Tuesday 14 June 2016, 14:00 Session 18-4 J. Hartvigsen, L. Frost, S. Elangovan, J. Elwell

P. Dimick (IntraMicron)

NETL Award DE-FE0023863, PM Anthony Zinn

Conversion of Coal and Biomass to Liquid Hydrocarbons Using Gasification and a Hybrid

Fischer Tropsch Catalyst

CBTL Process-Program Connectivity

Coal-Biomass Gasifier

Technology development

System Demonstration Scope

Project Goals and Objectives •  Jet fuel (Jet-A or JP-8 MIL-DTL-83133) •  Capable eventually of 1000’s of gallons of jet fuel •  Team led by Ceramatec

–  Team members: •  Ceramatec – Project lead and FT •  IntraMicron – Sulfur removal and catalyst support •  Chevron – Hybrid catalyst developer •  EERC – Gasifier partner

–  Demonstrate using 2 BPD pilot –  Provide fuel for evaluation by USAF –  Plant will produce over 1000 gallons per month –  Provide design basis for 100 BPD module

Ceramatec FT System Strategy •  Scale, Scope & Cost

–  Small 0.1% to 10% of “World Scale” GTL

–  Product syncrude with minimal upgrading

–  CAPEX << $100k/bbl/day •  Shop fabrication

–  Reduce cost versus site built plants –  Transportability to site (size limits on

road transport) –  Quality control and mass production vs.

traditional economies of scale

•  Catalyst loading and transport –  Catalyst servicing done in shop –  Replaceable reactor elements –  Catalyst reduced and ready to

operate •  Minimum infrastructure required •  Take advantage of a variety of small

distributed resources –  Biomass, biogas, coal-biomass

blend –  Stranded gas, associated gas –  CO2 co-electrolysis as intermittent

renewable energy storage

Small FT with Large Reactor Tubes?

MFEC Reactor Temperature Profile

0 0.5 1 1.5 2 2.5 3 3.5 4

0

200

400

600

800

1000

1200

0 0.05 0.1 0.15 0.2 0.25 0.3

Re in MFEC

Inis

de W

all H

eat T

rans

fer

Coe

ffici

ent

(W/m

2-kK

)

Face Velocity (m/s)

Cu_MFEC Cu_Packed Bed Al2O3_Packed Bed

Steam Condensing: 1000-3000 W/m2-K

Force Air Convection:10-200 W/m2-K

IntraMicron Fischer Tropsch Synthesis MFEC MFEC-Based GTLby Fischer-Tropsch

Synthesis

Natural Gas Fuel (Gasoline, Kerosene, Diesel)Traditional FTS Issues

•  Lack of efficient heat transfer•  Highly exothermic reaction•  Prone to hot spots, runaway, and high temperature

catalyst deactivation•  Selectivity is temperature dependent•  Low per pass conversions necessary to mitigate

severe temperature rises •  High capital plant costs

MFEC Benefits•  High heat transfer rates•  High mass transfer rates •  High volumetric reaction rates•  Near isothermal temperature profiles •  Easy to fabricate and operate•  Robust

0

10

20

30

40

50

0 0.1 0.2 0.3

EffectiveRadialThe

rmalCon

ductivity

W/m

-K

FaceVelocity(m/s)

CuMFECCatalystBed

TypicalPackedCatalystBed(0.17-0.21w/m-K)

50- to 200x bed thermal conductivity

IntraMicron Microfibrous Entrapped Catalyst (MFEC)

MFEC

MFECs consist of catalyst particles immobilized in media made of sinter-locked networks of micron-sized fibers. The fibers range from 2 to 25 µm, and the entrapped particles typically

range from 40 to 300 µm. The micron-sized fibers dominate the flow pattern, especially at low Reynolds numbers, significantly enhancing mass and heat transfer characteristics.

Microfibrous Matrix(1)  Uniform velocity

profile (2)  No channeling (3)  High thermal

conductivity (M)(4)  Better wall contacting (5)  Fast heat transfer (M)(6)  Near isothermal

temperature profile (M)

(M) Metal Microfibrous media only

Small Catalyst/ Adsorbent Particulates

(1)  High external surface area

(2)  Reduced intraparticle diffusion resistance

(3)  Fast mass transfer(4)  Improved selectivity

to large molecules

Microfibrous Entrapment(1)  Frozen fluidized bed(2)  Uniform particle

distribution(3)  Random reactor

orientation(4)  No further particle –

product separation Typical Packed

BedMFEC Bed

IntraMicron MFEC Preparation

Preformed MFM Sheets

ready to accept catalyst

Disc Formation Catalyst Entrapment

MFEC Preparation using wet lay techniques

MFM SinteringMFEC Assembled onto

Tree for Reactor Loading

Barrier Layer (bottom)

Catalyst Layer(top)

The composition of MFEC is tailored to provide the appropriate balance of heat and mass transfer for the target reaction. This included the fiber blend and entrapped catalyst size. MFEC typically contains 5 – 25 volume percent fibers and 5 to 30 volume percent catalyst.

Hot spots near center

Cold spots near wall

Parabolic fin

Ceramatec Alternative Thermal Structure •  Geometric optimization FE thermal model

–  Higher average temperature •  Production and thermal risk

–  Lower average temperature •  Production and thermal risk

Thickness Position

WidthThickness

Aluminum extrusion reactor insertfor thermal management

IntraMicron Desulfurization Technology Suite (IM-DTS) IntraMicron’s Scalable Desulfurization Technology Suite is a synergistic combination of an oxidative sulfur removal (OSR) Catalyst, a desulfurization sorbent (regenerable or disposable), and a bed life sensor that enables efficient sulfur removal from distributed energy resources.

OSR Reactor H2S + 0.5 O2 à H2O + S

RSH + 0.5 O2 à R-OH +S

Adsorbent Bed Regenerable

or Disposable

S-laden Gas Low-S Gas (< 5ppm)

S-free Gas (< 0.1 ppm)

Sulfur Condensation

Elemental Sulfur

Bed Life Sensor

Optical Signal

Oxidizer (Typically Air)

Patent Pending

Patent Pending Patents Issued and Pending

•  OSR converts majority of H2S to elemental sulfur without significant SO2 production

•  BLS optimizes adsorbent utilization to minimize waste

•  Process easily accommodates varying sulfur levels and outlet thresholds

•  Up to 75% cost reduction compared to current state of the art technologies

Ceramatec 100mm NPS FT Pre-Pilot Facility •  Plasma reformer •  Syngas compression •  Syngas drying •  Syngas storage •  Modular reactor •  Validate advanced FT

cooling structures in 100mm NPS reactor

Fresh SyngasF

Coriolis-11

FCV-11

PV-11

Cool DownTank A

HX-2

RC-31

PV-12

Cool DownTank B

HX-1

FCoriolis-12

FCV-12

Condenser

P-22

PRV-21

Recycle Syngas

E-13

Heated Tank A Heated Tank B

PV-14

PV-13

PV-15

ProductStorage Tank

Cool to 130 deg C

PRV-11

Water Vapor Drum

FCV-13

FCo

riolis

-13

PRV-12Pulse dampers

HB-11

PV-16

PP P

P

PRV-13BPR-11PRV-14

BPR-12

SPR-11

To flare To flare

½”

P-21 YS-21Drain

DFM-31 GV-31

P

GV-22

H2/N2 Line

Ht-21

Ht-31

PT-21 BPR-21

PT-13

DFM-23

PG-11PG-12 PG-14

PG-13

LS-11

RF-31P-31

Coolant Reservoir

CV-21CV-22

3/8"

Product

Finned Tubes

Finned Tubes

Fan

RecycleSyngas

Cold Trap

Hot Trap

Flare line

Coolant loop

Therminol Tank

Therminol Pump

P

To flare

Syngas From Ceramatec Plasma Reformer •  Nominal 0.7 barg operation •  Capacity for 2 BPD pre-pilot plant •  Demonstrating

–  80kW 6 barg steam generator –  Industrial pneumatic control valves –  80mm NPS, 1 barg, 3.4k m3/d (120 MCFD) capacity gas line

Syngas Compressor for 2 bbl/day Commissioning

Ceramatec Syngas Storage Facility 2 x 2000 liter, 55 bar storage tanks

10-14 bar Intermediate storage

Compressor

Single Tube 100mm NPS FT Reactor Test Bed System

FT Product Collection

Draining Product

Product Collection Scales, kg

Wax Free Product Hybrid Co as Trilobe, w/Fin

Wax Free Product Hybrid Co in MFEC

MFEC Chevron Hybrid Co Catalyst Product Distribution

0"

5"

10"

15"

20"

25"

0" 5" 10" 15" 20" 25" 30" 35"

Weight%

(

Carbon(Chain(Length(

((

033115"

040215"

040315"

040515"

051015"

051115"

051215"

Ceramatec 100mm FT Runs Q1-Q2 2015 •  FT operations March 19 to June 01 2015

•  74 Calendar Days •  54 Operating Days (nominal 1296 hours) •  2 catalyst regeneration cycles

•  Product collection –  45 sample collection periods –  375 kg (136 gal) FT oil collected and stored

•  Carbon number distribution by SimDis GC –  920 kg FT produced water

•  Treated, tested, discharged •  Production rate

–  Varying syngas composition, pressure, reactor temperature •  19.3 liters/day peak rate •  14.7 liters/day sustained over 12 day period •  9.6 liters/day average including startup

Selectivity & Productivity Extrudate-Fin •  23 Dec 2014

–  1.25 kg hybrid Co trilobe –  240°C reactor –  20 bar exit –  3.22 SCFM syngas

•  35% N2, 40% H2, 19% CO –  8 SCFM recycle –  92% H2 conversion –  86% CO conversion –  23.3% CH4 selectivity –  3.4% CO2 selectivity –  0.197 gC5+/g-cat/hr

•  16 Oct 2014 –  1.25 kg hybrid Co trilobe –  250°C reactor –  20 bar exit –  4.59 SCFM syngas

•  52% N2, 29% H2, 14% CO

–  10 SCFM recycle –  79% H2 conversion –  71% CO conversion –  32.5% CH4 selectivity –  2.6% CO2 selectivity –  0.091 gC5+/g-cat/hr

Selectivity & Productivity MFEC •  05 April 2015

–  2kg hybrid Co in MFEC –  240°C reactor –  20 bar exit –  5.88 SCFM syngas

•  26% N2, 45% H2, 22% CO –  10 SCFM recycle –  78% H2 conversion –  78% CO conversion –  18.8% CH4 selectivity –  0% CO2 selectivity –  0.359 gC5+/g-cat/hr

•  12 May 2015 –  2kg hybrid Co in MFEC –  220°C reactor –  20 bar exit –  4.64 SCFM syngas

•  23% N2, 48% H2, 24% CO –  8 SCFM recycle –  52% H2 conversion –  51% CO conversion –  15.3% CH4 selectivity –  0% CO2 selectivity –  0.185 gC5+/g-cat/hr

Ceramatec Reactor Loading at IntraMicron

Ceramatec 100mm NPS, 7-tube, 2 bbl/day FT reactor

Reactor tube sheet FunnelMFEC

Rollers

Loading a Reactor Tube With Intramicron MFEC

Ceramatec 2 bbl/d 100mm NPS FT Plant Layout

Construction Planned Summer 2016, Commissioning Fall 2016

Status & Summary •  Ceramatec 100mm NPS, FT reactor demonstrated

–  Tested with various catalysts (conventional Co & Fe, hybrid Co) –  Heat removal with aluminum fin insert and with Cu MFEC

•  Fabricating 2 BPD – 100mm NPS, 7-tube reactor –  Initial testing will use reformed natural gas –  Coal / biomas testing planned at EERC

•  Designs and costing on larger facilities –  1 MMSCFD (28.3k m3/day) plasma reformers for GTL (Built for NH3 plant) –  10 BPD pilot designed and costed –  100 BPD FT reactor module planned –  Costing on ~2000 BPD GTL plant performed by commercial partner

Energy Storage Via Electrolytic Synfuel

Gen IV Nuclear

Wind CO2 Electrolysis to FT Synfuels

Advanced Concentrator PV

Acknowledgements / Contact

•  The 2 BPD CTL / BTL system is being funded by the USAF with management by US DOE NETL

•  The Laboratory GTL system was partially funded by State of Wyoming, Office of Naval Research, US Department of Energy, Ceramatec, and other commercial entities

•  Some of the carbon distribution data was from catalysts provided by third parties

For further information contact: Lyman Frost lfrost@ceramatec.com 801 956 – 1039 (office) 801 910 – 1346 (cell)