ‘what quantity to introduee the high-octane fuel components to the engine. Rased on a combination of one or more of sueh factors such 36 engine speed, manifold temperature, throttle pedal position, the ECS can determine that the ‘engine requires the high-octane fuel components (e., CH ‘CH,OH, andlor C.H1,01) 0 mitigate andlor prevent knock. from occurring, The components will then be injected ‘acconting to the calibrated tables in the controle, with the zsoline injection command adjusted to maintain the engine ‘ata steady lood condition, Feodback will prefebly be through an engine knock sensor where the sensor signal can be used both to command a spark timing retard for knock ‘control andor an increased injection rate of the relatively high octane component, within limits dat can be defined ia the PCS maps. "Expanding on the above, the relatively high-octane fuel livery can be accomplished in multiple prefered manners to satisfy a specific engine's design nnd performance requirements, Gaseous components such as CH, ean be ‘nroduced through a metering valve or injector in the engine intake systom after any superchanging devices. The engine intake system may be understood as the system that allows sir and fael into the engine. The liguid components (eg. methanol or ethano}) ean also preferably be metered into the fie ail that supplies the fuel injectors. This induces a delay between the command of high octane fel delivery and the ‘engine recciving the fuel into the combustion charmer but is 4 proctical approach, For more direct timing contol, i is 0 o 4 ‘contemplated that the relatively high octane fuel co rents can be supplied to a secondary set of Fuel injectors Tocated in the intake ports or directly into the combustion chamber dedicated to the delivery ofthe high octane fuel ‘components, This approach would provide immediate deliv~ ‘of the high octane fel components upon a command from the ECS. “Among other contemplated benefits ofthe present inven ‘ion include reduced CO, emissions a the CO, is captured and recycled into aTuel component. In addition the present invention is contemplated to inerease th ellcieney of the engine asthe compression ratio ean be inerewsed. In add- tion, it is contemplated that the present invention will provide relatively higher fuel economy resulting in higher les driven per gallon of utilized fuel. The foregoing description of several methods and pre- {ere embotiments have been presented for illustration and is ot intended to be exhaustive or limit the scope of the invention as may be recited in the claims. “The invention claimed is 1. An intemal combustion engine comprising: fn engine contol system in communication with said ‘engine that detects and evaluates the presence of engine knock; «carbon dioxide separator to separate carbon dioxide fom internal combustion engine exhaust; a condenser and eleeirolyzee to separate water from said ‘engine exhaust and provide hydrogen: reformer that converts said separated carbon dioxide and hydrogen into one or more high oetane fuel compo- wherein ssid engine control system is configured to introduce ssid one or more high octane fuel co ‘heats into said engine upon determination that sid ‘engine requires sil one oF more components 10 ni {gale andior prevent engine knock 2. The intemal combustion engine of elaim 1, wherein sald carbon dioxide separator comprises a substrate layer of inorganic oxides, a barrier layer of in-situ Li,Z#O,, 111,200, sorbent layer and an inonganie oxide cap layer 3. The intemal combustion engine of elaim 1, wherein reformer converts sti separated carbon dioxide al hydro- gen into a mixture of methane, methano] and ethanol, 4. The intemal combustion engine of claim 1, wherein said reformer comprises a catalyst selected trom Cu, 250, AI,O, oF NisGay, 8. The intemal combustion engine of elaim 1, wherein said engine includes an intake system and said high octane ‘comportents are configured to be intzoduced into sad intake system. 6. The intemal combustion engine of claim 1, wherein sid engine includes a fuel ral that supplies fuel injectors ‘wherein’ said one or more high octane components are configured to be introduced said fuel rail 7. The internal combustion engine of claim 1, having fl injectors dedicated to delivery of said one oF more high fetane fuel components. 8. A method of operating ‘comprising: injecting. fuel into a combustion chamber (© form an ‘sir fael mixture and combusting said mixture and form ing exhaust pas: providing @ carbon dioxide separator and separating car- ‘bon dioxide from suid exhanst gs separating water from said exhaust gas and converting said water into a supply of hydrogens internal combustion engineUS 11,608,787 B2 5 combining said separated carbon dioxide and hydrox ‘and forming oe or more high octane fel eomponcats: sroviding an engine control system that detects and ‘evaluates the presence of engine knock; ‘mitigating or preventing engine knock by introducing said s ‘one oF more high octane fuel components into said internal combustion engine 9. The method of claim 8, wherein said carbon dionide separator comprises a substrate layer of inorganic oxides, & barrier layer of in-situ Li,Z0,,2 Li,Z10, sorbent layer and 10 ‘an inoruanie oxide cap layer. 10, The method of claim 8, whersin suid one or more high ‘octane fuel components comprise a mixture of methane, ‘methanol and ethanol 1. The method of claim 8 wherein carbon dioxide and 15 hydrogen are combined inthe presence ofa catalyst selected from Cu, Z40, ALO, or Nig 12. The method of claim 8, wherein said engine inludes an intake system and said one or more high octane compo- rents are configured to be inimxduced ino said ike 20 system. 13. The method of claim 8, wherein said engine includes fuel rail that supplies fuel injectors wherein said one oF more high octane components are configured to be intro- ‘duced 10 said fuel eal » 14, The method of claim 8, wherein said engine bas fuel injectors dedicated to delivery of said one or more high ‘octane fuel components,