S19 Louisiana State University LTC2013

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Hydrocarbon Fouling of Reverse

Osmosis MembranesGroup 3 Senior Design Project

Fall 2012



Task: Hydrocarbon Removal

• Design cost-effective pretreatment system for hydrocarbon fouling of a polymeric ROmembrane

• Must be demonstrable in applications where200 ppm of hydrocarbons exist and must beremoved from industrial water



Design Considerations

• Hydrocarbon recipe is a 50/50 (byvolume) mixture of mineral spirits anddiesel (non-vegetable oil or ethanoladditive)

• The water sample is 3000ppm NaCl and180ppm of the hydrocarbon mixture



What is Reverse Osmosis (RO)?

• Desalination process used to treatprocess wastewater/hydrocarbonrecovery water

• Apply pressure (enough to overcomeosmotic pressure) to feed water so thatit moves through a semi-permeable

membrane• Removes ionic and molecular sized

substances



http://www.sustainableplant.com/2012/04/make-the-most-of-reverse-osmosis-membranes/

http://www.lenntech.com/membrane-fouling.htm



Potential Solutions

• Pre-treatment of influent – Ultrafiltration

• clogging

–

Biological treatment• sludge disposal

– Mechanical Removal

• activated carbon

• Fouled Membrane Treatment – Chemical removal of hydrocarbons

• Expensive, destroys membrane, downtime

–

Replace Membrane



Rice

http://www.scu.edu/profiles/images/green_technologies.jpghttp://www.ricehusk.com/content/menu_102/productshttp://www.marksdailyapple.com/is-rice-unhealthy/

720 mil ton

158 mil ton



Rice Production

• United States:20 billion lbs.

• Louisiana: 2.7billion lbs.

http://www.menurice.com/all-about-rice/meet-us-rice-farmers http://www.usarice.com/doclib/188/219/3677.PDF

http://www.menurice.com/all-about-rice/meet-us-rice-farmers


http://www.usarice.com/doclib/188/219/3677.PDF


















Organic material andmoisture73.85%

Al2O31.23%

Fe2O31.28%

CaO

1.24%

MgO0.21%

SiO222.11%

MnO20.07%

Content of Rice Husk (wt%)



a-cellulose45.59%

Lignin23.17%

D-xylose18.45%

L-arabinose6.88%

Methylglucuronicacid

3.44%

D-galactose2.47%

Amount Organics present in RH (wt%)



Silica(SiO2)87.59%

Aumina(Al2O3)4.30%

Sulfur trioxide(SO3)0.85%

Iron oxide(Fe2O3)0.45%

Calcium oxide(CaO)4.20%

Magnesium-oxide(MgO)

0.27%

Sodiumoxide(Na2O)

0.73%

Potassiumoxide(K2O)

1.59%

Amount Present in Rice Husk Ash (wt%)



Rice Husk ASH

• What is it

– Rice husk that have been combusted in anoxygen deprived environment

• How we used it

– ASH has an affinity for hydrocarbon

• Why

– Sustainable use of waste byproduct



Ash Production in Bulk

• Limit the amount of Oxygen entering thereaction during the burning of the ricehulls

• Retains more volume

• Better Absorption

•

More efficient use of the rice hulls• Less cost



Ash Production in Bulk cont.



Standard for Measurement

Lab Standard based on 1 L

1L Deionized H2O+

3,000mg NaCl

+

.24mL Hydrocarbon solution



GC Peaks



Calibration Curve

y = 177.58x + 282.4R² = 0.98773

0

5000

10000

15000

20000

25000

30000

35000

0 20 40 60 80 100 120 140 160 180 200

G C P e k A r e a

Concentration (mg/L)



• Used Langmuir Isotherm to approximate massof Ash needed for lab standard (~17g)

y = 4.9053xR² = 0.99607

0

100

200

300

400

500

600

700

800

0 20 40 60 80 100 120 140 160

C s / C e

Ce (mg/L)

Langmuir Isotherm



Physical Application of

Rice Hull Ash – Direct application to LNAPL (manually on top)

• Determine ash affinity for hydrocarbons

– Ash as a simple filter

• Ash packed in cylinder

– Turbulent action utilizing density separation

•hydrocyclone



Prototype



Turbid Effluent



Cyclone – separation by density



Test Results



Full Scale (1,000 gpm)



What is the cost of this ash?

0

51015202530

35404550

Arkansas Louisiana California AverageSouthern

States

$/ton

4 Feb 2013 Rice Market News




$1,460 per day for ash

$534,000 annually for ash



0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200 1400

C o s t ( $ )

Miles

Transport of Rice Hulls

Cost per Ton

2004

2012

2004: $1.45 vs. 2012: $1.76

http://www.bls.gov/data/inflation_calculator.htm




$1,460 per day for ash

$534,000 annually for ash

+ $47,000 to transport from local source+ $267,000 in operational costs (i.e. wages, etc.)

= $848,000 for an entire year



Cogeneration Power

• Rice hulls as a biomass: 3.66 kwh/kg

• Generation of power from biomass: 0.12

$/kwh• Gain from burning: 0.44 $/kg

• Daily gain from kwh produced: $29,100

•

Annual gain from kwh produced:$10,600,000



Capital costs gains/losses

• Transformation of waste to use

• Recovers product and gains $700,000

in energy from burning hydrocarbons• Neglecting facility operational costs, a

factor of 12.5 EROI

•

Note with estimated costs and EROI of 6.8



Conclusion of Experiments• Filter design

– Great hydrocarbon removal

– not efficient and turbid effluent is problematic

• Cyclone design

– Good hydrocarbon removal

– Good mass separation

• Dispersed air floatation

– Combines best qualities of both designs

– Use of dispersed air increases hydrocarbonremoval

– Achieves goal of hydrocarbon removal



Special Thanks

• Dr. Malone - LSU C.E.

• Dr. Constant – LSU B.E.

• Dr. Theegala – LSU B.E.

• Dr. Dismukes – LSU E.C.E.

• David Hawley - Geosyntec

• Alex GC

• Adam Dassey

• Michael Cheatham

S19 Louisiana State University LTC2013

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