{M0 US 201603264 cu» United States 2) Patent Application Publication co) Pub. No.: US 2016/0326444 Al Van Thorre et al. (43) Pub, Date: Novy. 10, 2016 (54) MICROWAVE PRODUCED PYROLYSIS OIL, Publication Classification FROM BENEFICIATEI {GANIC-C ARBON-CONTAINING (1) Int cr. FEEDSTOCK C1OL 04 (2006.01) (2) US, (71) Applicants: Douglas M, Van Thorre, Minneapolis, co C101 04 (2013.01); C101. 2200/0469 MN (US); Carleton Drew ait, Novth (2013.01); Ci0r 229036 (2013.01); CIOL. Salt Lake, UT (US); Michael L. Catto, 2290/30 (2013.01); C101 229002 (2013.01) Moore, SC (US); Philip James Sealzo South Jondan, UT (US) on ABSTRACT M.Van Thorre, Minneapolis, 2 processed pyrolysis oll composition, a renewable lguid Carleton Drea Tait North, fil, having 2 high energy density, low water content and 2 Catto, ore neutral pI, and made with an oxygen-starved miro~ (2) Inventors: Dow MN Salt Lake, UT (US); Michael Moore SC (US); Philip lames Seelze, Wave sub-system from a processed organie-carbon-conain South Tondan, UT (US) ing feedstock made with a beneficiaton subssystem is described. Renewable biomass feedstock passed through 3 (21) Appl. Now 187215,281 ‘beneficiation sub-system to reduce water content to below at least 20 wt % and water-soluble salt reduction of ot lea (22) Filed: Jul, 20, 2016, {60% from that of unprocessed ompanic-carboo-contining feedstock on a dry basis, The processed feedstock is intro- Related US. Application Data duced ioto a substantially mierowave-trnsparent reaction ; chamber. Amierowave source emits microwaves which are (62) Division of aplication No, 141305223 fe on Ju, Shamber microwave sure emi microwaves hich re a Pla ate le eee reaction chamber to impinge on the feedstock within the (60) Provisional application No, 61/974,876, filed on Ape. resetion chamber, The microwave souzee may be rotated 3.2014, provisional application No. 61/71,329, fled relative to the reaction chamber. The fecdstock is subjected ‘on Mar-27, 2014, provisional application No. 61/867, 1 microwaves until the desired reaction occurs to produce 982, filed on Aug. 20, 2013. a Tiguid processed pyrolysis oil fuelPatent Application Publication Nov. 10,2016 Sheet 1 of 21. US 2016/0326444 AL 150 Xa IH 0H a IH H,OH HOH HCH Oe Fo OKT ao OH CHOH =H OH = CHOH =H OOH GHOH oH Fig. 1Patent Application Publication Nov. 10,2016 Sheet 3 of 21 US 2016/0326444 ALPatent Application Publication Nov. 10,2016 Sheet 4 of 21. US 2016/0326444 AL hy 1064S ANSEL SOLENT, \ NET SURREY FROM HOPPER Fig. 4Patent Application Publication Nov. 10,2016 Sheet 5 of 21 US 2016/0326444 ALPatent Application Publication Nov. 10,2016 Sheet 6 of 21. US 2016/0326444 ALPatent Application Publication Nov. 10,2016 Sheet 7 of 21. US 2016/0326444 AL ULTIMATE) ___ FAILURE POINT STRAIN ULTIMATE STRAIN Fig. 6A 14.0. 12.0 es RELATIVE BULK DENSITY (X) BULK DENSITY MULTILIER. epee ds 0 5000 10000 “0 100 200 300 P:RESSURE (PSI) RELATIVE ENERGY REQUIREMENT Fig. 6BPatent Application Publication Nov. 10,2016 Sheet 8 of 21. US 2016/0326444 AL ; BULK DENSITY VS. ENERGY: BAGASSE BULK DENSITY 97 MULTIPLIER 7 5 3 1 4 2 3 4 5 ENERGY DEMAND MULTIPLIER Fig. 6C 3500 4 3000 - 12 2500 10 PRESSURE 2000 RELATIVE BULK (PS!) 4500 DENSITY 4000 F 500 3. ON RO & 10 30 50 TIME (SECONDS) PRESSURE --- BULK DENSITY Fig. 6DPatent Application Publication Nov. 10,2016 Sheet 9 of 21 US 2016/0326444 AL Biomass Dewalering Alaratives 5% fo 12% Molsture: [Tasca Pst Thema! Pggaiena ‘craoHeieo | Hac03H0 [120 Only {Capabie of recucng mossy cnet to <2 be Yoo. Yes. a Yes Fue ss ece 6H] oh | TO | TO | a Fv Stir SE iain ve [we [Ye [va |e | We Fa Ss Costgw Ca > Ce Kasten we [we [Ya [ve | vr |r [Cacia Coo! Mule a a 085, ay 1 1 uns igre pecotaee| seria [ceed 1 1 Voy wa os 1 rl gfe fseg ra 7] tana Fag og Sra FE ta] a ist | Kocher eta ww tel) Flv Bru = ale] a est [71 (rial vamperature afar SS) a ni si = a 2 ello ; o_o tal aa Frigiecrte Sam a: i 7a [arg aces ten OT ae] 9 Ea Fy Receestor Sear a a 7 pot Yass (2-11) | a ad E Ese brit 3 ‘ cl yen (Ss 5 aed re cl yo ae oh Ey en ccf 06] bem) org a a Ca Fees a a a a Er Fs frum ‘and aa (Packaging [ert ol a sa wi 46 18 fla! Mechanical Enorgy Ragired ut Et ct £3.00) Bid $6 Fc rg on ha] — aa —— al — a 0 Total Energy RequredPoxnd [ett i #O5f 8768) 18374 aig cl oy eqn) hesrunrd oa] caf on ca] lerabe Caen Fey Deed GCA gui tan wag Ba teal [ect nched amet tow (2h ms cx Fig. 7US 2016/0326444 AI Nov. 10, 2016 Sheet 10 of 21 Patent Application Publication a) ig. 8Patent Application Publication Nov. 10,2016 Sheet 11 of 21. US 2016/0326444 AL LH} i) [iilPatent Application Publication Nov. 10,2016 Sheet 12 of 21 US 2016/0326444 AL ‘tits Feedstock | | Catalyst ‘tft c i is, 5 a Feedstock Reaction a Preparation Chamber im pees 3 Fuel \ Fig. 104Patent Application Publication Nov. 10,2016 Sheet 13 of 21 US 2016/0326444 AL Feedstock {{ ri (8) Heary hydocatons 08 sn Eby ‘tt (Condenser i en Chamber ‘1 Bensors ‘6h 1 js Or ‘0 Light yorocetons ANS Controller ToPalymetzatin Fig. 10B Gy:Patent Application Publication 1113: Nov. 10,2016 Sheet 14 of 21 US 2016/0326444 Al y'100 qt r A1N1 1112 4111 Fig. 11A 4111 Fig. 11BPatent Application Publication Nov. 10,2016 Sheet 15 of 21 US 2016/0326444 AL 1181 UaPatent Application Publication Nov. 10, 2016 Sheet 16 of 21 US 2016/0326444 ALPatent Application Publication Nov. 10,2016 Sheet 17 of 21 US 2016/0326444 AL ‘80 Fig, 18Patent Application Publication Nov. 10,2016 Sheet 18 of 21 US 2016/0326444 AL INPUTTING UNPROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK THAT HAS AT LEAST PLANT CELLS THAT INCLUDE INTRACELLULAR WATER-SOLUBLE SALT AND CELL WALLS COMPRISING LIGNIN INTO A REACTION CHAMBER EXPOSING THE FEEDSTOCK TO HOT SOLVENT UNDER PRESSURE. FORA TIME TO MAKE SOME REGIONS OF THE CELL WALLS COMPRISING OF CRYSTALLIZED CELLULOSIC FIBRILS, LIGNIN, AND HEMICELLULOSES MORE ABLE TO BE PENETRABLE BY WATER-SOLUBLE SALTS WITHOUT DISSOLVING MORE THAN 25 PERCENT OF THE LIGNIN AND HEMICELLULOSES { REMOVING THE PRESSURE SO AS TO PENETRATE AT LEAST SOME OF THE CELL WALLS TO CREATE POROUS FEEDSTOCK WITH OPEN PORES IN ITS PLANT CELLS WALLS i PRESSING THE POROUS FEEDSTOCK WITHA PLATE CONFIGURED TO PREVENT FELT FROM BLOCKING ESCAPE OF INTRACELLULAR WATER AND INTRACELLULAR WATER-SOLUBLE SALTS FROM THE REACTION CHAMBER SO AS TO CREATE PROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK THAT HAS A WATER CONTENT OF LESS THAN 20% BY WEIGHT AND A WATER-SOLUBLE SALT CONTENT THAT IS DECREASED BY AT LEAST 60% ON A DRY BASIS FROM THAT OF THE UNPROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK Fig. 14Patent Application Publication Nov. 10, 2016 Sheet 19 of 21 US 2016/0326444 AL INPUTTING UNPROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK THAT HAS AT LEAST PLANT CELLS COMPRISING INTRACELLULAR WATER-SOLUBLE SALT AND PLANT CELL WALLS INCLUDING LIGNIN INTO A REACTION CHAMBER eee eee ee ec eee Eee eee eee eee EXPOSING THE FEEDSTOCK TO HOT SOLVENT UNDER PRESSURE. FORATIME TO MAKE SOME REGIONS OF THE CELL WALLS. COMPRISING OF CRYSTALLIZED CELLULOSIC FIBRILS, LIGNIN, AND HEMICELLULOSES MORE ABLE TO BE PENETRABLE BY WATER-SOLUBLE SALTS WITHOUT DISSOLVING MORE THAN 25 PERCENT OF THE LIGNIN AND HEMICELLULOSES y REMOVING THE PRESSURE SO AS TO PENETRATE AT LEAST SOME OF THE CELL WALLS TO CREATE POROUS FEEDSTOCK WITH OPEN PORES IN ITS PLANT CELLS WALLS. i PRESSING THE POROUS FEEDSTOCK WITH A PLATE CONFIGURED TO PREVENT FELT FROM BLOCKING ESCAPE OF INTRACELLULAR WATER AND INTRACELLULAR WATER-SOLUBLE SALTS FROM THE REACTION CHAMBER SO AS TO CREATE PROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK THAT HAS A WATER CONTENT OF LESS THAN 20 WT %, A WATER-SOLUBLE ‘SALT CONTENT THAT IS DECREASED BY AT LEAST 60% ON A DRY BASIS FROM THAT OF THE UNPROCESSED ORGANIC-CARBON-CONTAINING FEEDSTOCK, AND A COST PER WEIGHT OF REMOVING THE WATER THAT IS REDUCED TO LESS. THAN 60% OF THE COST PER WEIGHT OF SIMILAR WATER AND WATER-SOLUBLE SALT REMOVAL FROM KNOWN MECHANICAL, PHYSIOCHEMICAL, OR THERMAL PROCESSES Fig. 15Patent Application Publication Novy. 10,2016 Sheet 20 of 21 US 2016/0326444 Al a Test Wear Waa Daman ° Solvent medium [War Wet ae > aides ae, al Bae we STempertis profile, 13010180 T0715 ‘© Pressure profile, max psig 260 to 280 ‘375 to 425 40-950 LO/MCOH spiasae Resue Dip pa | B0wIT | Bw TAT 00-520 14O/MeOH > pleave aon, 3 30 3 pipers Comes ‘¢ Pressure plate patterned, Y/N. | Y_ ‘Both Y and N_ ‘Both ¥ and N_ Sing water content, 26 [701080 B07 #010 3. Prosesed water conten, [tos dois dots ‘% Fixed carbon (a/b) (before- ‘25 to 50—> 40 to | 20 to 35 —-> 40 to SS [40 to S0-—> 45 to abe 6 35 3 las Ry aaa | a0 TOS I PMA S WS | wow ST 4% A % Ash (a/b) (before->after) 5 to 15 —> 5 to 10 [3 to 6 —> 1 to3 Ito 5 > <3 ‘Heat Content, LHV (before- 1,500 to 2,500 -—-> | 1,900 to 4,600-—> 3,000 to 5,000. Saien, BUA 700 fp 10,500 | 0009 11,000 [00 1,000 Fig. 16Patent Application Publication Nov. 10,2016 Sheet 21 of 21 US 2016/0326444 AL INPUT CARBON-CONTAINING FEEDSTOCK INTO MICROWAVE TRANSPARENT REACTION CHAMBER ¥ DIRECT MICROWAVES THROUGH THE WALLS OF THE MICROWAVE TRANSPARENT REACTION CHAMBER ¥ HEATARRADIATE THE FEEDSTOCK VIA] THE MICROWAVE UNTIL DEPLETION OF THE FEEDSTOCK ¥ COLLECT THE PRODUCTS YIELDED BY THE FEEDSTOCK Fig. 17 4710 1720 1730 1740US 2016/0326444 Al MICROWAVE PRODUCED PYROLYSIS OU. FROM BENEFICIATED ORGANIC-CARBON-CONTAINING FEEDSTOCK, RELATED APPLICATIONS [0001] This application is a divisional application of US. patent application Ser. No, 14/305,223, filed Jul. 1, 2014, ‘ow allowed which claims priority to Prov. Pat. App. Set No. 61/974,876, filed Ape 3, 2014, now expired: 61/971, 329, filed Mar-27, 2014, now expired; and 61/867 982, filed ‘Aug. 20,2013, now expired all of which are incorporated by reference in their entirety FIELD OF THE INVENTION [0002] The present invention relates generally 10 the pro- Auction of liquid pyrolysis oil fuel from an organic-carbon- containing feedstock. BACKGROUND OF THE INVENTION {0003} The vast majority of fuels are distilled from crue oil pumped from limited underground reserves or mined from coal, As the eaah's crude oil supplies become more dificult and expensive To collect and there i8 growing ceoncenns about the environmental effets of eoal other tha clean anthracite coal, the world-wide demaad for energy is simultaneously growing. Over the next ton years, depletion ofthe remaining world’ easily accesible crude oil eserves anc clean anthracite coal reserves will lead to a significant ‘increase in cost for fuel obtained from crude oil ad coal [0004] ‘The search to find processes that can eliiently convert biomass 1 fuels and by-products suitable for trans- portation andlor heating isa important factor in meeting the ever-inereasing demand for enezey. In addition, processes that have solid byproducts that have improved uility are also incteesingly in demand. [0005] Biomans isa renewable organie-earbon-contsining Jeedstock that contains plant cells and has shown promise as fan economical sourced of fuel. However, this fecdstock ‘ypically contains too much water and contaminants such as ‘Water-soluble salts to make it an economical alternative 1 ‘common sources of fel such as coal, petroleum, or natural a [0006] Historically, through traditional mectsnicaVchei- cal processes, plaals would give up a litle less than 25 ‘weight percent oftheir moisture, And, even if the plants were sun or kiln-drod, the natural and man-made chemicals ‘nd water-soluble salts that remain inthe plant cells combine to create corrosion and disruptive glazes in furnaces. Also, the remaining moisture lowers the heat- producing MMBIU per ton energy density of the feedstock thus limiting © furnace’s efficiency. Centuries of data obtained through experimentation with « mulitude of biomass materials all ‘uppor the conelusion that ineredsingly’ larger increments of nergy are roquired to achieve increasingly smaller incre- ments of buik density improvement. Thus, municipal waste facilities that process orgmic-carbon-coataining feedstock, 1 broader class of feedstock that inclodes materials that contain plant cells, generally operate in an enerpy defleient ‘manner that costs municipalities money. Similarly, dhe energy needed to process agricultural waste, also included ‘ander the general term of ofganic-earbon containing feed- sock, forthe waste fo be aa effective substitute for coal oF Nov. 10, 2016 petroleum are not commercial without some soe of gover ‘ent subsidies and generally contain unsatisfactory levels of either of both water of water-soluble salts, The cost to Suitably propare such feedstock ina large enough volume to be commercially successful is expensive and. currently ‘uneconomical. Iso, the suitable plant-cell-cantaning foed- stock that is available in sufieient volume to be commer- cially usoful generally has water-soluble salt cootents that result in adverse fouling and contamination scenarios with conventional processes. Suitable land for growing a sul cient amount of energy erops to make economic sense typically are found in locations that result in high water Sohible sat content in the plant cells, ie, often aver 4000 imgikg on a dry basis. 0007] Effors to make a synthetic liquid fuel called pyrolysis oil, also known as bicerude or biool, Irom ‘rganic-earbon-containing feedstock have been tied a substitite for petroleum. Present methods of making pyroly- ‘isl have not resulted ina satisfactory liquid feedstock for petroleum refineries, The elfors to date have not been ‘economically viable as the processed feedstock generally contain unsitisfactory amounts of water-soluble salts that fan contribute to corosion, fouling, and slagging in com bastion equipment, and have high water content that reloces the energy density to well below that of petroleum in large part because of the retained moisture. However, there emsins a need for processed pyrolysis oil as @ clean renewable source of liquid fuel if it could be made cost- cfletively witha more substantial reduction in its content of ‘water and water-soluble sal. SUMMARY OF THE INVENTION [0008] _ processed pyrolysis oil composition from ben eficited feedstock anda process af making the composition is provided. The renewable processed pyrolysis oil compo sition comprises a liquid earbon fuel with charaeteisis that include an energy density of at least 33.0 MMBTUiton (38.4 GMT), a water content of les than 15 w1 %, anda pH of at least as high as 4.0. The processed pyrolysis ol is made {rom unprocessed orginic-carbon-containing feedstock that is converted inio the processed ongunic-carbon-contining feedstock with a beneficiaton sub-system, and to the pro- cessed pyrolysis oil with a microwave sub-system. ‘The process of making a pyrolysis oil composition, 3 Tiguid Petroleum substitute Mc), comprises three steps. The first ‘ep isto input into a system comprising a fist sub-system and a second sub-system an unprocessed organic-carbon- containing feedstock that includes free water, intereellar water, intracellular water, otraellular watersaluble salts, and. at least some plant cells comprising cell walls that include ligni, hemicellulose, and mierofbrils within fbi The second step is to pass the unprocessed organie-carbon- containing feedstock through the frst sub-system, a benef ciation sub-system process, to result in processed onzanic ‘arbon-containing feedstock having a Water content of less than 20 wt % anda salt content that is recuced by atleast 60 ‘w0 % on a dry basis om that of the unprocessed organic: carbon-contaning feedstock, The third step is to pass the processed ontanic-carbon-contaning feedstock through Iicrowave subsystem process t result inthe pywolysis il composition, a liquid fuel having an energy density of at least 33.0 MMBIUiton 8.4 GIMT), a water content of Jess than 15 wt %, and a pH of at least as high as 40,US 2016/0326444 Al [0009] The invention is a processed pyrolysis oil that is a ‘itble clean petroleum subsite for refineries that convert Petroleum into usefil fuels, and other products, Thus a wide range of renewable organic-carbon-containing feedstock can now be made into a clean economically viable petroleum substitute. The uniform low water content and uniform, high energy density of the beneiciated organie-carbon-contain- ing feedstock used to make the processed pyrolysis oil allows for a wide variety of renewable organic-carbon- containing feedstock to he used in the microwave section of the process in a cost elicient manner, In addition, the processed pyrolysis oil is much less acidic that even pyroly- "is oll mae witha similar microwave sub-system but using linprocessed.onganic-carbon-contsining Feedstock with its higher water and water-soluble salt content instead of feed- sock that hes been processed in the beaeficstion sub- system, Further, the energy needed to remove water from unprocessed orgaaic-carbon-containing foulstock described above 1© a content of below 20 wt % and a substantial ‘amount of the water-soluble salt with the invention is significantly less than for conventional processes, embodiments, the total cost per weight of the benef Teedstock is reduced by atleast 60% ofthe cost to perfom ‘similar ask with known mechanical, physiochemical, oF thermal processes 1c prepare renewable orginic-carbon- containing feedstock for use in subsequent fuel making operations [0010] The above summary is not intended to describe each embodiment or every implementation of the present invention. Advantages and attainments, together with amore complete undersianding of the invention, will become fspparent and appreciated by referring to the following ‘etsiled description and elms taken in eonjunetion with the accompanying drawings BRIEF DESCRIPTION OP THE DRAWINGS [0011] FIG. 1 isa diagram of atypical plant cell with an exploded view of a region of its call wall showing the ‘sangement of fibrils, microfibrils, ad cellulose in the cell wall [0012] FIG. 2isa diagram of a perspective side view of a part of two fibrils in a secondary plant cell wall showing ‘ibils coatsining microfibrils and connected by strands of hemicellulose, an Tigain [0013] FIG. 3 ie 8 diagram of a erose-xectional view of a section of bagasse fiber showing where water and water foluble salts reside inside and outside plant cell [0014] FIG. 4 is a diggram ofa side view of an embodi- ‘ment of a reaction chamber in a beneticiation sub-system, 0015] FIG. SA isa diggram ofthe front views of Various embodiments of pressure plates ina beneficiation sub- [0016] FIG. SB isa perspective view ofa close-up of one embodiment of a pressure plate shown in FIG. 58, 10017] FIG. SC is a diagram showing the cross-sectional view down the center of a pressure pate with fluid vectors tnd particle of pith exposed to the Noid vector [0018] FIG. 6 is a graphical illustration of the typical slreststrain curve for lignocellulosic fib [0019] FIG. 6 is a graphical illastration of pressure and energy required to decrease the water content and increase the balk density of typical organiccarbon-containing feed- stock. Nov. 10, 2016 0020] FIG. 6C is a graphical illustration of the ener demand multiplier needed to sehieve @ bulk density mul ple [W021] FIG. 6D is a graphical illustration of an example of f pressure eyele for decreasing Water content in an onganie: carhon-contsining. Feedstock with an embodiment of the invention tailored to a specific the organie-earbon-contai- ing feedstock, [0022] FIG. 7 isa table iThstating the estimated enerpy ‘consumption needed to remove at lest 75 wt water-soluble salt from organic-cabon-containing feedstock and reduce ‘water content from 50 wt % to 12 wt % with embodiments of the beneficiation sub-system of the invention compared swith known processes 0023] FIG. 8 is a diggram ofa side view of an embodti- ‘meal of @ benefciation sub-system having four rezetion chambers in parallel, pretrestment chamber, and a vapor ‘sondensation chamber, 0024] FIGS. 9A and 9B illustrate side and cross sectional views, respectively, ofa reaction ebanber of an embodiment ‘ofa microwave sub-system configured to convert enganic- ‘arbon-containing materials to processed pyrolysis ol [002] FIG, 9C is a diagram of a tted reaction chamber ‘of an embodiment ofthe microwave sub-system, 0026] 1G. 9D isa diagram ofa side view of an embod ‘meat of the microwave sub-system 0027] FIG. 10A isa block diagram ofan embodiment of the microwave sub-system that uses the reaction chamber illustrated ia FIGS, 9 and 91 for water/airextretion ad 4 reaction process, 0028} FIG. 108 illustrates an embodiment of the micro ‘wave sub-system tht includes feedback control [0029] FIG. ILA shows @ microwave subssystem which ‘includes multipe stationary magnetrons arrangedon a drum that is disposed outside cylindrical reaction chamber hhaving one or more microwave-ransparent walls, [0030] FIG. 14B illustrates an embodiment of « miero- wave sub-system having @ drum supporting magnetras ‘which may be rotated around the longitudinal axis of the reaction chamber while the reaction chamber is concurrently rotated around its longitudinal axis; 0031] FIG. ANC shows an embodiment of a mierowave- subsystem reaction chamber with a feedstock trasport ‘mechanism compesing balls 0032] FIG, 12 illustrates @ system having a rotating ‘magnetron in addition to @ socondary heat source. 0033] FIG. 13 depicts a microwave sub-system wherein 2 ‘magnetron is moved along the longitdinal axis of the reaction chamber and is ated! around the longitudinal sxis of the reaction chamber 0034] FIG. 14 is block diagram of an embodiment of a process for passing unprocessed onganie-carbon-containing Feedsiock through a beneficiaion sub-system 10 create processed organic-carbon-containing feedstock with a water ‘ntent of less than 20 wt % aad a water-soluble salt content that is decreased by more than 60 wt % om a dry ass from that of unprocessed organic-cirbon-containing Feedstock, [0035] FIG. 15 is block diagram of an embodiment of process for passing unprocessed organic-carbon-containing Teedstock trough a beneticiaton sub-system to create @ processed organiccarbon-containing feedstock with a water content of les than 20 wt %,a water-soluble sll conten hat js decreased by more than 60 wt 6 om dry basis from that of unprocessed organiccarbon-containingfeedstoek, and anUS 2016/0326444 Al energy cost of removing the water soluble salt and water that fs raced to less than 60% ofthe cost per weight of similar removal from known mechanieal, known physiochemical, or knowa themnal processes [0036] FIG. 16 isa table showing relative process condi- tion ranges and Water and water-soluble salt content for three ‘ypes of omzanie-carbon-containing feedstock used in the beneficiation sub-system, [0037] FIG. 17 isa block diagram of an embodiment of a process for passing. processed organic-earbon-contsining Teedstock through a microwave sub-system wo eretea liquid fuel pyrolysis oil having an energy density of atleast 33.0 MMBTU/ton (38.4 GJIMT), a water content of less than 1S ‘wt %, and a pi at Teast as high as 4.0 [0038] While the invention is amenable to various modi- Fieations aad alternative forms, specifies have been show by way of example inthe drawings and will he desribed in detail below. It is to be understood, however, that the intention is aot to limit the invention to the particular embodiments described, On the contrary, the invention is Jntended to cover all modifications, equivalents, and alter- natives falling within the seope of the inveation as defined by the appended claims, DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS, [0039] The processed pyrolysis ol of the invention is a liquid fuel made by passing beneficiated processed organic- eatbon-contzining feedstock through @ mierowave system. 0040} The processed pyrolysis oil ofthe invention is at Jeast equivalent io petroleum in energy density. The pyeoly= sis oil ofthe invention has the advantages of coming from renewable source, agricultural and plant materials, without the burdens of current biomass processes that are inelicient, «do not remove enough water, and remove less iF any of the salt found in unprocessed renewable biomass. There are several aspects of the invention that will be discussed: processed pyrolysis il unprocessed renewable omzanic- tarhon-containing feedstock, benefiiation sub-system, microwave sub-system, beneficiation sub-system process, and microwave sub-system process. Processed Pyrolysis Oil [0041] Bio-oil made from renewable unprocessed organic- carbon-contzning feedstock by the process discussed below js refered to as processed pyrolysis oil inthis document. The pyrolysis ol of the invention comprises aliguid carbon, fuol Comprising an enoray donsity ofa least 33.0 MMBTU! ton Q84 GJIMD, a water content of less than 15 wt % water, and a pli at least higher than 4.0. Because the Denelication sub-system removes most of the intracellular ‘water, some embodiments ofthe processed pyrolysis oil may have water contents of less than 10 wt % ani some les tha 5 wt%, Further, the pH of the resulting processed pyrolysis oil is higher than even that of pyrolysis oil made by a similar microwave sub-section but using tnprocessed organic-car bon-coataining feedstock instead of processed organic-car bon-containing feedstock made by passing unprocessed organic-carhon-containing feedstock through the beneticia- tion subsystem, The processed pyrolysis oil is made from unprocessed omganie-carbon-contaning feedstock that is converted into processed organic-carbon-containing feed- ‘tock in a beneficiation sub-system, and that is then passed Nov. 10, 2016 through a microwave sub-system to become a liquid petro eum substitute having the properties mentioned. As used in this document, processed pyrolysis oil isthe liguidl product of the devolatizaion of heacficiated organic-carbon-con- taining feedstock. Organiearbon-containing feedstock used fo make the processed pyrolysis oi of the invention ‘may contain mixtures of more than one renewable feed- stock. The eneray density of processed pyrolysis oil is desired 10 be near that of petroleum or crude cil. Typical nid ol has an energy density of 378 MMBTUiton (43.9 GMT), Pyrolysis oil made by currently known processes hasan energy density that is substantially below that value, sometimes on the order of haf hat value, thus making many sources of feedstock economically impractical as 2 petro- eum substite in refineries, [0042] Petroleum is currently the primary supply of figuic fuel, It is fom biomass that has been underground [or millions of yeas. It isnot considered w be renewable iguid Tel beeause it cannot e replenished over the Hfetime of Jhuman. Depending on the source impurities ean vary. The rele impurity is sulfur and the types of peroleum range from swoot crude to sour crude depending on the sulfur content, less than 0.42 wt % or greater than 0.5 Wt %, respectively. Sweet crude oil contains small amounts of hhydrogen sullide and carbon dioxide. The sulfur content ranges from as litle as 0.0 to less than 0.42 wt ®%, High- ‘quality, low-sulfur crude oi is commonly use or process: ing ito gasoline and is in high demand, particularly in the industrialized nations. “Light sweet cre oil” is the most sought-after version of erade oil as it contains a dispropor tionately large faction that is directly processed (Lraction- ation) into gasoline (naphtha), kerosene, and high-quality diesel (gas ol), Sour erude oi s ede oll containing a high mount ofthe impurity sulfur, i. fom 0.5 wt Y to 80 wt "%. The majority of the sur in crude el oceurs booded 10 carbon atoms, with @ small amount occurring as clemental sulfur in solution and as hydrogen sulfide gas. Sour oil can be toxic and consive, especially when the oil contsins higher levels of hydrogen sulfide. At low concentrations the cil has the smell of rotten exes. Sour crude oil needs to be stabilized by having hydrogen sulfide gas (11,8) removed from it before being transported by oll tankers for safety [043]. _As supplies of easily reached! peteoleum dwinatle, efforts increase to find altematives that are preferable renew able, clean, and cost effective. Pyrolysis il is the liguid product of the decomposition of renewable ongan-carbon- feonaining feedstock that has been unxier investigation as 8 substitute for petroleum. Fiforts to extract it from biomass ‘biological material derived from living or resent living plans, hive resulted in kind of liquid oil that normally ‘contains unsatisfactorly high levels of oxygen fo become & hydrocarbon useful in distillation processes designs! 10 ‘make specific hydrocarbon liquids and gases. Present meth- fd to exiract pyrolysis oi from ompanic-carbon-contning feedstock involves the thermal, chemical and biochemical athods forthe destructive distillation of dried biomass in 4 reactor at temperature of about SO0° C. with subsequent cooling [0044] In pyrolysis oil made by thermal hest or infared radiation (IR), the heat is absorbed on the surface of any organic-carbon-containing feedstock and then is re-radiated to the next level at @ lower temperature. This process is repeated over and over again until the IR radiation pen-US 2016/0326444 Al rates t0 the inner most part of the feedstock. All the ‘material in the feedstock absorbs the IR radiation at its surlaces and different materials that make up the feedstock fbsord the IR at different mes. A delta temperature of several hundreds of degrees C. can exist between the surfoce and the inner most layers or regions ofthe feedstock. AS a result the solid orzanie-carbou-contining feedstock locally passes through a guid phase before it is volatilized. This ‘variation in temperature may appear in a longitudinal dinee- tion as well as radial direction depending on the character Jstes of the Feedstock, the rate of heating, and the localiza- tion ofthe heat souree. This variable bea transl frm the surface tothe interior ofthe fesdstock ean ease cold and hot spots, thermal shocks, uneven surface and intemal expan- son cracks, fragmentation, eject surface material and ereate ferovols. All of this can result in mieroeavironments that cause side reactions with the creation of many ciferent end products. These side reactions are not only ereate in the Teodstock but also in the volatiles that evaporate from the {eedstock and occupy the vapor space inthe intemal reactor eaviroament before being collected. [0045] A common IR radiation process, pyrolysis, pro- duces biockar, liguids, and gases from biomass by heating the biomass in s lowino oxygen environment. The absence ‘of oxygen prevents combustion. The relative yield of prod- ‘ets from pyrolysis varies with temperature. Temperatures of 400-500" C. (752-932" F) produce more char, while temperatures above 700° C. (1,292° F) favor the yield of Jiguid and gas fuel components. Pyrolysis occurs more quickly atthe higher temperatures, typically requiring sec- fonds instead of hours. Typical yields are 60% bio-oi, 20% biochar, and 20% organic volatiles. In the presence of stoichiometric oxygen concentration, igh temperature Pyrolysis is also known as gasification, and produces pri- ‘marily synges, By comparison, slow pyrolysis can produce substantially more char, on the order of about 50%. [0046] Recently, microwave system similar to the miero- wave sub-system has been used convert unprocessed ‘organie-carhon-coniaining feedstock discussed in this doeu- ‘ment into pyrolysis oil. Such pyrolysis oi has a. water content of over 20 wt % because of the tenaciously held fntracellular water found ia al plat material used as fecd- sock, With microwave radiation, the solid part of the Toedstock is nearly transparent to the microwave radiation and most ofthe microwave radiation just passes through. In fens to the small absorption eoss section of the solid feedstock. gaseous and lid water strongly absorb the microwave radiation increasing the rotational and torsional vibrational energy of the water molecules. Therefore, the gaseous and liquid water thot is present is heated by the Imicrowaves, and these water molecules subsequently indi- recily heat the solid processed organic-carbor-coalining feedstock. When the free water and intercellular waters all evaporated then some othe microwaves start tobe absorbed by the remaining feedstock and further beat it up within @ refleting enclosure that eause the microwave Fidiation 0 pass through the feedstock numerous times. Microwave radiation can complete the conversion of feedstock at lower ‘temperatures than IR and thermal heating and oocur during shorter timeframes. Operating temperature reduetions may range from 10-30% lower on a degrees C. bass and heating times may be reduced by a quantity equal to one-half 10 ‘one-tenth of that needed by IR radiation to accomplish similar degree of decomposition ofa specified feedstock. All Nov. 10, 2016 this can result in an evenly heated feedstock from the inside fout so there are reduced micmenvironments, fewer side reactions, and cleaner volatiles to collet 0047] The atmosphere inthe resetion chamber is free of | extemally supplied oxygen. In some embodiments, the atmosphere is inet, suchas, for example, nitrogen. In some embodiments, the atmospiere may contain a small amount ‘of water that previously had aot been complctely removed from the orginic-carbon-containing feedstock boing. pro cessed hefore it entered the reaction chamber. 0048] ‘The resulting reneseable pyrolysis oil from the microwave process system discussed herein is the devola- tilized carbon residue of an irmdisted processed onganic- carbon-containing hydrocarbon feedstock. The microwave system discussed horein can process organic-carbon-con- taining feedstock that does aot contain much Water when it enters the reaction chamber. However, the conversion is ‘more ellcien, i, faster rates and at lower temperates, ‘when Water o water-asociated molecules are present, Some ficient conversions occur when the ater content i. the ‘onzanic-containing feedstock as it enters the reaction cham ber is at least § percent by weight and less than 1S percent by weight. Some occur wisen the water is atleast 6 percent bby weight and fess than 12 percent by weight, For piposes of this document, water includes free water, interstitial ‘water, cellular water, and the water portion that may be combined with other molecules to form hydrated com pounds. During the early exposure of the feedstock to the microwaves, the uniform heating of the water Uuroughout the volume of the feedstock particles results in the cretion of pore numerous and more uniform pore, Because processed ‘oganiccarbon-containing. feedstock contains water, the below discussion will focus on those Feedstock, However, similar resulis may occur for those not containing Water but less ecient. 049] Tae resewable pyrolysis oil made with the micro- ‘wave irdiation ofthe unprocessed organic-carbon-contain- ing feedstock has several improved characteristics when compared to similar feedstock that is processed with IR radiation a diseussod above. In general, it is more like petroleum in its disillaion behavior than that made by thermal processes, containing minimal oxides, water, cor rosve impurities, and undesirable contaminants such as ta; 4 thicker hydrocarbon associated with hydnicarbons with chains of over Cz. Fest, hocause most of the free water is removed evenly’ from the surface to the center of the ‘oranie-carbon-containing feedstock, this free water does fo then mix withthe pyrolysis ol, only to next have wo be removed by further processing to be a useful distillation ‘feedstock In addition, omzanie-carbon-containing feedstock tat contain Tignin experience a better conversion of the lignin o pyrolysis ol with the desirable properties discussed below because the lignin is more dehydrated inthe miero- wave process discussed herein, [0050] Because the pyrolysis oll has significantly less ‘oxygen conten, the specific gravity is less than 1.2 oF lower than that of pyrolysis ol made with similar feedstock by an IR process and is dependent on feedstock. Spevlie gravity of pyrolysis il by the oxyen-starved microwave process of this disclosure is Tess than 1.2 and greater than 1,05 com- pared to that ofa themual process of over .2 and under 1.3. Same embodiment of tne pyrolysis oil ofthe invention have specific gravity of less thon 1.2, ome of less than 1.15, and sone of fess than 11. For reference, the specific gravity ofUS 2016/0326444 Al Waters 1.0 and diesel fue i 08. Some embodiments of the pymlysis oil have specific gravity that is at least O.1 less than it would have been in a pyrolysis oil composition made withthe same focdstock but using a thermal process that creates a liquid phase during the process, some embod ‘mens a least 0.15 less, and some'at lest 2.0 less. Also, some embodiments of the pyrolysis oil ofthe invention have fn oxygen content that is at least 20 percent less than that ‘made with the same feedstock by an IR process. [0081] Second, the pyrolysis oil has lower seid content than that made with the same feedstock by aa IR process. As ‘result the pyrolysis oil ofthe invention is more stable, less Corrosive, and less reactive to various ether components in the pyrolysis oil than the pyrolysis oil made with he same feedstock by an IR process. The pH of pyrolysis oil made With the microwave process disclosed herein typically ranges from 30 10 40 and is dependent on feedstock Pyrolysis made hy an IR process has pl of hetween 0:5 and 2.5 for similar feedstock. The pyrolysis oil made wit the oxygen-starved microwave process has a pH of a least 30, in some at least 3.2, n some atleast 3.4, some at last 3.6, and in some at least 38, 10052] ‘Third, the pyrolysis oil has fewer undesirable Impurities such as higher molecular weight tar and ehar particles tha are common in pyrolysis oil made with an TR process, Because of the uniform conditions in an oxygen Sarved atmosphere, the pyrolysis oil contains fewer char particles than pyrolysis ol made withthe same feastock by fn IR process, Some embodiments of the pyrolysis oil ofthe invention have at least 50 percent by weight less char Particles, some embodiments have at least @ percent les, ome embodiments have at last 70 percent less, and some embodiments have at least 80 percent les. For similar reasons, the pyrolysis oil contains Jess tar than pyrolysis il ‘made with the same feedstock by an IR process. Some embodiments of the pyrolysis oil ofthe invention have at ast 30 percent by weight less tr, some embodiments have at least 40 percent less, some embodiments have atleast 50 Perecat les, and some embodiments haveat last 60 percent fess. [0053] Fourth, the renewable pyrolysis il of the invention js as clean or cleaner than all formas of petroleum. What litle sulfur content, there is in the processed ofgsnic-cerbon- containing feedstock, less than 0.1 wt % i confined in the processed bioch [0054] In contrast, the process to make the processed pyrolysis oil ofthe invention usos a bencication sub-system ‘© remove a substantial amount of the difficult to remove intcellular water and water-soluble salt fom the unpre cessed onganic-earbon-conianing feedstock and microwave radiation from the oxygen-slarved microwave sub-system. The heneficaton sub-system tse any unprocessed organic- carbon-containing feedstock that includes free water, inter colllor water intracellular water intacellular water-soluble salts, and at least some plant cells comprising cell walls that Include lignin, hemicellulose, and microfibrils of cellulose ‘within cellaosie fibrils, Wit conditions preselected foreach type of unprocessed organie-carbon-containing feedstock, the benefcfation sub-system converts the unprocessed feed. sock to processed fasistock having less than 20 wt % wat and a salt content that is reduced by at least 60 wt % on 2 dry besis from that of the unprocessed ongsnic-cerbon- containing feedstock. Nov. 10, 2016 [008s] The effect of total water content reduction is sub. stantial. Now the microwave system is able to produce processed pyrolysis ol having a water content of less than TS wt, Some embodiments have a water content of less than 10 Wt 2: some have a water content of less than 5 Wt "Asa resul the energy density of the processed pyrolysis oil is approaching that of petroleum but from a cleaner renewable organie-carbon- containing feedstock. [0056] The processed pyrolysis oil ofthe invention has an energy density of atleast 33.0 MMBTUton (38.4 GI/MT). ‘Other embodiments have an enersy density of atleast 34.0 MMBTUMon (39.5 GUM), at least 35.0 MMBTUiton (20.7 GMT), at least 36.0 MMBTUton (41.9 GUM), at least 37.0 MMBTUiton (4/0 GJIMD, and at least 37:8 MMBTUlton (43.9 G1/MT) depending on the amount of ater that i in the processed pyrolysis oil, 10057] Moreover, different unprocessed organic-carbon- containing feedstock having widely different energy densi- tics i able to obtaia similar energy densities once they pass through the beneficiaton sub-system to become processed ‘onganic-carbon-containing feedstock. This allows processed eedstock from such unheneficiated feedstock as herbaceous plants to be mixed with processed feedstock from such "unheneficiated feedstock as wood! waste in the microwave subsystem to produce the processed pyrolysis oil of the invention. Processed ofzanic-carbon-containing, feedstock ‘sed to make the processed pyrolysis il ofthe invention can contain mixtures of more than one renewable feedstock, even if they have very dillerent energy densities before parsing through the benelicition subsystem, 0058] The effect of water-soluble salt on pyrolysis oil is indirect, not direct, Water-soluble salts wil stay bebind in the solid phase or processed biochar in the microwave stibsystent and not be distilled into the oil. Therefor, reduction of water-soluble salt in processed orzaniearbon- containing feedstock passing into the microwave sub-system ‘ill not havea direct eoresponkting reduction in salt content in the processed pyrolysis oil, Some salt may transfer by contact of pyrolysis oil with char or surface ejected frag- ‘meals and aerosols, so reducing salt will reduce salt in bio-ol. However, the removal ofthe water-soluble salt has an indirect effect of reducing side reactions that adversely affect the uniformity of the processed pyrolysis oil. These ‘ide reactions will contribute o some levels of aidic oxides, cortosive impurities, and undesirable contaminants such as tar Less sill may reduce non-uniform heating during miero- wave process. Microwaves are likely to bave ifferent ‘microenvironments near salt ares than non-salt areas, [0059] Processed pyrolysis oil that is less acidic also is ‘more purely liquid hydrocarbon because there are less side reactions that result in corrosive materials and undesirable contaminaats. The acidity of the processed pyrolysis oil of the invention is greatly redveed—approaching. neataliy i.e, a pli of 70. The beneficiated processed organic carbon: containing feedstock has less volatile species that lead to acidity in pyrolysis oil, One example of a reduced acid ‘causing volatile is acetic aid from acetyl groups in hemi- cellulose. The pH ofthe processed is atleast us high as 40, In some embodiments, the pl is atleast a high as 4.5, in some 50, and in some 3. [0060] The processed pyrolysis cil is more homogeneous thon that made by processes using unprocessed organic carbon-containingTeedstock, The greater homogenization ofUS 2016/0326444 Al the provesied onzanie carbon-coataining feedstock reduces nonsuniform heating during microwave part of the system [061] In addition, adverse decomposition compenents fare decroased. The processed organic-carbor-conisining Teedstock contains less adverse volatiles as discussed below under the benefciation sub-system. Als, dhe bio char par- tices that pass with the processed pyrolysis ol before the particles are filtered out cause decomposition of the pro- tossed pyrolysis ol, Thus tis important to quikly separate the processed pyrolysis oil from biochar t minimize this decomposition. I is believed biochar that contains substan- tially less water-soluble salt is less likely to decompose processed pyrolysis ol than hiochar containing more water foluble sal. [0062] As a resltof the above changes to the processed organie-carbon-conisining. feedstock, the resulting. pro- cessed pyrolysis cil has a lower spect gravity than pyroly- ‘sol from passing unprocessed organic-carbon-containing Feedstock though a microwave systom similar to the miero- wave sub system ofthe invention. The specific gravity ofthe processed pyrolysis oil i at least at low as 1.05. Some embodiments are as least as low as 1.0 and some embex menls are less than 1.0, Some embodiments have a pro- cessed pyrolysis oil wih a specifi gravity that is at least 100 less than it Would have been in 8 pyrolysis oil compo- sition made with the same microwave system as the micro- ‘wave sub-system of the invention bat with unprocessed organi-carbon-conisining. feedstock and some’ embodi- ‘mens atleast 0.10 less. [0063] Also, as a result of the above changes, the pro- cessed pyrolysis ol has less undesirable impurities such as higher molecular weight tar than the pyrolysis oil made with 8 similar microwave system but using unprocessed organic- carbon-contsining, feedstock. Because of the even more ‘uniform conditions in an oxygea-starved atmosphere than ‘with unprocessed organic-carbon-conleining feedstock in @ Iicrowave system similar o that of the microwave sub- system of the invention, dhe pyrolysis oi contains fewer char particles than pyrolysis oil made withthe same foastock by ‘aa IR process, Some embodiments ofthe processed pyeoly- siscil ofthe invention have atleast 30 percent by weight ess tar, some embodiments have at ast 40 percent less, some embodiments have at least SO percent less, and some embodiments have at leat 60 percent les. The tar is less because there is less tar created because of a removal Water-soluble salts rather than more tar is removed. Unprocessed Organic-Carbon-Containing Feedstock [0064] Cellulose bundles, imerwoven by hemicetivose tnd Tignin polymer strands, are the sta that makes plants song and proficient in retaining moisture, Cellulose has evolved over several billion years to resist being broken down by beat, chemicals, or microbes. In a plant cll wal the buoles of cellulose molecules in the mieroibrils pro- vide the wall with tensile stength, The tensile strength of cellulose microfibrils is as high os 110 k/mm”, or approxi- mately 25 times that of the strongest steel in laboratory conditions. When cellulose is wetted, as inthe cell walls, its tensile srength declines rapidly, significantly reducing its ability to provide mechanical suppor. But in biological systems, the cellulose skeleton is embedded in a matrix of pectin, hemicellulose, and lignin that act as waterprooling fnd strengthening material. That makes it dificult to pro- ‘dice fuels fom renewable cellulose-contaning biomass Fst Nov. 10, 2016 ‘enough, cheap enough, oF on a lange enough scale to make feconamical sense. AS used herein, organic-carbon-contain- ‘ng material means renewable plant-containing material that can be renewed in less than S0 years and includes pla ‘material such as, for example herbaceous materials such as grasses, energy crops, and agricultural plat waste: woody materials sueh as tree pars, otber woody waste, and dis- carded items made from wood such as broken furiter and railroad ties; aod animal material containing undigested plant cells suchas animal manire. Organic-carbon-contai- ‘ng material that i used as a feedstock in a process is called fan organic-carhon-containing feedstock [0065] Unprocessed oryanie-carbon-containing material, also refered to as renewable biomass, encompasses a wide ‘nay of organic materials as stated above. Is estimated that the U.S. alone generates billions of tons of onzai-carbon- containing material annually. As used in this document, bencficited organic-carhon-containing Teedstock is pro- cessed organic-carboo-contaning Feedstock where the mo ture content has heen reduced, a significant amount of dissolved sats have been removed, andthe energy density of the material has been increased. This processed fewistock can be used as input for processes that make several energy= producing products, including, for example, liquid hydro- carbon fuels, solid fuel to supplant coal, and synthetic natural pas. 0066] As everyone in the business of making organic- ‘arbon-contsning feedstock is reminded, the energy balance is the metric that matters most. The amount of energy used to beneliciate organie-carbon-containing feedstock and, thus, the cos of ust energy must be substantially olfet by offset by the overall improvement reslizad hy the ene ciation process inthe first place. For example, committing 1000 BTU to improve the heat content of the processed onganie-carbon-contaning feedstock by 1000 BTU, all other things being equal, does not make economic sense unless the concurent removal of a significant amount of the water Soluble salt renders previously unuseble organie-carbon: containing feedstock usable as el substitute for some processes such as boilers. [0067] As used herein, orzanie-carbon-contsining fede stock comprises free water, interelivlar water, intracellular ‘water, intreelular waterslts and atleast some plant cells ‘comprising cell walls that inhi lignin, hemicellulose, and celhlosie microfibrils within iris, In some embodiments, the water-soluble salt content of the unprocessed onganic- carbon-contaning feedstock i atleast 4000 mg/kg on a dry basis. [nother embodiments the salt content may he more than 1000-mgrk, 2000 mgr, oF 3000 mgrkg. The conte is largely dependent on the soil where the orzanie-carbon- containing material s grown, Regions that are land rich and ‘more able to allow land use for growing energy erops in ‘commercial quantities often have alkaline soils tet result in ‘onzanic-carbon-containing foodstock with water-soluble salt teantent of over 4000 marks. [0068] Water-soluble salts are undesirable in processes that use organic-earbon-containing feedstock to reat faes. ‘The salt tends to shorten the operating life of equipmes throvgh comosion, fouling, or slagging when combusted, Some boilers ave standards that limit the conceateation of salt fuels to less than 1500 mighkg. Tiss to find a balance between availability of fuel for de boilers and expense of frequency of cleaning the equipment nd replacing parts. If economical, less salt would be preferred. In fact, salt redue-