Hydrocarbon Fouling of Reverse Osmosis Membranes

Group 3 Senior Design Project Fall 2012

Task: Hydrocarbon Removal

Design cost-effective pretreatment system for hydrocarbon fouling of a polymeric RO membrane Must be demonstrable in applications where 200 ppm of hydrocarbons exist and must be removed from industrial water

Design Considerations
Hydrocarbon recipe is a 50/50 (by volume) mixture of mineral spirits and diesel (non-vegetable oil or ethanol additive) The water sample is 3000ppm NaCl and 180ppm of the hydrocarbon mixture

What is Reverse Osmosis (RO)?

Desalination process used to treat process wastewater/hydrocarbon recovery water Apply pressure (enough to overcome osmotic pressure) to feed water so that it moves through a semi-permeable membrane Removes ionic and molecular sized substances

http://www.water-technology.net/projects/perth/perth4.html

http://www.sustainableplant.com/2012/04/make-the-most-of-reverseosmosis-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
720 mil ton

158 mil ton

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

Rice Production
United States: 20 billion lbs.

Louisiana: 2.7 billion lbs.

http://www.menurice.com/all-aboutrice/meet-us-rice-farmers http://www.usarice.com/doclib/188/219/367 7.PDF

Content of Rice Husk (wt%)

MnO2 0.07%

SiO2 22.11% MgO 0.21% CaO 1.24% Fe2O3 1.28%

Al2O3 1.23%

Organic material and moisture 73.85%

Amount Organics present in RH (wt%)

Methylglucuronic acid L-arabinose 3.44% 6.88% D-galactose 2.47%

D-xylose 18.45%

a-cellulose 45.59%

Lignin 23.17%

Calcium oxide(CaO) 4.20% Iron oxide(Fe2O3) 0.45% Sulfur trioxide(SO3) 0.85% Aumina(Al2O3) 4.30%

Magnesiumoxide(MgO) 0.27%

Sodium oxide(Na2O) 0.73%

Potassium oxide(K2O) 1.59%

Silica(SiO2) 87.59%

Amount Present in Rice Husk Ash (wt%)

Rice Husk ASH

What is it
Rice husk that have been combusted in an oxygen 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 the reaction during the burning of the rice hulls 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

35000

Calibration Curve

30000

25000

GC Pek Area

20000

y = 177.58x + 282.4 R = 0.98773

15000

10000

5000

0
0 20 40 60 80 100 120 Concentration (mg/L) 140 160 180 200

 Used Langmuir Isotherm to approximate mass of Ash needed for lab standard (~17g)
800

Langmuir Isotherm

700

600

500 Cs/Ce

y = 4.9053x R = 0.99607

400

300

200

100

0 0 20 40 60 80 Ce (mg/L) 100 120 140 160

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?

50 45 40 35 30 $/ton 25 20 15 10 5 0 Arkansas Louisiana California Average Southern States

4 Feb 2013 Rice Market News

What is the cost of this ash?

$1,460 per day for ash $534,000 annually for ash

Transport of Rice Hulls Cost per Ton

100 90 80 70 60 Cost ($) 50 40 30 20 10 0 0 200 400 600 Miles 800 1000 1200 1400

2004 2012

2004: $1.45 vs. 2012: $1.76

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

What is the cost of this ash?

$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 hydrocarbon removal 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