the challenges and opportunities of designing …...the challenges and opportunities of designing...

The Challenges and Opportunities of Designing Pioneer Catalytic Technologies for the Production of Sustainable

Fuels and Chemicals from Biomass

KAUST Future Fuels WorkshopMarch 7, 2016

Prof. George W. Huber University of Wisconsin-MadisonChemical & Biological Engineering

http://biofuels.che.wisc.edu/1

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The discovery of inexpensive oil revolutionized our world

Aug. 27, 1859 “Colonel Edwin Drake” Strikes Oil for First Time in Titusville, PASee “The Prize” by Daniel Yergin for a history of oil production

2

Cellulosic Biofuels are best technology option for decreasing petroleum usage and greenhouse gas emissions

CCS =Carbon Capture and Storage

Greenhouse Gas Emissions

The biomass conversion challenge

O

OH

HOOH

HOHO

Biomass-derivedFeedstocksHigh functionalityLow Thermal Stability

Liquid Fuel or Commodity ChemicalLow functionalityHigh Thermal Stability

Selective conversion of a highly functionalized oxygenated molecule, into a flammable liquid product that fits into current infrastructure.

Chemical Engineering Challenges• Economics• Low overall carbon yield• Low energy density feedstock (high oxygen content)• Distributed non-volatile feedstock• Separations of dilute mixtures• Unknown chemistry

4

Integrated Biorefinery Program• Over $2 billion has been

spent to develop 2ndgeneration biofuel technology in the past decade.

• Goal is to help share cost for 1st generation plants in biomass reforming

• Fund:• Pilot plants (up to $20

million)• Demonstration Plants• Commercial plants (up to

$500 million total)• Provides 20-50% funding

from DOE 5


2nd Generation Biofuel Companies have Struggled

Stock Price KiOR

Stock Price Amyris

Stock Price GEVO

6$95/barrel $94/barrel $94/barrel $93/barrel Average Oil Price

7

KiOR Columbus, MS Facility built in 2011-2012

KiOR• Technology to produce renewable transportation fuels from biomass by pyrolysis oil and

hydrotreating.• 2007 - Founded• 2011 IPO raised $150 million (received $75 million loan from MS)

– IPO documents claim they can produce 67 gallons of fuel per ton of biomass

• 2011 groundbreaking of Columbus, MS demonstration plant with capacity of 13 million gallons/year

• 2012 CEO claimed yields of 72 gallons per ton of biomass with potential to get 92 gallons per ton of biomass

• 2012 Management claimed that Columbus, MS demonstration facility was online that was going to produce 0.5-1.0 million gallon in 2012

• 2013 Management now says no biofuels have yet shipped but plant will produce 3-5 million gallons soon

• 2013 Columbus facility output was 25% of capacity• 2014 CEO claim actual yields in Columbus facility in low 30 gallons per ton

(whistleblower lawsuit claims 22 gallons per ton)• 2014 KiOR files for bankruptcy• Spent over $600 Million with $2 million in revenues

8http://fortune.com/kior-vinod-khosla-clean-tech/

Challenges with Pioneer Process Plants

• Rand Study, 1981 prepared for US DOE because of underestimate for costs for coal to liquids technologies in 70s.

• Looked at 44 chemical process plants from 34 companies in chemical, oil, minerals and design

• “The occurrence of cost misestimation and performance shortfalls does not surprise the few people who have experience with first of a kind technologies.”

• Severe underestimation of capital is common in new technology• Performance problems are common in new technology• First generation plants will not have a high performance. Over 50

percent of the plants failed to meet production goals in the 2nd six months after start up.

E. W. Merrow, K. E. Phillips, C. W. Myers, Understanding Cost Growth and Performance Shortfalls in Pioneer Process Plants, Rand Corporation, 1981, Prepared for US Department of Energy, R-2569-DOE.

Conventional View of Estimating Project Costs

10


Actual Views of Estimating Project Costs of Pioneer Plants

11


Estimating Plant Performance

12

NEWSTEPS = Number of new process areasBALEQS = Percentage of Material Balances based on commercial dataWASTE = 0 or 5 factor of waste disposalSOLIDS = 0 or 1 1 for solids

Every year Plant Performance increases by 20%Year 1 40%; Year 2 48%.... Year 6 100%

If Plant Performance fails to reach 40% capacity after year 1 it is unlikely to achieve nameplate capacity without a significant capital investment.

(Eq 1)


Correct Way to Estimate Economics for Pioneer Process Plants

13

MM Wright, JA Satrio, RC Brown, DE Daugaard, DD Hsu; Techno-Economic Analysis of Biomass Fast Pyrolysis to Transportation Fuels; NREL/TP-6A20-46586, November 2010

Impossible to predict economics without a working prototype.

New Technologies in the Petrochemical Area do Make Money

14McKinsey on Chemicals; Chemical innovation: An investment for the ages; M. Miremadi, C. Musso, J. Oxgaard.

IRR = 8-12%

IRR = 13-18%

IRR = 20-25%

IRR = 18-23%

Pyrolysis is Cheapest Biomass Conversion Technology

• Pyrolysis is the cheapest technology to convert biomass into a liquid fuel.• Several companies are producing pyrolysis oils on commercial scale today.• Iowa State (Robert Brown), Conoco Phillips, and National Renewable

Energy Laboratory concluded minimum cost of biofuel:– Hydrolysis $5-6/GGE > Gasification $4-5/GGE > Pyrolysis $2-3/GGE (GGE = gallons of

gasoline energy equilvalence.)– (Study assumption: nth plant economics; 10% IRR; 2000 tons/day feedstock; Feedstock

cost $75/ton; 100% equity financing.)

• Challenges with pyrolysis technology:– Controlling the chemistry– Low quality fuel– Upgrading of pyrolysis vapors– Catalysts and reaction engineering– Hydrogen requirements for upgrading (Hydrogen is more expensive than actual pyrolysis

oil)

M. M. Wright, D. E. Daugaard, J. A. Satrio, R. C. Brown, Fuel 89 2010 S2-S10.R.H. Venderbosch, W. Prins (2010) Fast pyrolysis technology development. In: Biofuels, Bioproductsand Biorefining (p 178-208).

Pyrolysis Oils

http://www.btgworld.com/uploads/documents/Fast%20Pyrolysis%20Development_Venderbosch%20et%20al.%202010.pdf

ENSYN Commercial Fast Pyrolysis Plant

Processes 100 metric ton of biomass/day.

Plant located in Western Ontario.

Formed joint venture with UOP to license technology

Bio-oil: Characterization C: 47.0%H: 8.2%O: 44.8%

ElementalComposition

pH: 2.75

Acidity

Solubility

OakWood Bio-oil

Water: 62%Methanol: 98%

Toluene: 14%Diesel Fuel: 4%

Ash: 0.03 wt%

Non-Combustibles

Viscometry

Viscosity: ~150 cP

S. Czernik, A. V. Bridgwater, Overview of applications of biomass fast pyrolysis oil. Energy Fuels 18, 590-598 (2004).

Bio-oil CompositionComponent Formula C # MW Carbon % overall wt%

C5 sugars (xylose) C5H10O5 5 150 11.65 11.51%Acetic acid C2H4O2 2 60 9.73 9.61%

Levoglucosan C6H10O5 6 162 7.17 6.37%Hydroxyacetaldehyde C2H4O2 2 60 6.17 6.10%

2,5-dimethyl tetrahydrofuran

C6H12O 6 100 2.49 1.37%

Sorbitol C6H14O6 6 182 1.97 1.97%

2-methyl tetrahydrofuran C5H10O 5 86 1.71 0.97%

Hydroxyacetone C3H6O2 3 74 1.68 1.36%Catechol C6H6O2 6 110 1.07 0.65%

Hexanoic acid C6H12O2 6 116 1.02 0.65%1-hydroxy-2-butanone C4H8O2 4 88 0.93 0.67%

Cyclohexanol C6H12O 6 100 0.8 0.44%5-hydroxymethylfurfural C6H6O3 6 126 0.57 0.39%

Furfural C5H4O2 5 96 0.54 0.34%

Other Light Oxygenates - - - 2.94 2.24%49.00 45.00%

Oxygenates / Sugars

Carbon % Overall wt%Pyrolitic Lignin 51.00 30.00%Sugars/sorbitol 20.79 19.85%

Oxygenates 28.21 25.15%Water/ash 0 25.00%

Overall Composition

• Carbon % values obtained from Kamala, Huber et. al (not yet published)

• Weight % normalized based on typical bio-oil feedstock

18

Bio-oil undergoes phase separation when heated

1 day 5 day

7 day•Bio-oil phase separates on accelerated aging (heated to 90oC)•A thick tarry phase is formed at the bottom and a less viscous top phase

Hydrodeoxygenation (HDO) of Biomass

• Selective removal of oxygen (as H2O or CO2) from biomass derived feedstocks• Make targeted products (alkanes, alcohol, polyols, ethers) that fit into existing infrastructure

• Process a range of biomass derived feedstocks (carbohydrates, pyrolysis oils, hydrolysis products)

• Lots of water present (up to 95 wt% H2O)

• Minimize hydrogen consumption

• Design of Catalyst is crucial 20

Liquid Products produced from HDO of pyrolysis oils

9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 240

3

6

9

12

15350 oC

Carb

on (w

t%)

Carbon number

Iso paraffins N-paraffins Cyclics Aromatics

Time (hrs) Distribution of C (in terms of %) with time on stream (hrs)

25 45 66 Overall

Pressure 2030 2099 2158 -

Organic phase 0.00 56.43 73.61 40.52

Aqueous phase 0.70 5.70 4.16 3.32

Gas phase 46.53 18.49 14.45 27.8

Missing 52.77 19.37 7.79 28.3

• Pyrolysis oil produced from pine wood

• HDO in two stage reactor

• Reactor plugs after 66 hr

• Make C10-C24 cycloalkane

• 73 % carbon yield at 66 hr

• 41 % carbon overall (low yield)

21

Current Technology for Hydrotreating

• Catalyst deactivation

• Shift to high boiling residual oil products

• Extensive coke formation early

• Gasoline and gas products favored over distillate-range fuels

• Low value of residual oil?

22

Renewable Aromatics from Catalytic Fast Pyrolysis (CFP) of Biomass

IHS Chemical Week (http://www.chemweek.com)Biochemical startup announces para-xylene breakthroughDecember 5, 2012 | Rebecca CoonsAnellotech, a New York City-based start-up developing biobased routes to aromatics, says it has licensed technology from the University of Massachusetts-Amherst that will triple the para-xylene yields of its catalytic fast pyrolysis (CFP) technology.

www.anellotech.com


Block Flow Diagram for Catalytic Fast Pyrolysis

Torren R. Carlson, Yu-Ting Cheng, Jungho Jae and George W. Huber, Production of Green Aromatics and Olefins by Catalytic Fast Pyrolysis of Wood Sawdust, Energy and Environmental Science (2011) 4 145-161.

All chemistry occurs in one single reactor.

Reactors for Catalytic Fast Pyrolysis

Distributor Plate

FreshCatalyst

Spent catalyst to regenerator

Products(to separation)

Biomass from hopper

Fluidization Gas

Phenomena occurring in CFP1. Fluidization of particles2. Heat transfer to

biomass particles3. Solid biomass pyrolysis4. Bubbles formation and

growth5. Mass transfer between

phases6. Reactions in gas phase7. Catalytic reactions

Feed:PineWoodSawdust

Process Development Unit(Continual flow of catalyst and biomass on stream since April 2011)

Raw Liquid Product (Contains aromatics and water)

AromaticProducts

GCMS of raw liquid only observe aromatics

Catalytic Fast Pyrolysis:Process Development Unit

26

CFP involves reactions in solid biomass, gas phase and inside catalyst

Desired Chemistry:Pyrolysis (homogeneous)Dehydration (heterogeneous & homogeneous)Oligomerization & decarbonylation (heterogeneous)

Undesired Chemistry:Homogeneous and Heterogeneous coke formation

Aromatic Yield Increases with Heating Rate

Reaction Conditions: Temperature 600oC; ZSM-5; Feed: Glucose; Catalyst to Feed Ratio 19C6O6H12 → 12/22 C7H8 (63 % Yield) + 48/22 CO (36 % Yield) + 84/22 H2O

0

5

10

15

20

25

30

35

40

45

1 10 100 1000Nominal heating rate (°C s-1)

Carb

on y

ield

(%)

Aromatics Carbon monoxideCarbon dioxide coke

Carlson, T.R.; Vispute, T.P.; and Huber, G.W.; Green Gasoline by Catalytic Fast Pyrolysis of Solid Biomass-derived Compounds, ChemSusChem, 1, 397-400 (2008).

Selectivities (2)

BenzeneBenzeneBenzeneBenzene

TolueneTolueneTolueneToluene

Xylenes, ethyl-benzeneXylenes, ethyl-benzeneXylenes, ethyl-benzeneXylenes, ethyl-benzene

Methyl-ethyl-benzene, trimethyl-benzeneMethyl-ethyl-benzene, trimethyl-benzeneMethyl-ethyl-benzene, trimethyl-benzeneMethyl-ethyl-benzene, trimethyl-benzene

IndanesIndanesIndanesIndanes

NapthalenesNapthalenesNapthalenesNapthalenes

CokeCokeCokeCoke

Glucose

Cellobiose

Cellulose

Xylitol

Selectivity (%)

12.9792209643

12.9238172581

11.0495115501

11.5419684189

21.5656347771

22.0954515898

20.3152491336

19.733840689

14.2728383261

14.471321865

15.8625765825

16.9804699675

3.2459675372

3.2872082023

4.0669216011

4.7095296295

4.2802810346

4.8589898264

5.5333155842

6.9736185411

43.6560573608

42.3632112584

43.1724255484

40.060572754

37.4990650292

36.8036772439

34.2557261186

35.7290723283

coke runs

sample numberconditionpercent CC per mginitial carbonyield

31000/400/2401.510.01510.020800646772.5938968248

81000/500/2400.930.00930.020800646744.7101483755

11000/600/2400.690.00690.020800646733.1720455689

71000/700/2400.570.00570.020800646727.4029941656

21000/800/2400.530.00530.020800646725.4799770312

41/600/2400.810.00810.020800646738.9410969722

55/600/2400.740.00740.020800646735.575816987

650/600/2400.710.00710.020800646734.1335541362

91000/600/240 cb0.630.00630.020973733130.0375711129

101000/600/240 ce0.60.0060.020973733128.6072105837

111000/600/240 xy0.790.00790.021066558637.5001923564

zsm1010%1.30.0130.040232029832.3125630904

zsm1120%3.450.03450.079195899243.5628616367

zsm1230%50.050.119959014141.6809027509

zsm1340%7.010.07010.159824578943.8605879409

nap expw+cw+c+smassmass naparea outmass napyeildarea/mass in

trc02p430.00E+000.000.50

trc03p43400108.48122.041.36E+010.13900163037895868750.070.505680414488.880.11

trc04p43800108.46122.791.43E+010.14689479087037492260.060.424790838547.10

trc05p43800.00108.40125.121.67E+010.15265656128880826870.080.515817520584.34

trc06p43400.00106.82124.481.77E+010.161238927710054117370.090.556235539714.900.520.0345821407

0.470.0639582945

0643520969

0631511537

0510842863

0486061264

0547373330

GlucoseCellobioseCelluloseFurfural

0000

0000

0000

1001001000

calibrations

CO, CO2 calnew runs

sample nameml dil CO (2%)mass COarea ion 28aveml dil CO (2%)mass CO (mg)sample namearea ion 28average

0.50.012537279057370295260.50.01145trc20p131.94E+0719111082

0.50.0125367799950.50.01145trc21p131.88E+07

10.0254229618343232201.510.0229trc22p133.14E+0731386458

10.0254416822010.0229trc23p133.14E+07

2.50.0625185883937214797326.6666672.50.05725trc24p135.86E+0758254240

2.50.06252225244392.50.05725trc25p135.79E+07

2.50.06252359836041.50.03435trc26p134.29E+074.29E+07

ml dil CO2mass CO2area ion 44ml dil CO2mass CO2sample namearea ion 44

0.250.0198192783916144506394.66666710.0792272.15E+082.13E+08

0.250.019812487524210.0792282.11E+08

0.250.01981158600260.250.0198297.52E+077.41E+07

0.50.0396299717644280786629.50.250.0198307.31E+07

0.50.03962618556150.50.0396311.49E+081.49E+08

10.0792328988971336992908.3333330.50.039632

10.079236435107620.1584332.70E+082.75E+08

10.079231763867820.1584342.80E+08

2.50.19835302206699294033471

2.50.19836285860243

0.29740391560263391560263

0.29741402403957

ml dil CO (30%)

0.250.085875trc01p15162725660167207264.5

0.250.085875trc02p15171688869

0.50.17175trc03p15257766352258659856

0.50.17175trc14p15259553360

10.3435trc04p15362769741357051579.5

10.3435trc05p15351333418

weight loss from the catalyst1.50.51525trc06p15457922351457922351

1.50.51525trc07p15

sample namecap+woolcap+wool+sampmass cat (mg)area of water (ion 18)20.687trc08p15516580296516580296

trc01p10115.94127.2911.3522577183420.687trc09p15

trc02p10113.03119.146.112151471972.50.85875trc10p15672955337

trc03p10112.4116.754.352004747042.50.85875trc11p15672955337

trc04p10114.71123.328.614048076170.10.03435trc12p158835577986344533

trc05p10113.28126.1212.846122000890.10.03435trc13p1584333287

trc06p10110.22116.436.213068243590.050.017175trc15p154686024544484281.5

0.050.017175trc16p1542108318

BTEXN calibration

sample nameamount injectedarea benzavearea tolarea xylenearea napmass compound (mg)area/mass

trc18p111ml758828916.43E+07632871695451977659937805570585216.02E+07552468490.002299689025000.99530327181.05092147391.2600810071

trc19p111ml6430769252864152587994525.49E+070.002293997260001.07085174480.96275845241.1711674487

trc20p111ml5264877847408007524383065.06E+070.002262191530001.03610794780.93671624021.0402665816

trc21p112ml899543948.97E+07746847257221070575916934747661316.68E+07696558440.004189792335001.13609504771.11765507041.3461652909

trc22p112ml8938962469736685736153287.25E+070.004184038320001.01553802820.96203137991.2331475654

trc23p113ml1069412029.38E+078224462479928143.66666678609993383649081.66666677.69E+0775762728.66666670.00614349988833.33331.11916312271.06905019571.3900666981

trc24p113ml8855088081070238832426667.68E+070.00613873777666.66671.08439070741.05609078811.1535400777

trc25p113ml8604373076469569816046467.36E+070.00613600774333.33331.10888982511.03911151081.169210595

trc26p115ml1219467841.24E+0810102264698884715.66666671070889351017699539.87E+0797766242.66666670.01107088935001.08487211481.02341714021.2353906167

trc27p115ml10477015592162751982753129.72E+070.0198275312001.01129768480.94839665041.0781325751

trc28p115ml146753075103468750999456129.74E+070.0199945612001.02602838791.0621964551.5065475907

1.0625943531.02075866881.234883277

nap cal

sample namewt%/100 napmass injectedareaave area

trc01p130.000140180.00011060221625232259571168533.3505748940.0745864372

trc03p130.000140180.0001106022302001

trc04p130.000140180.0001106022314189

trc05p130.000851630.00067193611225104312395637

trc06p130.000851630.000671936112540231

trc07p130.0016860.0013302542158171421933061

trc08p130.0016860.00133025422284408

trc09p130.0040240.0031749364429838844784706.5

trc10p130.0040240.00317493645271025

trc11p130.0064320.0050748487262862471814150.5

trc12p130.0064320.00507484870999677

trc13p130.0146020.011520978139097037136441921

trc14p130.0146020.011520978133786805

trc15p130.0183510.014478939151977601167098089.33333328773638.8627270.1721960974

trc16p130.0183510.014478939180617251

trc17p130.0183510.014478939168699416

trc18p130.0114780.009056142124649524121465509

trc19p130.0114780.009056142118281494

trc37p130.03550.0280095296386556293080559.50.0319051192

trc38p130.03550.0280095289774563

trc39p130.026890.021216212490559482490559489350770.17491597

0

furfural calibrationmass injectedareaarea ion 96

trc12p430.00748502150.00590568194264560644336637.584889888598994.5

trc13p430.00748502150.0059056819460276698709001

trc14p430.0154291680.012173613686031887809099201865053417631800

trc15p430.0154291680.01217361367578795316613066

0

0

calibration

0.789 mg injected

cal numbermass benzarea benzarea/massmass tolarea tolarea/massmass naparea naparea/mass

cal 10.020277324271624311969850177.29180.0091445113039141214258982930.74210.003597847591029521098852366.9757

cal 20.003305915051965415281618071.87730.021460822053547910276200281.44340.010651512219676211472258555.1331

cal 310778306404607802702198297390

cal 1 (2)0.020277324508826512086829360.9110.0091445113352899714602094262.02170.003597846077729016892716185.2667

cal 2 (2)0.003305913821150811558544545.97980.02146082077425189680091981.659580.010651512153861011410468948.0355

cal 3 (2)10515788004042927802101963340

aromatic cal plot

225957144336637.58598994.5

123956378090992017631800

21933061

44784706.5

71814150.5

136441921

167098089.333333

121465509

293080559.5

249055948

napthalene

furfural

ion 96

area

mass (mg)

calibration for aromatics

0.000110602

0.0059056819

0.0059056819

0.0006719361

0.0121736136

0.0121736136

0.001330254

0.003174936

0.005074848

0.011520978

0.014478939

0.009056142

0.0280095

0.02121621

water calibration plot

13.3612.879.048.31

11.417.5610.7713.18

6.736.694.84

22-Sep

mass of catalyst (mg)

area of water peak

adsorbed water calibration

442535602

667226283

529216956

234618817

408440047

325455039

530515479

230456933

317698851

398861672

272114287

gas cal plot

167207264.5212704994

25865985674149032

357051579.5148774726

86344533275404142.5

44484281.5294033471

391560263

CO

CO2

area

mass (mg)

0.085875

0.0792

0.17175

0.0198

0.3435

0.0396

0.03435

0.1584

0.017175

0.198

0.297

main

sample namecapillary + wool (mg)capillary + wool + sample (mg)total sample mass catalyst and reactat (mg)mass of reactant (mg)mass of carbonmass of catalyst (mg)loss from cat (mg)comments

trc06p07115.48124.128.641.73641900120.693962311120%physical mix

trc07p07113.71123.039.323.75119129081.499168907940%mass glucose (july 10)mass catfraction glucose

trc08p07114.63122.577.940.39519584510.15794057875%

trc09p07108.97117.418.440.83895487850.335289504510%glucose/zsm 5%0.06901.31730.0498

trc10p07115.01123.178.162.42984063170.971089247130%glucose/zsm 10%0.10310.93410.0994

trc11p07111.21121.8710.662.14238733250.856208129320%glucose/zsm 20%0.13200.52480.2010

trc12p07113.32121.468.140.40515040030.16191893085%glucose/zsm 30%0.20740.48910.2978

trc13p07111.67119.798.120.40415494480.16152109565%glucose/zsm 40%0.25880.38420.4025

trc01p09113.58122.528.940.88865599690.3551526268mass glucose (july 25)

trc02p09112.79121.99.110.90555437720.36190608835%0.05471.01280.0512

trc03p09115.51124.028.510.84591303510.338070341610%0.09890.86320.1028

trc04p09112.12121.869.740.96817778630.3869336224aug 10 glucose

trc05p09110.14120.2410.11.00396259160.40123507055%0.0000

trc06p09113.93122.898.960.89064404170.355947151610%0.09180.81990.1007

trc02p17106.36116.8710.514.23015241061.69058639729/18/07

trc03p17106.21114.748.530.43708758780.1746826735%

trc04p17104.37115.0510.680.54725620610.218711717234.83597.520.0551

trc05p17106.94116.639.690.49652740050.19843787839/22/07

trc06p17107.31118.5911.281.15953850950.463411206329.61558.140.0504

trc07p170009/23/2007 G1

trc08p1700046.71880.410.0504

trc09p17108.54117.949.40.48166744730.1924990779/23/2007 G20.0000

trc10p17107.72120.2212.50.64051522250.255982815153.52991.750.0512

trc11p17108.78119.8911.110.56928992970.22751752619/24/2007 G3 p350.0000

trc12p17108.47118.29.730.97972359330.391547920539.98758.360.0501

trc13p17109.58119.8210.241.03107601180.41207098739/27/2007 G4 p35

trc15p17109.22119.6310.411.04819348470.418912009539.7721.960.0521

trc16p17106.84116.399.550.96159921030.38430448529/29/2007 G5 p350.0000

trc01p19107.39118.6311.241.13176702860.452312294668.861264.480.0516

trc02p19104.31116.1411.831.19117472850.4760546669/30/2007 G6 p350.0000

trc03p19106.82118.1311.311.13881539980.455129186136.38630.050.0546

trc04p19109.56121.9712.411.24957551830.49939462429/30/2007 G7 p350.0000

trc05p19108.7119.4110.711.07840078970.430984401772.47646.240.1008

trc06p19107.8120.112.31.23849950640.49496808049/30/2007 G1 p390.0000

000156.46589.880.2096

NEW RUNS (9-18-2007)0009/30/2007 G2 p390.0000

trc01p33106.27117.0110.740.59156195150.236418571163.58388.90.2961

trc02p33106.29117.2810.990.60533201550.24192179669/30/2007 G3 p390.0000

trc03p33108.4121.1912.790.70447647660.2815450208202.06301.610.4012

trc04p33106.89119.3212.430.68464758440.27362037610/01/2007 xy1 p390.0000

trc05p33108.13119.5211.390.6273641180.2507269576area water42.72797.760.0508

trc06p33105.69119.0513.360.73587222270.2940923752442535602water cal 110/01/2007 c1 p390.0000

trc07p33108.91120.3211.410.62846572310.2511672156408440047water cal 29/18/0738.79720.440.0511

trc08p33105.35112.086.730.37069012410.1481468327317698851water cal 310/01/2007 g4 p390.0000

trc09p33106.83119.712.870.70888289710.283306053667226283water cal 1 fresh vacuum 9-1930.11546.80.0522

trc10p33106.79114.357.560.41640673680.166417541632545503910/01/2007 g5 p390.0000

trc11p33105.46112.156.690.36848691390.147266316639886167249.5907.680.0517

trc12p33107.48116.529.040.49792551590.198996637152921695610/01/2007 cb1 p390.0000

trc13p33108.96119.7310.770.59321435910.237078958153051547943.62769.420.0537

trc14p33108.46113.34.840.26658843990.106542447327211428710/08/2007 p39n10.0000

trc15p33107.11115.428.310.45771692890.1829272184234618817water cal 19/22/0743.21312.660.0319

trc16p33107.63116.568.930.49186668780.1965752178water cal 210/08/2007 p39f10.0000

trc17p33105.04118.2213.180.72595777650.2901300527230456933water cal 381.391294.780.0591

trc18p33104.56113.418.850.44585027650.178184693910/08/2007 p39n20.0000

trc19p33104.21117.6813.470.67859923440.271203144330.881239.160.0243

trc20p33106.26117.5911.330.5707891110.22811667610/10/2007 p39g70.0000

trc01p35107.81116.078.260.41615389590.16631649349/23/0755.711033.770.0511

trc02p35104.44113.789.340.47056626970.188062475610/12/2007 p39g80.0000

trc03p35107.95116.138.180.41212334970.164705679944.9862.70.0495

trc04p35106.73117.8411.110.55974210460.2237017242silicalite0.0000

trc05p35106.89118.3411.450.5768719260.230547681615.8233.060.0635

trc06p35106.62118.6111.990.61391296030.2453511834sio2al2o30.0000

trc07p35105.74117.5611.820.60520860640.24187247656.911059.170.0510

trc08p35106.85116.239.380.47258154280.188867882441688491water cal 14444402.02558635beta0.0000

trc09p35106.92112.785.860.29523750970.117992088640690220water cal 26943723.5494880645.52844.530.0511

trc10p35105.14113.948.80.44336008280.177189484583209323water cal 39/24/079455604.886363640.0000

trc11p35105.45115.8410.390.52346718870.209204402875201029water cal 4(sealed after calcination 0n 9-23-07)7237827.622714150.0000

trc13p35106.92119.4812.560.63279575460.252897718898102403water cal 17810700.875796180.0000

trc12p35105.7117.411.70.59906435660.2394169179g20.0000

trc14p35107.9119.1511.250.56338777960.2251587234g30.0000

trc15p35107.72119.5811.860.5939359170.2373673298g30.0000

trc16p35107.77117.9410.170.50930255280.2035434860.0000

trc17p35106.11116.099.980.49978755920.19974080530.0000

trc18p35106.21115.839.620.50142320720.2003944944g49/27/070.0000

trc19p35104.54113.098.550.44565160310.1781052938g40.0000

trc20p35103.99113.619.620.50142320720.2003944944g4

trc21p35106.17115.128.950.46650080090.1864377052g4

trc22p35106.75117.210.450.54468529270.217684248water cal 1

trc23p35105.41116.410.990.57283170970.2289330034g49/29/07

trc24p35107.27118.5411.270.58203623980.2326116069g5

trc25p35105.45113.958.50.43898030510.1754391002g5

trc26p35105.83115.59.670.4994046530.1995877763g5

000

000

000

trc27p35106.54115.749.20.47513162430.1898870261g5

trc28p35106.9116.379.470.48907570460.1954597975g5

trc29p35106.47115.418.940.46170399150.1845206536g5

trc30p35105.93115.199.260.47823030880.1911254197g5

trc01p37105.27113.137.860.40592767040.1622295679g5

trc02p37106.84114.797.950.41057569710.1640871584g5

trc03p37100.91111.3710.460.5402039990.2158932927g5

trc04p37104.43115.6311.20.57842110790.2311668143water cal 1

trc05p37106.96116.549.580.5229662530.2090042031water cal 19/30/07

trc06p37106.91117.1210.210.55735756190.2227487384g6

trc07p37106.89116.9810.090.55080683640.2201307317g6

trc08p37105.83115.149.310.50822712060.203113688g6

trc09p37106115.789.790.53443002270.2135857149g6

trc10p37106.64116.569.920.5415266420.2164218888water cal 2

trc11p37105.27112.26.930.69877572320.2792667066g7

trc12p37106.39111.575.181.08591633840.4339880014g1

trc13p37106.21112.025.811.72024290470.6874975113g2

trc14p37105.74110.815.072.03395913990.8128746486g3

trc15p37105.84117.4311.590.58909765850.2323092968xy1

trc16p37105.8114.78.90.45237007420.1783910907xy1

trc17p37103.55114.7411.190.56876641920.2242917197xy1

trc18p37106.14117.4911.350.57988554190.2439483437c1

trc19p37106.74117.6810.940.55893813470.2351361128c1

trc20p37104.37116.9712.60.6576173060.262817687p39g4

trc21p37106.58117.611.020.57515418350.2298611834p39g4

trc22p37107.83119.6411.810.61638574470.2463394352p39g4

trc23p37106.09116.8410.750.55592991910.2221781789g5

trc24p37105.53115.8110.280.53162414590.2124643423g5

trc25p37107.17118.1210.950.56627280140.2263117264g5

trc26p37104.85116.4711.620.60092145680.2401591106g5

trc27p37105.59118.2312.640.65367015610.2612402029g5

trc28p37106.56118.6912.130.62729580640.2506996568

trc29p37105.63116.0210.390.53731273110.2147377934

trc30p37108.82121.1212.300.63608725630.2542131721

trc31p37104.35116.4712.120.62677866230.2504929794

trc32p37104.52116.0111.490.59419858330.2374723047

trc01p41105.6116.5810.980.56782423370.2269317586

trc02p41109.09120.6611.570.62073624910.2611335667

trc03p41104.9116.8511.950.6411234380.2697101229

trc05p41105.58114.018.430.26859410260.2514729837n1

trc06p41104.26112.978.710.27751537770.2598255857n1

trc07p41105.25113.868.610.2743292080.2568425136n1

trc08p41106.83117.1110.280.60798389730.3796735412f1

trc09p41105.68115.9710.290.60857532140.3800428735f1

trc10p41106.68113.77.020.17068564770.159805553

trc11p41106.83115.478.640.21007464330.1966837575

trc13p41105.85115.8510.000.51134486180.2043596976g7

trc14p41106.26117.3411.080.56657010680.226430545g7

trc15p41105.96115.569.600.49089106730.1961853097g7

trc18p41104.41114.7710.360.52975327680.2117166468

trc19p41107.65117.359.700.49600451590.1982289067

trc20p41105.47116.410.930.54071947990.2160993054

trc21p41106.78117.210.420.51548920230.2060159892

trc22p41108.27118.269.990.49421661520.1975143697

trc07p43106.99117.7310.740.68187736080.2725132522

trc08p43107.91120.0712.160.77203246810.3085438684

trc09p43105.49118.5613.070.66645195680.2663484677area of ion 28 (carbon monoxide)mass of CO (mg)percent yeild (mass CO/mass xylitol)mass carboncarbon yeild %selectivityarea of aromatics all peaks after 4 min except 7.56 (furfural)mass of aromatics (mg)mass carbon (mg)carbon yield %selectivitytotal carbon percentcomments

trc10p43108.68123.0414.360.73223030610.292636878

trc11p43110.01121110.56410943210.2254471328

xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1xsa1




Reaction time plot (600)

111

333

555

101010

303030

606060

120120120

240240240

Aromatics

Carbon Monoxide

Carbon Dioxide

t / s

Carbon yield (%)

2.8869243581

7.8953494628

6.7925233424

12.6063503672

9.803141366

8.4280412004

17.1044315609

11.1373168179

9.682680622

21.3255676372

10.8356007564

8.919867692

25.7107152741

13.3695544625

10.8280696993

27.7596010456

14.1364086955

11.6572795157

28.9295287882

14.6218210685

11.6833173964

31.3826941419

15.2908075456

12.6218920059

Percentage plot

55555

1010101010

2020202020

3030303030

4040404040

Aromatics

Carbon Monoxide

Carbon Dioxide

Oxygenates

coke

Glucose (%)

Carbon Yield (%)

31.3826941419

15.2908075456

12.6218920059

0

33.1720455689

27.1751449508

13.5553158551

11.0338284337

1.1730979757

32.3125630904

22.8546203764

11.4133152209

9.3425622504

3.4674435619

43.5628616367

16.5454626954

8.7303691642

7.2795637247

8.6050250628

41.6809027509

13.2399004427

7.0533624196

6.2552176745

10.257665918

43.8605879409

Percentage plot (2)

555555

101010101010

202020202020

303030303030

404040404040

Aromatics

Carbon Monoxide

Carbon Dioxide

C3 Oxygenates

coke

C5 oxygenates

Glucose (%)

Carbon Yield (%)

31.3826941419

15.2908075456

12.6218920059

0

33.1720455689

0

27.1751449508

13.5553158551

11.0338284337

1.1730979757

32.3125630904

0

22.8546203764

11.4133152209

9.3425622504

2.4247550677

43.5628616367

1.0426884942

16.5454626954

8.7303691642

7.2795637247

2.2698588765

41.6809027509

6.3351661863

13.2399004427

7.0533624196

6.2552176745

2.1332549078

43.8605879409

8.1244110102

Selectivities

Benzene12.923817258111.049511550111.5419684189

Toluene22.095451589820.315249133619.733840689

Xylenes, ethyl-benzene14.47132186515.862576582516.9804699675

Methyl-ethyl-benzene, trimethyl-benzene3.28720820234.06692160114.7095296295

Indanes4.85898982645.53331558426.9736185411

Napthalenes42.363211258443.172425548440.060572754

b)

Glucose

Cellobiose

Cellulose

Xylitol

Selectivity (%)

11.2849327983

18.2680737143

12.485200852

3.3831827197

8.320080819

46.2585290967

feed comparison

XylitolXylitolXylitolXylitol

GlucoseGlucoseGlucoseGlucose

CellobioseCellobioseCellobioseCellobiose

CelluloseCelluloseCelluloseCellulose

a)

Aromatics

CO2

CO

coke

Carbon yield (%)

47.4867980788

7.2005721062

12.7695211799

37.5001923564

31.3826941419

12.6218920059

15.2908075456

35.575816987

28.1808120589

10.3637902859

13.0335056327

30.0375711129

31.0902547732

8.6010430382

15.2122322168

28.6072105837

Temperature plot

400400400400

500500500500

600600600600

700700700700

800800800800

Aromatics

Carbon monoxide

Carbon dioxide

coke

T/°C

Carbon yield (%)

8.1963868745

7.4015742412

6.7388391689

72.5938968248

19.190131076

10.1574227985

9.1069020058

44.7101483755

31.3826941419

15.2908075456

12.6218920059

33.1720455689

26.1277666136

10.3620419643

7.7983033485

27.4029941656

26.0483230109

11.760267854

8.4313490384

25.4799770312

heating rate

1111

5555

50505050

1000100010001000

Aromatics

Carbon monoxide

Carbon dioxide

coke

Nominal heating rate (°C s-1)

Carbon yield (%)

14.8556099406

8.9710840324

6.611488372

38.9410969722

23.6266449035

10.4602482553

8.5466103949

35.575816987

29.3530728097

13.3430477586

11.9569584425

34.1335541362

31.3826941419

15.2908075456

12.6218920059

33.1720455689

catalyst comparison

ZSM-5ZSM-5ZSM-5ZSM-5

SilicaliteSilicaliteSilicaliteSilicalite

Amorphous silica-aluminaAmorphous silica-aluminaAmorphous silica-aluminaAmorphous silica-alumina

β-zeoliteβ-zeoliteβ-zeoliteβ-zeolite

Aromatics

CO2

CO

dehydration porducts

Carbon yield (%)

31.3826941419

12.6218920059

15.2908075456

0

6.5193290323

5.6326912099

6.1468432975

12.3029162134

0.5562347567

4.5340802887

4.2824652518

1.4797633829

4.2679122229

10.5422704206

7.7609171797

1.1018939417

aromatic breakdown

Reaction time (10% Glucose on ZSM-5)

old cal

sample nameReaction time (600C)initial mass of carbonarea benzenemass carboncarbon yieldselectivity (just aro)area toluenemass carboncarbon yieldselectivityarea xylenes, ethylbenzmass carboncarbon yieldselecarea methy-ethyl-benz, trimeth-benzmass carboncarbon yieldselecarea indanesmass carboncarbon yieldselecarea napthalenesmass carboncarbon yieldsecltotal areatotal aromatic yieldtotal carbon yieldarea ion 44 (CO2)mass Carboncarbon yieldarea ion 28 (CO)mass carboncarbon yieldarea ion 18coke

trc01p090.50.3551526268000000000000000000004.9612472703-2.98E-03-0.8390758720.02065.8003231423Benzene

trc02p0910.36190608838.92E+060.00067075120.185338478524.3079750934.70E+060.00034943610.09655437112.66354004524.54E+060.00033503060.092573900712.14148346723.23E+060.00023822850.06582604538.63338192755.50E+060.00041038850.113396417114.87245014489.89E+060.00075555260.208770341527.3811693222367802380.762459554112.46836291657.35E+071.21E-023.3548842578.31E+070.03022284668.3510191054417724088TolueneXylitolGlucoseCellobioseCelluloseFurfural35.575816987sample numberconditionpercent CC per mginitial carbonyield

trc03p0930.33807034163.17E+070.00238549240.705620135312.429379076.01E+070.00446740671.321442953323.27699361955.79E+070.00427457741.264404729322.27227497281.97E+070.00145410410.43011879837.57646972153.18E+070.00237128140.701416572512.35533402495.55E+070.00423950791.254031289722.08954859132567180105.677034478427.55323648041.07E+082.56E-027.56778191921.22E+080.048372524614.3084200828449697493Xylenes, ethyl-benzeneAromatics47.486798078831.382694141928.180812058931.090254773222.034971911630.037571112931000/400/2401.510.01510.020800646772.5938968248

trc04p0950.38693362246.99E+070.00525937811.359245563911.24259665911.31E+080.00973405282.515690611820.80778898121.18E+080.00869408742.246919587218.58472914333.34E+070.00246128770.63610074455.26131870146.52E+070.00486196711.256537777410.3930796562.06E+080.01577003984.075644720733.710486858962364236812.090139005641.30273025141.36E+084.06E-0210.50037987311.58E+080.072403837318.7122113727528616008Methyl-ethyl-benzene, trimethyl-benzeneCO27.200572106212.621892005910.36379028598.60104303824.848441137328.607210583781000/500/2400.930.00930.020800646744.7101483755

trc05p09100.40123507051.01E+080.00758254111.889800188811.3883651331.75E+080.01300092163.240225629119.5263355331.39E+080.01024804562.554125084215.39173782833.69E+070.00272462980.67906073994.09217424127.77E+070.00579286911.44375940858.70042208963.57E+080.02723246466.787159597340.90096517588563624716.594130647846.14018957961.37E+084.09E-0210.18463951991.64E+080.077684804819.3614194119484902074IndanesCO12.769521179915.290807545613.033505632715.212232216810.73631952437.500192356411000/600/2400.690.00690.020800646733.1720455689

trc06p09300.35594715161.17E+080.00882135252.478275894811.8789929121.91E+080.01422315143.9958604319.15315313551.38E+080.01014623422.850488945313.66310266233.46E+070.00255504280.71781522263.44066694088.05E+070.00600037481.68574878098.0802132894.26E+080.03251394819.134487496943.783871060398679176920.862676770450.3311843061.26E+083.49E-029.80200859621.55E+080.070002342819.6664989393456334000Napthalenescoke37.500192356435.57581698730.037571112928.607210583771000/700/2400.570.00570.020800646727.4029941656

trc09p07600.33528950451.43E+080.01078291533.216001434712.2362058512.29E+080.01702272865.077024003719.31700345331.55E+080.01140172893.400562414112.93842137623.87E+070.00285516710.85155278473.23997839519.41E+070.00702156022.09417834567.96790606145.11E+080.039038929311.643349630744.300484863117071457626.282668613558.92227638941.31E+083.75E-0211.19475335241.57E+080.071902346121.4448544235190010453CokeOther32.543108635140.704606306748.421892022545.096469971762.380267427121000/800/2400.530.00530.020800646725.4799770312

trc13p17900.41207098731.84E+080.01387273573.366588795212.60337621412.78E+080.02065500955.012488165518.76506991541.92E+080.01418499453.442366712412.88706325064.96E+070.00365595030.88721371233.32142975521.26E+080.00939558822.28008970828.53588903866.32E+080.048307304711.72305407843.8871718261146238261226.711801171766.40702265641.60E+085.53E-0213.4139256421.98E+080.108297595226.2812958427sum104.957083721394.871210680381.615679090483.510740611941/600/2400.810.00810.020800646738.9410969722

trc12p171200.39154792051.86E+080.01398174293.570889318112.44016873942.83E+080.02101831515.368005795618.70091507792.03E+080.01496637733.822361593413.31624112885.13E+070.00378303390.96617391733.36593086241.19E+080.00888540422.26930185067.90573311766.51E+080.049757033612.707776225444.2710110738149316925028.704508700471.61171251021.63E+085.74E-0214.65891848392.00E+080.110605573828.2482853259CO255/600/2400.740.00740.020800646735.575816987

trc15p171800.41891200951.74E+080.01305822553.117176221512.03171359472.69E+080.01998151334.769859273318.4107591571.95E+080.01442174973.442667992813.28805057775.15E+070.00380241630.90768854093.50350695051.11E+080.00829131241.97924916037.63952928456.41E+080.048976501411.691357675645.1264404356144164838725.907998864464.50081396731.59E+085.46E-0213.03703054951.97E+080.107056250625.5557845534selec35.729072328337.499065029236.803677243934.2557261186650/600/2400.710.00710.020800646734.1335541362

trc16p171800.38430448521.54E+080.01160956713.020929386612.11399701022.40E+080.01786360244.648294020318.63976699161.76E+080.01298061923.377691319613.5446206484.91E+070.00362213840.94251786083.77951851441.01E+080.00753957841.96187625627.86716935785.53E+080.042220469210.986202566544.054927478127340500624.9375114158.43753081291.42E+084.38E-0211.38976894131.73E+080.084970684222.110250461591000/600/240 cb0.630.00630.020973733130.0375711129

reaction time (400C)00000000000000-2.98E-0300.02060101000/600/240 ce0.60.0060.020973733128.6072105837

trc03p1950.45512918618.05E+050.00006053390.01330037198.16E+050.00006071970.01334119375.86E+050.00004327010.00950721223.52E+050.00002597060.00570619490.00E+00000.00E+00000.041854972613.5694912219.72E+072.12E-024.66135561791.07E+080.04035303098.8662806304111000/600/240 xy0.790.00790.021066558637.5001923564

trc01p19100.45231229461.66E+070.0012470680.27570951776.66E+060.00049519160.10948001175.66E+060.00041791920.09239616131.81E+060.00013372690.02956517041.03E+060.00007698880.01702116040.00E+00000.524172021421.24382187271.27E+083.53E-027.8144844191.38E+080.058371649912.9051654324

trc02p19300.4760546663.45E+070.00259275760.54463442184.51E+070.00335477290.70470328284.30E+070.00317213920.66633926311.22E+070.00090150040.18936910091.14E+070.00084844720.17822474610.00E+00002.283270814634.72266955931.70E+086.23E-0213.07767803241.81E+080.092172374919.3617207123zsm100.11.30.0130.040232029832.3125630904

trc06p19600.49496808041.38E+080.01035541142.09213720721.07E+080.00795184671.60653727688.37E+070.00617590411.24773786252.48E+070.00182890190.36949896542.84E+070.00211970030.4282498933.80E+070.00290067450.58603262826.330193833150.84155513362.08E+089.09E-0218.37205767622.18E+080.129381209426.1393036242zsm200.23.450.03450.079195899243.5628616367

trc04p19900.49939462421.22E+080.00921288661.84481092871.54E+080.01147505572.29779320571.23E+080.00904456841.81110648113.03E+070.00223535370.44761269773.39E+070.00253182080.50697799227.83E+070.00598005911.19746165238.105762957649.33982204872.09E+089.15E-0218.32036338462.04E+080.114429764622.9136957064zsm300.350.050.119959014141.6809027509

trc05p191800.43098440178.55E+070.00643123281.49221938571.25E+080.00932445182.16352420471307458190.00964678222.238313525648530230.00478503241.1102565239273614370.00204068160.4734931545979368760.00748018351.73560423789.213411031545.67060694081720086576.34E-0214.70512257191828344160.093748043121.7520733374zsm400.47.010.07010.159824578943.8605879409

-2.98E-030.0206

percentage glucose000000-2.98E-030.0206total

trc12p075000000-2.98E-030.0206

trc13p075000000-2.98E-030.0206

trc08p0750.15794057877.46E+070.0056143433.554718510711.83671042781.27E+080.00944631755.980931288719.91565620138.35E+070.00615959123.899942120812.98625627581.90E+070.0014047040.88938763462.96153516985.01E+070.0037373092.36627536017.87936264032.76E+080.02106935113.34004924244.420479284963012650030.031304156960.33687803247.68E+071.33E-028.3906336189.45E+070.034612583521.91494025751825071511957699638.11E-0234.28496522472502044390.168741707671.3741339455643520969Compositionheating ratereaction temperaturereaction timearomatic yieldoxygenate yieldCO2 yieldCO yieldcoke yieldtotal carbonunidentified

trc09p07100.33528950451.27E+080.01028231273.066696845611.28493279832.07E+080.01664503014.964375511618.26807371431.43E+080.01137594183.392871428912.4852008523.87E+070.00308260080.9193848083.38318271979.41E+070.00758087572.26099402268.3200808195.11E+080.042148647912.570822334146.2585290967112066012927.175144950859.81475272671.31E+083.75E-0211.19475335241.57E+080.071902346121.44485442351900104531813201547.01E-0228.95920859572469513450.164526042668.00794509546315115375% glucose100060024031.4

P-xylene selectivity can be enhanced by modifying the catalyst

Overall p-Xylene carbon selectivity (left axis) and xylenes distribution (right axis) obtained from the conversion of 2MF + propylene over various ZSM-5 catalysts (*modified catalyst)

Y. Cheng, Z. Wang, C. Gilbert, W. Fan, and G. W. Huber, Production of p-Xylene from Biomass by Catalytic Fast Pyrolysis Using ZSM-5 Catalyst with Reduced Pore-opening Size, Angew. Chem. Int. Edit, (2012), 51, 11097-11100.

• Modification of ZSM5 catalyst increases p-xylene distribution from 33% to 95%.

• Aromatic selectivity can be tuned to produce targeted aromatics.

• Ratio of p-xylene, m-xylene, and o-xylene can be adjusted.

Pilot Plant being built for CFP Technology

www.anellotech.com

INTEGRATED CATALYTIC PROCESS TO PRODUCE RENEWABLE DISTILLATE FUELS FROM BIOMASS

32CBE 562 Lecture 1

Convert 80% carbon present in the biomass to C8+ alkanes using stable, catalytic processes with residence times below 1 hour

Project Goal and Key Technical Challenges

33

COH2

Project Goal

Gasification

Hydrolysis Catalytic Conversion

Fischer-Tropsch Synthesis

Breakdown of Biomass Polymers C-C Bond Formation

Cellulose

Hemicellulose

Sugars

C8+ Alkanes1

Syn-gas

+Lignin

2Chevron, Typical carbon number distribution- No. 2-D Diesel Fuel

Reaction Chemistry

Cellulose

Hemicellulose

Petroleum derived feedstock made from biomass

•Red and Blue process optimized for tridecane production.•Red process optimized for production of a petroleum refinery feedstock: mixture of C7-C30 mostly cyclic alkanes.•Red is a high quality petroleum feedstock similar to heavy cycle oil (HCO) or light cycle oil (LCO).

H. Olcay, A. V. Subrahmanyam, R. Xing, J. Lajoie, J. A. Dumesic, G. W. Huber; Production of Renewable Petroleum Refinery Diesel and Jet Fuel Feedstocks from Hemicellulose Sugar Streams; Energy and Environmental Science, (2013) 6 (1), 205-216.

35

Sankey Diagram for Carbon Yields and Capital Costs

H2

Hemicellulose

C5 Humins

Formic AcidCO2

Acetone

HMF

Acetic Acid

Lignin + C6 Humins

Maple Wood

Pretreatment

Furfural Purification

Aldol Condensation Dimer

Hydrogenation

Hydrodeoxygenation

Cellulose Deconstruction

LA Hydrogenation DecarboxylationOligomerization

AlkeneHydrogenation

GVL Purification

LA Extraction

Biphasic Dehydration

Cellulose + Lignin

Dehydrated Products

Dehydrated Products

LA GVL GVL Butene C8+ Oligomers Hydrocarbons

Furfural Dimer H-Dimer Hydrocarbons

Process Heat (98 MW)

Combustor + Boiler

H2

H2H2

0-25% carbon

26-50% carbon

51-75% carbon

76-100% carbon

Height of the box corresponds to estimated fixed cost of the unit

Reactor System

Separation system

Boiler and Combustor

Height of each stream corresponds to amount of carbon in the stream

Darkness of each stream represents the carbon concentration as shown below:

36

J Bond, A Upadhye, et al.; Production of renewable jet fuel range alkanes and commodity chemicals from integrated catalytic processing of biomass Energy and Environmental Science (2014) 7, 1657-1660.

Conclusions We can convert biomass into all the same fuels and chemicals that

are produced from petroleum

We do a poor job of predicting the economics of pioneer process technologies

Pyrolysis can produce a low quality liquid fuel called a bio-oil or pyrolysis oil

Pyrolysis oil can undergo hydrotreating

Catalytic Fast Pyrolysis can produce aromatics directly from biomass

Distillate Range Fuels can be produced from biomass

Methane conversion can be understood with theoretical model

37

38

The Challenges and Opportunities of Designing Pioneer Catalytic Technologies for the Production of Sustainable Fuels and Chemicals from BiomassThe discovery of inexpensive oil revolutionized our worldCellulosic Biofuels are best technology option for decreasing petroleum usage and greenhouse gas emissionsThe biomass conversion challengeIntegrated Biorefinery Program2nd Generation Biofuel Companies have StruggledSlide Number 7KiORChallenges with Pioneer Process PlantsConventional View of Estimating Project CostsActual Views of Estimating Project Costs of Pioneer PlantsEstimating Plant PerformanceCorrect Way to Estimate Economics for Pioneer Process PlantsNew Technologies in the Petrochemical Area do Make MoneyPyrolysis is Cheapest Biomass Conversion TechnologyENSYN Commercial Fast Pyrolysis PlantBio-oil: Characterization Bio-oil CompositionBio-oil undergoes phase separation when heatedHydrodeoxygenation (HDO) of BiomassLiquid Products produced from HDO of pyrolysis oilsCurrent Technology for HydrotreatingRenewable Aromatics from Catalytic Fast Pyrolysis (CFP) of BiomassBlock Flow Diagram for Catalytic Fast PyrolysisReactors for Catalytic Fast PyrolysisSlide Number 26CFP involves reactions in solid biomass, gas phase and inside catalystAromatic Yield Increases with Heating RateP-xylene selectivity can be enhanced by modifying the catalystPilot Plant being built for CFP TechnologyIntegrated Catalytic Process to Produce Renewable Distillate Fuels from BiomassSlide Number 32Project Goal and Key Technical ChallengesReaction ChemistryPetroleum derived feedstock made from biomassSankey Diagram for Carbon Yields and Capital CostsConclusionsSlide Number 38

the challenges and opportunities of designing …...the challenges and opportunities of designing...

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