DeS Presentation 8112008.pdf

Development of Desulfurization Systems for Marine Fuels

NIST ATP contract # 70NANB7H7013 Navy ONR contract # N00014‐08‐C‐0197

Diane Aagesen Durai Swamy

Intelligent Energy Long Beach, CA Aug 11, 2008

NIST ATP Program Grand Scheme

Membrane based solutions: Diane Aagesen, Durai Swamy Oxidative desulfurization: Donovan Peña Emulsification issues: Durai Swamy Overall PI: Anand Chellappa

Membrane Based systems Background and need for liquid fuels desulfurization Commercial Drivers History of Membrane based desulfurization

•PV‐polymeric membrane

Process configurations (2) Test data from

•Jet A

•JP5

• Marine Diesel Oil (MDO)

Engineering Aspects and conclusions ODS tests and results Acknowledgments

Background and Need for Liquid Fuels Desulfurization

• Petroleum reserves becoming heavier and difficult to desulfurize by traditional hydrotreating ‐ Sterically hindered S compds

• A less energy‐intensive sulfur removal technology is sought

• SOx and PM emissions reduction regulations for ocean going vessels getting tighter

–main engines (1.5% S 0.5% S)

– auxiliary engines (0.5% 0.1% S)

Background and Need for Liquid Fuels Desulfurization

• Fuel cell power systems (military or commercial)

– For use upstream of sorbent beds to reduce maintenance cycle

–Dibenzothiophene and heavier S compounds clog active adsorption sites

• Niche applications

Commercial Drivers April 09, 2008

• “An historic agreement was struck last week when the International Maritime Organization’s (IMO) Marine Environmental Protection Committee (MEPC 57) reached agreement on a package of amendments and revisions to MARPOL(*) Annex VI (Prevention of Air Pollution from Ships) which, subject to formal adoption at MEPC 58 in October 2008, will enter into force through the tacit amendment procedure in February 2010.” The revisions of Annex VI allow new emission control areas (ECAs) to have sulfur limits down to 1.0% in March 2010 and to 0.1% in January 2015

• World trading fleet ~ 90,000 vessels

July 24, 2008

CARB’s new measure requires ocean‐going vessels within 24 nautical miles of California's coastline to use lower‐sulfur marine distillates in their main and auxiliary engines and auxiliary boilers, rather than the dirtier heavy‐fuel oil called bunker fuel. The regulation will be implemented in two steps, each requiring lower sulfur content in the fuel‐ first in 2009 and final in 2012. For main and auxiliary engines and auxiliary boilers, the same distillate fuel restrictions will start on July 1, 2009. Ships will be required to use 1.5% sulfur marine gasoil (MGO) or 0.5% sulfur marine diesel oil (MDO) in auxiliary engines from July 1, 2009. All these sulfur requirements will reduce to 0.1% as of January 1, 2012.

Commercial Drivers

Merchant and naval ships APU demand growth (new FC systems and retrofits)

History of System Development

• IE requested by Boeing to remove sulfur from jet fuel for FC APU‐2005 ( on‐board slip‐stream approach first envisioned)

• Interest from U.S. navy to use membranes for sulfur removal upstream of adsorbent beds‐JP 5 tested in 2006

• NIST‐ATP awards funding to IE to develop PV, NF and ODS desulfurization solutions‐2007

• U.S. navy (ONR) orders a membrane‐based (PV) system for sulfur removal from JP‐8‐2008 (USMC APU application)

Process Configurations Slip‐Stream Approach*

*Same approach can apply to aircraft to reduce emissions at airports or dock-side to create high value product

Slip‐Stream Approach‐Simple

~ 45% S Reduction at ~ 60% yield for JP5

Pervaporation Test Data*‐Jet A 4” Diameter Spiral Module

0.4

0.8

1.2

1.6

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

0 5 10 15 20

Fl ux

(k g/ hr m 2)

Su lfu r Re du ct io n

Cumulative Hours Suflur Reduction % Flux

T=130C, Pu/s=20 psig, Pd/s=0.3psia, avg. stage cut = 15.4% *10/07

Pervaporation Test Data‐MDO 4” Diameter Spiral Module

Performance of the spiral wound module – MDO Stage cut = 3%, T=130 C, P u/s = 20 psig, Pd/s=68mbar

Pervaporation Test Data*‐Jet A 4” Diameter Spiral Module –Simple

Run Clean Fuel %

Sulfur Reduction %

1 9.4 73.7

2 12.1 68.1

3 16.0 64.4

4 19.8 62.8

Throughput Characterization

0.6

1.1

1.6

2.1

2.6

Temperature

P er m ea tio n

(k g/ hr

Effect of increasing feed temperature from 114C to 131C on permeation rate *8/07

Test Rig‐Simple

Membrane‐ 4” diameter upright spiral

Liquid ring vacuum pump

Vent

Slip‐Stream Approach‐Advanced ~ 85% S reduction at ~10% yield

Pervaporation Test Data‐Jet A 2” Diameter Spiral Module‐Advanced

Flux (kg/hrm2)

Split (overhead/ bottoms)

% Stage Cut After PC

% S Reduction

3.2 0.49 8.3 90.1

2.6 0.54 8.9 89.3

2.7 0.50 8.8 89.2

T = 115C, Pu/s = 20 psia, Pd/s = 0.24 psia

Flat Module

Sulfur Compound Permeate (ppm)

Whole MDO (ppm)

Percent Removal

Benzothiophene 843 285 -195.5 C1-Benzothiophene 2265 1162 -95.0 C2-Benzothiophene 721 561 -28.6 C3-Benzothiophene 472 540 12.6 C4+-Benzothiophene 115 275 58.4 Dibenzothiophene 35 110 68.4 C1-Dibenzothiophene 114 781 85.5 C2-Dibenzothiophene 47 853 94.4 4,6-Dimethyldibenzothiophene 13 88 84.7 C3+-Dibenzothiophene 14 4157 99.7

Feed Permeate

Data from 6% permeate stage

Fuel Kinematic Viscosity (cSt)

Flash Point (C)

Whole MDO 11 85 Permeate MDO 1.12 60

Lighter permeate still within fuel specification for most important physical properties

Data from 6% permeate stage cut

Engineering Aspects PV System Power Requirement is Low

Pervaporation System Energy Requirement-Current Lab Scale Sensible heat (electric heater) 270 Vacuum energy 186 Condensing energy 150 Pumping energy + ancillary BOP components 100 Total (btu/lb of cleaned fuel) 706 System Energy Requirement/Heating Value of Clean Fuel* 0.0353

* based on heating value of 20,000 btu/lb

System Energy Requirement-Future Ship Scale Replace with ship waste-heat 0 Vacuum energy 186 Condensing energy –sea water 0 Pumping energy +ancillary BOP components 120 Total (btu/lb of cleaned fuel) 306 System Energy Requirement/Heating Value of Clean Fuel* 0.015

System Footprint

System Assembly (24" x 18" x 16")

Feed Pump Membranes

Vacuum Unit

System Footprint‐Ship Scale

4’ 7’

Typical 2MWe Unit (100 kg/hr of clean fuel)

MGO, MDO

Weight: 800kg Sulfur Removal up to 90% Start‐up time: 45 minutes

Oxidative Desulfurization ‐ ODS Method 1 for Distillates using Soluble Organic Peroxide:

- Liquid phase ODS of Jet Fuels and MDO using fuel-soluble tert-butyl hydroperoxide (TBHP) - maximum conversion (67%) at 120°C operating at 70 psig and LHSV of 8/hour.

-Adsorption of the sulfones is the second step in the ODS process -reducing 1050 ppmw S oxidized Jet A to less than 100 ppmw S at 7 ml fuel / g adsorbent.

Method 2 for IFO using Inorganic Alkali Superoxides:

- IFO380 with 10% MDO added for room temp fluidity – oxidized with KO2 at 50C at atmospheric pressure in a 50 g batch.

-Sulfur content was reduced from 2.6% to 0.65%, ~75% S reduction by adsorption of the sulfones from the ODS step.

-These results are very encouraging but too early to predict economical viability.

Conclusions

• Pervaporation membranes can produce a sufficiently low sulfur slip stream for use in SOx emissions reduction in/near ports

• Pervaporation membrane may help extend sulfur specific adsorbent life spans/capacities in fuel processors for FC systems

• Preliminary results from ODS methods show potential for sulfur reduction in IFO.

Emulsification

• Emulsions of oil and water can reduce NOx – needs surfactant and stabilizer additives.

• Sulfones separated from ODS process can range from 5 to 30% of feed (~10 times the S in feed).

• Sulfones can form oil‐water emulsions probably without needing surfactants and stabilizers.

• We plan to perform emulsification of sulfone‐rich fuel fractions produced from the ODS process; here sea‐water scrubbers may be employed to reduce S from burning Sulfone‐rich fuels.

Acknowledgments Dr. Lloyd Steve White, et al., W.R. Grace

Dave Daggett, Boeing Co.

John Heinzel & Ian Peek, Naval Sea Systems Command (NAVSEA)

Don Hoffman, U.S. Office of Naval Research (ONR)

National Institute of Standards and Technology (NIST‐ATP)

Donald Minus, Wright Patterson Air force Research Laboratory

Thank You