2009 DOE Biomass Synthesis Gas

to Liquid Fuels EvaluationDOE Contract No. FG36 - 08GO18040

4/15/2009

Thermochemical Platform Review

Dennis Leppin, P.E.

Gas Technology Institute

This presentation does not contain any proprietary, confidential, or otherwise restricted information

2

Overview

• Start: July 1, 2008 (at risk)

• End: September 2009

• Percent Complete - 35%

• Barriers addressed– M 6.11.4 C Validate cost-effective gas

cleanup performance

• Total project funding (Phase I)

– DOE share: $ 768K

– GTI share: $ 347K

• Funding received in FY08 -

$600K

• Funding for FY09 - $168K?

• Balance of Funding ~$1.2 MM

Timeline

Budget

Barriers

• UPM/Carbona/Andritz – cofunding of gasification testing under separate program – allow use of their syngasin cleanup program, provide tar reformer technology knowhow

• Velocys – provides FT Test Skid (Phase II) (Cancelled)

Stage• Stage 3 – Development

Partners

DOE BTL Project Schedule: 2009*

March April May June July August September

Week Week Week Week Week Week Week

1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4

DOE BTL

Phase No.

Carbona

Test No.

Schedule for

Carbona

Tests

Total

Weekly

Run Time

Total

Phase

Run Time

1 3DOE BTL

Test #1100

1 4DOE BTL

Test #2200 300

2 5DOE BTL

Test #3120

2 6DOE BTL

Test #4120

2 7DOE BTL

Test #5120

2 8DOE BTL

Test #6140 500

DOE BTL Phase I: Validation of Syngas Cleanup

DOE BTL Phase II: Validate Liquid Fuel Production from Clean

Synthesis Gas using a proprietary FT Technology

•100hrs

•200hrs

•120hrs

•120hrs

•120hrs

•140hrs

* One test eliminated in current program – this was our working schedule

4

Goals and Objectives

• To validate syngas (from wood gasification at a scale equiv. to 20 kg/hr wood) cleanup processing for 100 continuous and 300 total hrs., to stringent specs. suitable for FT . Obtain information to allow the specific gas cleanup approach to be scaled-up and commercialized in the future and to lessen risk of large-scale wood gasification projects

• Forest residues are a significant resource. Steam/oxygen gasification is a promising approach to converting these resources to syngas. An existing industrial test program with UPM-Kymmene Group, Carbona and Andritz is scheduled to operate several tests at GTI’s Flex-Fuel Test Facility in 2009. This project was to piggyback on that effort and process ~10% of the gas through a novel, high-efficiency cleanup approach.

• In Phase II the deeply cleaned syngas would be fed to a participating FT test unit

5

Approach

• Using new gas cleanup techniques combined with some

existing steps, build a slipstream test unit to minimize gas

quenching, cooling and heating cycles to achieve higher

efficiency and lower cost– Tar Reformer directly downstream of gasifier to eliminate tar repercussions on

downstream processes and catalysts and eliminate need for deep scrubbing

and cooling - advanced catalysts

– Remove S and halides using a (simulated) filter-reactor to simplify downstream

gas handling (S-free)

– Advanced physical solvent for CO2 removal

• Piggyback on existing test program– Gasification tests (no costs to this program)

– Analytical Measurements (common stream analyses available), use major

instruments already available

– Work within schedule constraints - UPM wood gasification project on inflexible

schedule, late start getting under contract, needed to do design engineering in

parallel with equipment purchasing

6

Approach (cont’d.)

• Decision Point– Phase 1, review after 100/300 hr operations w/o FT unit

– Meet gas quality criteria appropriate to FT unit provided by FT vendor (details

follow)

– Only then can proceed into Phase II

7

Technical Merits vs. SOA

• Advanced tar reforming catalysts – high yields at moderate

temperatures

• Eliminate S during hot stage – minimize problems in

downstream separations

• Filter Reactor effective way to use absorbents (proven in coal

gasification program)

• No need for complex selective acid gas removal process or

additional S recovery steps

• Use advanced solvent (Morphysorb) with order of magnitude

lower H2 and CO solubility for CO2 removal (only)

• Scheme minimizes cool down/reheat steps

8

Technical Accomplishments/ Progress/Results

• This is first review opportunity for this project

• Process Design efforts completed– Obtained gasification data from earlier testing, laboratory tar reformer advanced

catalyst screening results

– Simulated entire process in HYSYS

– Selected specific catalysts and processes• Screened tar reforming catalysts in bench-scale unit

– Initial design approach modified for higher efficiency

– Mechanical design completed, preliminary equipment layouts developed

– Analytical techniques and sampling plans developed

– Major equipment ordered

– HAZOP review performed

– Developed more accurate estimate of cost to complete based on detailed process and mechanical design and vendor estimates of equipment and fabrication costs

9

Technical Accomplishments/ Progress/Results

• Gas Cleanup System approach appears feasible, post-detailed engineering, in all respects to meet the objectives and to translate to a commercial project– No “show stoppers”

– No developmental catalysts/absorbents* or solvents**

– Minimize precious metal catalysts/sorbents

– Reasonable operating conditions

– No requirement for exotic metallurgy

– No specialty mechanical components

– No novel process equipment***

*Tar reforming catalysts planned here have only been tested in the laboratory but are being offered commercially

**Morphysorb commercial for natural gas treating, but can be replaced w/o any other changes by Selexol here if needed

***Tar reformer not conventional process equipment but similar equipment has been used elsewhere

10

Syngas Cleanup Process Scheme: High-

Pressure Option

Partners

Schematic of the GTI DOE Bio-Syngas Cleanup

Pilot Unit

11

Syngas Cleanup Process

Scheme: Low-Pressure Option

12

Photos of Filter-reactor setup at GTI Flex-Fuel

• Successfully tested in Gasification program

• Will not be used per se in slipstream project – sorbents will be used in batch fixed beds

•Expensive to scale-down

13

HYSYS Simulation of the DOE BTL Syngas

Cleanup Project

14

15

Preferred Maximum Contaminant Levels for

a Typical FT Process

Contaminant Max. Level Units

Inert level (CO2+N2+CH4) 15 vol.%

Total sulfur 20 ppb

Total halogens as Cl 20 ppb

Total ammonia + HCN 50 ppb

Total oxygen as O2 20 ppm

Total NO 100 ppb

Feed + product water 0.2 mol%

Total iron + nickel 30 ppb

Total aromatic hydrocarbons 20 ppb

16

Tar Reforming

• Advanced tar reforming catalysts – high yields at moderate temperatures

– Very positive results:• F‐35 noble metal catalyst was determined to be more effective for reforming both tars

and methane than F‐37 Ni‐based catalyst

• Both F‐35 and F‐37 catalysts had slightly higher tar reforming capability than RKS‐3

catalyst, and achieved > 93% tar reforming even at the lower temperature of 850°C

• High methane reforming activity

Catalysts for Bench-scale Unit

Catalysts for Slipstream Unit

17

Designed Slipstream Tar Reformer Vessel

• Tar Reformer Design Criteria:– Pressure Vessel MAWP 410 psig

– Two Zone Electric Furnaces• Preheat Syngas to 1500 °F

• Reforming Catalyst (1500 to 1650 °F)

– Catalytically Reform 1000 ppmv Tars using steam

– Gas Flows to 1,500 scfh

– Removable Reforming Monolith Catalyst

– 98%+ Conversion Target of Tars

• ASME Coded Vessel– Pressure Balanced Shell

– Water Cooled Product Gas for 800 °F• Ability to analyze product gas for tars

• Maintain Class I, Div II, Group C Rating

– Extreme temperature Conditions Requires:• Detailed Engineering for Thermal Expansion

• Contains High Temperatures

• Contains Syngas to Heated zones

• Install two furnace elements

18

Designed Process Vessels

• Process Vessel Design Criteria:– Low Pressure Vessels (Shift, Sulfur

capture, and Water Knockout)

• MAWP over 200 psig

• Gas Flows up to 4,000 scfh

• Sulfur Capture Four day capacity

– High-Pressure Vessels (Morphysorb Tower, Dryer Unit, Carbon Bed, Final Dryer)

• MAWP over 1,200 psig

• Gas Flows up to 4,000 scfh

– Metal Carbonyl Vessel MAWP 600 psig

– Gas Flows to 4,000scfh

– ASME Coded for Class I, Div II, Group C Rating

• Vessel Materials Purchased

• Vessel Fabrication and Assembly near Completion

• Morphysorb Process design by UHDE GmbH – 80%+ CO2 Removal at 150 psig Pressure

19

Process Vessels on Skid

20

Building Utilities for Biomass to Liquids Project

• Determined Utility Requirements from Process Flow Diagrams– Medium-Pressure Nitrogen, Instrument Air,

High-Pressure Steam, Flare Line, Cooling Water and Drainage

– Electrical Loads for Tar Reformer Electric Furnace, Process Gas Compressors, Morphysorb Heater and general equipment

– Data System, Safety Alarms and Control

– Process Gas Piping

• Pipe sizing and Insulation

• Pipe Location

– Structural Load Calculations and Design Completed for Tar Reformer

– Area Monitors

• Building Engineering Study to determine Utility requirements• Electrical, steam ,nitrogen, sewer and

flare impacts, permit impacts

• Determined process Layout for Installation

• Designed two Skids to Support Process Vessels and Equipment

Flex-Fuel Test Facility and

Advanced Gasification Test Facility

DOE Slipstream

Bay 3, ground level

UPM Carbona BTL Project Gas

Cleanup Systems:

•Bay 1

Flex-Fuel Gasification

Bldg

PWR Advanced Compact Gasifier

System: Bay 2

Acid Gas Treatment Pilot Plant

21

22

AGTF and FFTF BuildingsBack View

23

Tar Reformer Location and Syngas Piping

• Tar Reformer Location– Positioned just after Hot Gas Filter

• No fines in Syngas to plug reforming catalyst

• Syngas Temperature above 800 °F

• Shortest distance to prevent Syngastemperature dropping below 800 °F

• Deliver Hot Syngas to Bay-3– Limited space in Bay-1 for cleanup

system

24

Velocys FT Unit Location and Syngas Piping

25

Velocys FT Unit Location and Syngas Piping

26

Biomass Syngas Gas Cleaning Requirements

ImpurityMax. allowable

concentration

Estimated concentration based

on previous Carbona-GTI

tests

Estimated concentration based on

100% release from solid fuel

Percent removal

required

Total sulfurs < 60 ppbv about 360,000 ppbv about 400,000 ppbv 99.995%

H2S not stated 151 ppmv about 331 ppmv

COS not stated not measured, usually

0.1 H2S concentration

about 15 ppmv

Total halides < 10 ppbv at least 49,000 ppbv about 123,000 ppbv 99.98%

HCl not stated 49 ppmv about 117 ppmv

HF not stated not measured about 6 ppmv

Alkali metals <10 ppbv not measured about 2,000,000 ppbv 98.9%

Na not measured about 200,000 ppbv

K not measured about 1,800,000 ppbv

NH3 <10 ppbv 2,950,000 ppbv

HCN <10 ppbv not measured

Metal carbonyls <100 ppbv not measured 20,000 ppbv** 99.5%

Hg <1 ppbv not measured 0.25 ppbv* No cleaning necessary

As <1 ppbv not measured 10 ppbv* 90%

*Based on literature estimate for alfalfa gasification

•

27

Sour Shift

Chloride Sorbent

Sulfur Sorbent

Sulfur Sorbent

Metal Carbonyl Sorbent

Mercury Sorbent

Catalysts and Sorbents Selected

•Determined for each:

Supplier, size, active temperature range, service temperature, capacity (wt%), days to breakthrough

28

Completed Process Flow DiagramsTar Reformer Unit

29

Completed Process Flow DiagramsAdjust Hydrogen to Carbon Monoxide Ratio and Sulfur Capture Section

30

Completed Process Flow DiagramsSteam Condensing/Removal, Primary Compression and Drying System

31

Completed Process Flow DiagramsMorphysorb System

32

Completed Process Flow DiagramsMercury Removal, Final Dryer, Metal Carbonyl,

and Gas Storage System

33

Completed Analytical PlanMercury Removal, Final Dryer, Metal Carbonyl,

and Gas Storage System

34

Syngas Analysis

Hot, High-pressure gas

500 micron

orifice

E

E

T/C

6-foot internal

heater

12-foot internal

heaters

Current proposed design

Ba

tch H

2O

Dump

Separate Dump

T/C

Dumps possibly to an

entry to the flare line

Batch Tar

Batch

NH3/HClBatch H2O

To

jar

Dry

Test

Meter

Dessicant

Columns

Dry

Test

Meter

Dry

Test

Meter

Impingers in bath

Impingers

Gas

Cyl

inder

CV 2

psig

E

PI

T/CT/C

Key

Check valve

Internal heater (s)

Orifice: depressurizes ;

sized for flow

Metering valve to 900°F

Swagelok SS-4BW

Ball valve

E Electrical box

T/C Thermocouple

Pressure IndicatorPI

• Sample Stream Monitored by the FTIR is Diluted by a Factor of 10-15 with Dry Nitrogen to keep tars in the gas phase– Measures online: H2O, CO, CO2, CH4,

C2H6, C10H8, C6H6, and NH3

• Gas Grab Samples– Majors (% Level Components)

• Helium, Hydrogen, CO2, O2/Ar, Nitrogen, CO, Methane, Ethane, Ethyne, Propane, Propene, Hexanes, Ammonia

– Sulfur (ppmv Level Components)

• H2S, SO2, COS, CS2, MeSH, EtSH, DMS, DMDS, DMTS, Thiophene, C1-Thiophenes Gas Samples

• Micro-GC for N2, H2, CO, CO2, CH4, H2S

• GTI Developed Gas Sample Probe for online hot gas stream sampling

35

Syngas Tar Analysis by European Tar Protocol

36

Completed HAZOP Review for Process Flow Diagrams

NodeDeviati

onCause Consequence

Risk Matrix

SafeguardRecommendati

on

Respo

nsibilit

y

StatusS F RR

1. SSTR,

Reformer V-

120

1.

Compo

sition

1. Too much

Tar from

gasifier

1. Equipment

fouling

(3)

Se

rio

us

(2)

Sel

do

m

6 1. PDAH-121 18. Add Low

Temperature

Alarm to TI-

121 & TI-122

2. TI-121 & TI-

122

3. Upstream

Gas

Composition

3.

Low/N

o Flow

1. GV-102

Failure

1. Loss of

Operations

(3)

Se

rio

us

(2)

Sel

do

m

6 1. Pre startup

checklist

19. Review

Checklist

2. Residual

unpurged gas;

potential

release to

atmosphere

and personnel

contact

(4)

Ma

jor

(2)

Sel

do

m

8 2. PAL-102 20. Verify

maintenance

procedures;

Open BV-101

3. Nitrogen

purge BV- 104

4.

Maintenance

procedures

2. Loss of

Nitrogen

Purge

1. Equipment

Damage

(2)

Mi

nor

(3)

Oc

ca

sio

nal

6 1. PDT-120 21. Consider

Low Alarm on

PDT-120

2. Loss of

Operations

(3)

Se

rio

us

(3)

Oc

ca

sio

nal

9 22. Consider

adding manual

valves to

checklist

3. catalyst

decrepitating

1. Loss of

Operations

(3)

Se

rio

us

(3)

Oc

ca

sio

nal

9 1. PDT-121 42. Verify

startup

procedure vs

catalyst

properties

4. High

Tempe

rature

1. TIC-124 &

TIC-125

Failure

1. Loss of

Operations

(3)

Se

rio

us

(2)

Sel

do

m

6 1. TAH-124 &

TAH-125

23. Consider

adding

separate High

Temperature

Alarm(s) for

funace controls

2. Location of

Reformer

Prevents

incidental

contact

24. Examine

Alarm Mode

Function for

TAH-124 &

TAH-125 (If TC

fails, Alarms

still active)

5. Low

Tempe

rature

1. TIC-124 &

TIC-125

Failure

1. Loss of

Operations

(3)

Se

rio

us

(2) 6 1. TI-124 & TI-

125

25. Consider

adding TAL(s)

26. Examine

Alarms and

Operating

modes TIC-124

& TIC-125

• Hazop Review Includes– Identifying 9 NODES

• Tar Reformer

• Tar Reformer Indirect Cooler

• Syngas Heat Exchanger

• Sour Shift Reactor and Sulfur Sorbent

• Steam Condensation and water Knockout

• Drying System

• Morphysorb system

• Gas Polishing

• Data Monitoring/ Safety Alarms/ Control

• Identifying Safeguards

• Determine Risk Management

• Recommend additional equipment or procedures

• Used outside facilitator

37

Cost Assessment to Complete ProjectOffsite FT Unit Validation of Syngas by Storage Trailer

Phase I Required Purchases

Purchased

Equipment

Installation Time,

manhoursInstallation Cost

Bay 1 Fifth Floor Area

Tar Reformer ASME Design, Materials, Fabrication and Installation $39,000 $59,421 360 $72,000

Hardware (Valves, Pressure Transmittters, Thermocouples) $6,275 160 $32,000

Data System and Safety Monitoring $15,500 80 $16,000

Total $60,775 $59,421 $120,000

Bay 3 First Floor Gas Cleanup Area

Materials and ASME Coding/Welding $9,880 $60,570

Equipment $163,794 $86,715

Catalysts $18,000 $18,380

Data System and Safety Monitoring $30,000

HAZOP Study $13,000

Shakedown and Calibrations

Equipment Total $221,674 $178,665

BTL Fabrication/Installation

Equipment/Vessel/Skid Assembly 880 $176,000

Data System and Safety Monitoring 160 $32,000

BTL Skid Piping 120 $24,000

BTL Utility Piping 80 $16,000

BTL Equipment Shakedown 160 $32,000

BTL Fabrication/Installation Total 1,400 $280,000

BTL Testing

Test #1, Gas Cleanup ( 1 Test - 4Days/ea ) 192 $38,400

Gas Cleanup Storage Area Total

Utilities for Bay 1/ 5 Floor and Bay 3/ 1 Floor

AGTF Building Ultilities Engineering Study $60,000 $81,000

AGTF Building Ultilities Installation $55,000

Bay 3 Piping Utilities Extended from Pipe Rack $8,900 220 $44,000

Total $123,900 $81,000 220 $44,000

Analytical Area

Analytical Equipment $10,000

Analytical Piping & Heating Equipment $2,891

Analytical Setup

Gas Sampling Lines 80 $16,000

Gas Chromotography Equimpment Setup and calibrations 40 $8,000

BTL Fabrication/Installation Total $10,000 $2,891 120 $24,000

BTL Testing

Test #1, Gas Cleanup ( 1 Test - 4Days/ea ) 288 $57,600

Analysis of Samples 60 $12,000

BTL Testing Total 288 $69,600

Phase IIRequired Purchases

Purchased

Equipment

Installation Time,

manhoursInstallation Cost

Gas Storage Compressor Fabrication/Installation

Piping for Gas Storage Trailer Installed to Trailer 205 $41,000

BTL Testing

Tests #2, 3, and 4 Gas Cleanup ( 3 Tests - 4Days/ea ) 576 $115,200

BTL Testing Total 576 $115,200

Gas Cleanup Storage Area

Storage Trailer, 258 Water CUFT, max pressure 2,400 psig $8,400

Stone Road Preparations $0

Transport Trailer, 6 round trips $15,600

Gas Cleanup Storage Area Total $15,600 $8,400

Analytical Area

Analytical Equipment $10,000

Analytical Piping & Heating Equipment

Analytical Setup

Gas Sampling Lines 160 $32,000

Gas Chromotography Equimpment Setup and calibrations 80 $16,000

BTL Fabrication/Installation Total $10,000 240 $48,000

BTL Testing

Tests #2, 3 and 4 Analytical ( 3 Tests - 4Days/ea ) 864 $172,800

Analysis of Samples ( 3 Tests ) 180 $36,000

BTL Testing Total 864 $208,800

Total Equipment Purchased for Project $330,377 a

Total Labor/Non-Labor $415,000 b

Additional Equipment Required for Project $441,949 c without Primary Compressor

Additional BTL Fabrication/Installation $485,000 d

Additional Analytical Fabrication/Installation $72,000 e

Testing, DOE BTL/Analytical Test 1 $108,000 f

Testing, DOE BTL/Analytical Tests 2, 3 and 4 $324,000 g

Additional Cost to Complete Phases I & II $1,430,949 h = c+d+e+f+g

CTD $745,377 I = a+b

Project Cost $2,176,326 h+i

38

Success Factors and Challenges

• Biomass Gasification needs syngas cleanup scheme that is proven, effective and low-cost– Large-plant process approach will not scale down well

– Tars are unique to biomass gasification

– Relatively low S in biomass feed affords unique opportunity to simplify the approach

• Operate the tar reformer successfully to reduce the tar load significantly. Remove other components with absorbents, solvents. Getting 100/300 hour continuous run times is challenging in pilot plant environment.

• Biomass gasification needs subsidies at present energy (oil) prices. Escalation of cost of capital intensive projects and lack of financing will slow down and inhibit commercial introduction. RPS, RFS, Government incentives and funded programs and corporate Green initiatives are positive factors.

• This project’s funding is tight and too much is in Phase II relative to what is needed in Phase I. However, it appears doable within the overall budget.

39

Future Work

• At this time the project is under “Stop Work” order

• GTI and partners developing alternative approach – relocate the gas cleanup slipstream to Auburn University where a suitable scale gasifier is being built by GTI on a separate project, get commitment from a BTL technology provider for the revised program (several have been contacted)

• Approval from DOE needed to pursue this alternate approach in more detail

• Propose that the Project would re-start with a Task to define costs to complete at new site before proceeding any further (Decision Point) –(budget adjustment for Phase 1 required)

40

Summary

• Syngas Cleanup is a major cost item of biomass gasification

but has not been adequately demonstrated except for power

production. Extrapolation from coal gasification gas cleanup

not cost effective.

• GTI has developed an attractive, efficient, lower-cost scheme

for biomass gasification syngas cleanup that merits testing– Preliminary, Process and Detailed engineering completed

– HAZOP conducted

– Major equipment ordered, most received

– Detailed, accurate cost to complete budget developed

• Schedule, funds availability on the project not compatible with

original plan at this point.

• GTI is evaluating an alternative plan which will be presented to

DOE in the near future.