World Water Forum College Grant Program 2017-2019 Grant Proposals

College CSU BAKERSFIELD

Faculty Dr. Cabrales

Project

#004

Designing and Building an Electroxidation Fluidized Bed Reactor

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Name: Department of Physics and Engineering, California State University Bakersfield

Project Title: “Designing and building an electroxidation fluidized bed reactor”

Faculty: Luis Cabrales Student Project Manager: Julian Arellano

Photo: Originclear advanced oxidation reactor

Project Strand: Local

Summary

Name: Department of Physics and Engineering, California State University Bakersfield

Project Title: “Designing and building an electroxidation fluidized bed reactor”

Faculty: Luis Cabrales

Student Project Manager: Julian Arellano

Photo: Originclear advanced oxidation reactor

Project Overview

This work is related to the designing, building, and evaluation of a fluidized bed reactor capable of treating produced oilfield water. Dr. Cabrales will be involved in design and construction of the proprietary design. Originclear company will provide technical assistance for the development. The study will evaluate the efficiency of the novel reactor on produced water from the region. In this study, Dr. Cabrales and his students will design, built, and evaluate the capacity of electroxidation for the removal of oil content from produced water. In electroxidation, reactive species are generated in an anode, and these species react with organic molecules to oxidize them. The advantage of this type of reactor is that no chemicals are required, thus reducing labor cost and operational costs. Fluidized bed reactors are very efficient type of reactors due to the high mass transfer rates. CSUB has recently signed a Memorandum of Understanding (MOU) with OriginClear (www.originclear.com). The proposed proprietary design could increase the efficiency of the electroxidation phase, thus, reducing the operational cost. The treated produced water should have values of oil and grease content below the maximum upper limits for irrigation.

Application Strand Identify Region LOCAL Designing and building an electroxidation fluidized bed reactor

California Central Valley

Contact information

Faculty Project Manager Luis Cabrales Student Project Manager Julian Arellano College California State University Bakersfield Department Physics and Engineering Overview / History Centrally located on a 375-acre site in the southern San Joaquin Valley,

California State University, Bakersfield is a continuously growing comprehensive regional university that is committed to transforming the lives of its students and community through its established excellence in academia, diversity, service, and community engagement since its founding in 1965. It serves around 10,000 students. The mission of CSUB is to be a comprehensive public university committed to offering excellent undergraduate and graduate programs that advance the intellectual and personal development of its students. An emphasis on student learning is enhanced by a commitment to scholarship, diversity, service, global awareness and life-long learning. The University collaborates with partners in the community to increase the region's overall educational attainment, enhance its quality of life, and support its economic development. In the past, I have worked with electrocoagulation and electroxidation processes to clean wastewater from different industrial sources, such as carwash, irrigation runoff, dairies, and oilfields. Currently, Dr. Cabrales is principal investigator in several grants related to produced water.

Make Check Payable To: California State University Bakersfield

Address 9001 Stockdale Highway Phone 661 654 2844 Email lcabrales@csub.edu

Member agency

Name: Deb Whitney Agency:USBR Email: dwhitney@usbr.gov Phone: (951) 201-6282.

10. PROJECT DESCRIPTION

Project description

Produced water is a by-product of oil and gas production. On average about 7 to 10 barrels

of produced water are obtained per barrel of oil (USBR, 2011). The annual consumption of water in municipal/industrial and agricultural uses in Kern County is around 0.4 million acre-ft and 2.7 million acre-ft, respectively (Water Association of Kern County (WAKC, 2015). Due to the water shortage in the state of California, the economy and society would benefit from maximizing the potential of the water produced from the oil and gas industry. With proper treatment, produced water can be used for different applications, such as groundwater recharge, irrigation of crops, or even drinking water. In an average year, ground water supplies approximately 31% (1 million acre-ft) of it. In drought years with limited surface water deliveries, groundwater supplies the bulk of the water used in the county. On the other hand, the oil fields of the Kern County produce almost 0.2 million acre-ft of water annually while producing oil (CA DOGGR, 2012). Much of this water could potentially be used for agricultural and industrial purposes in this drought-stricken area. Around 150,000 acre-feet per year (3.4 million barrels per day) of produced water is potentially available for reuse in Kern County (CALFLOWS, 2017).

With current treatment methods, the water production resulting from oil and gas production operations has been used for reinjection into the wells by steam or water flooding. It has also been treated to be used for irrigation (e.g. Cawelo Water District’s produced water program). There are various physical/chemical treatment methods that either have been successfully used in treating and reclaiming water resulting from oil and gas production operations or may become available to oil industry in future. Some of the most important quality parameters of produced water are salt content, the oil and grease content, inorganic compounds, and radioactive material. Salt content is sometimes expressed as conductivity, salinity, or Total Dissolved Solids or TDS (Clark, 2009). The TDS in produced water range from <2000 ppm to more than 150,000 ppm (All consulting, 2005). The characteristics of this produced water depend on the geological formation and location, lifetime of reservoir, and hydrocarbon produced (Fakhru’l-Razi 2009). In order to use the water in other applications, such as agricultural use, the concentrations of these components must be decreased to certain limits. One of the first stages to treat produced water is to remove the dispersed and dissolve oil components.

In 2007, OriginClear developed a process for the removal of non-soluble contaminants from large quantities of water. The initial focus was on the extraction of lipids from algae cultures. This technology is titled by OriginClear as Electro Water Separation (EWS). The process is two step: electroflotation and electroxidation. Figure 1 shows the schematic process of Originclear. This is a type of electrolytic separation, and the concept was developed more than 100 years ago. There are many applications of electrolytic separation across many industries. One advantage of EWS of OriginClear is the concentric anode/cathode configuration, which makes it amenable to high throughput. It is a continuous process configuration easy to scale up, and minimizes electrical energy input. This technology is used to remove dispersed and dissolved oil from produced water as a precursor to downstream desalination process. In the first step of EWS, the objectives is to use electrical pulses to produced small oxygen and hydrogen bubbles which will attach to the oil droplets from 1 to 25 microns and suspended solids. The bubbles will lift the suspended oil and solids to the surface, making it easier to separate. This electroflotation treatment will be used to

separate emulsified oil. This procedure will be compared to the traditional flocculation method using a modified version of the jar test (USEPA, 1999).

In the second stage, an electrochemical reaction is used to produce reactive species, such as

chlorinated and peroxyl radicals. These reactive species oxidize any dissolved oil, or any hydrocarbon remaining after the electroflotation process. The oxidation process converts any hydrocarbon molecule in carbon dioxide. This process also has the capability of disinfecting and killing microorganisms present in the water. OriginClear equipment has been tested in the field. In one project, the OriginClear equipment was able to decrease the oil content in water from 176 mg/L to 7 mg/L only with electrocoagulation and flotation. An additional decrease in the oil content was observed by using ultrafiltration (Origin Clear, 2015).

Fig. 1. Schematic EWS process: electroflotation and oxidation stages (Originclear, 2015).

Once the oil is removed, if the water samples contain a TDS value higher than the optimum

for agricultural applications, one option is to use reverse osmosis to decrease the TDS values. Reverse osmosis is the standard treatment for desalination applications in industry. After all these treatments, the treated water should have values of oil and grease content and TDS below the maximum upper limits for irrigation. Boron is an element of special concern for agriculture. Low boron content is very important in irrigation water since several crops are injured by this element (Grattan, 2002). Reverse osmosis or ion exchange resin can be used to decrease boron content (Busch 2003) to the allowable levels. One major problem with reverse osmosis is membrane fouling. In order to make more efficient this process, the water entering the reverse osmosis system should be free of organic contaminants. The electroxidation process could help to reduce the fouling of the membranes by reducing the amount of organic compounds.

CSUB has recently signed a Memorandum of Understanding (MOU) with OriginClear (www.originclear.com). Originclear has lend a laboratory scale equipment to CSUB. This equipment is already in use to test its capabilities on produced water, and it features the concentric tube design. The Originclear technology is an effective cost solution to treat produced water. In this project, a novel electrochemical fluidized bed reactor will be designed, build, and tested in order to improve the efficiency of this electroxidation technology. Due to the configuration of fluidized bed, a high mass transfer is achieved within the system. The high mass transfer rate will mean that a higher amount of organic molecules or dissolved oil is oxidized with less energy. In the figure below a drawing of the fluidized bed reactor is shown.

Figure 2. Electroxidation fluidized bed reactor (Kumar, 2008).

Fluidization is a technique in which small solids are contacted with fluid to transform into a fluid-like phase with the purposes to enhance mass and heat transfer between the phases. This process can occur with or without chemical reaction. The fluid may be a gas or liquid. Fluidized bed finds many applications in industrial chemical process industries. A fluidized bed provides large interfacial area, high degree of mixing, and temperature uniformity (Kumar, 2008).

In this project, a prototype of fluidized bed reactor will be designed, built, and tested. The design will be based on a concept developed by Dr. Cabrales, and with the technical support of Originclear team. Several size of stainless steel bed particles will be tested in order to find the optimum size to have a fluidized bed with different flow conditions. In the first phase, the electroxidation potential will be tested against a blue dye (methylene blue) which will be used as a controlled organic molecule to be oxidized. The concentration of the dye will be measured with a UVVIS spectrometer currently in the laboratory. In the second phase of testing, the reactor will be tested with produced water which has been treated with electroflotation, thus with a reduced amount of suspended oil. Dr. Cabrales will be involved in the acquisition of produced water from oilfields. The amount of oil will be measured by analyzing Chemical Oxygen Demand

(COD) on the samples. Other laboratory equipment currently at CSUB which will be used for this project: pH meters, turbidimeter, conductivity meter, and UV/VIS spectrometer. Engineering student will perform all the water treatment studies and some analysis under the supervision of the faculty. As with any other experimental area, there are chemical and physical hazards in the laboratory. Student will be trained in laboratory safety before starting the experiments.

References

All consulting, 2005. Technical summary of oil and gas produced water treatment technologies. http://www.all-llc.com/publicdownloads/ALLConsulting-WaterTreatmentOptionsReport.pdf (accessed June 22, 2015). Busch M., Mickols W.E., Jons S., Redondo J., De Witte J. 2003. Boron removal in seawater desalination. BAH03-039, IDA World Congress, Bahrain. CA Division of Oil, Gas and Geothermal Resources (DOGGR), 2012, 2012 preliminary annual report of California oil and gas production statistics: CA Dept. of Conservation, Sacramento, CA, ftp://ftp.consrv.ca.gov/pub/oil/annual_reports/2012/PR03_PreAnnual_2012.pdf (accessed June 12, 2015). CALFLOWS, Putting produced water to work. https://www.calflows.com/wp-content/uploads/2017/04/putting-produced-water-to-work-singles.pdf (accessed November 27th, 2017) Clark C.E. and Veil J.A., 2009. Produced water volumes and management practices in the United States, Argonne National Laboratory. http://www.ipd.anl.gov/anlpubs/2009/07/64622.pdf (accessed June 22, 2015). Fakhru’l-Razi, A., Alireza, P., Lugman C.A., et al. 2009. Review of technologies for oil and gas produced water treatment. Journal of Hazardous Materials 170(2): 530-551 Grattan, S. 2002. Irrigation water salinity and crop production. Publication 8066. University of California Agriculture and Natural Resources. http://vric.ucdavis.edu/pdf/Irrigation/IrrigationWaterSalinityandCropProduction.pdf (accessed June 22, 2015) Kumar, S., Ramamurthy, T., Subramanian, B., et al. (2008). Studies on the Fluidized Bed Electrode. International Journal of Chemical Reactor Engineering, 6(1), pp. -. Retrieved 10 Dec. 2017, from doi:10.2202/1542-6580.1610 OriginClear, 2015. High-efficiency water treatment for oil & gas markets, North American Petroleum Accounting Conference, http://www.originclear.com/pdf/north-american-petroleum-accounting-conference.pdf (accessed June 21, 2015). US Environmental Protection Agency, 1999. Enhanced Coagulation and Enhanced Precipitative Softening Guidance Manual http://www.epa.gov/ogwdw/mdbp/coaguide.pdf (accessed June 24, 2015)

United States Bureau of Reclamation, 2011. Oil and gas produced water management and beneficial use in the Western United States, Science and Technology Report No 157 https://www.usbr.gov/research/AWT/reportpdfs/report157.pdf (accessed June 22, 2015) Water Association of Kern County (WAKC), 2015. (http://www.wakc.com/index.php/water-overview/overview/69-water-in-kern-county (accessed June 23, 2015).

Team Members

Dr. Luis Cabrales

Luis Edgar Cabrales Arriaga received a BS in Chemical Engineering at the IEST in Altamira, Mexico. He gained experience working as an engineer at M&G Polymers. Afterwards, he went on to earn an MS in Chemical Engineering and a Ph.D. with specialization in Fibers and Biopolymers from Texas Tech University (TTU). Later, he joined the Fiber and Biopolymer Research Institute (FBRI) at TTU as a research associate. Currently, he is an Associate Professor at the Department of Physics and Engineering at California State University, Bakersfield. At CSU Bakersfield, he continues to work on research related to materials engineering and water treatment technologies. He has obtained federal and state funded grants to work on innovative technologies to reuse produced water for agricultural purposes. Some of the examples of funded projects are: • U.S. Department of Agriculture- Capacity Building Grants for Non Land Grant Colleges of Agriculture, “Assessing Potential Human Health Impacts Associated with the Use of Oilfield Produced Water for Crop Irrigation”. Faculty participant, $450,000, January 2017 to December 2019. https://sites.nicholas.duke.edu/oilfieldwater/ • Agricultural Research Institute CSU, “Forage Yield and quality under Irrigation with Produced Waters”. Co-PI, $150,000, September 2017 to August 2020. • Agricultural Research Institute CSU, “Physiological performance and nutritional quality of forages irrigated with oilfield waters”. Co-PI, $450,000, September 2016 to August 2019. • U.S. Department of Agriculture- Capacity Building Grants for Non Land Grant Colleges of Agriculture, “Investigate the use of treated unconventional water for potential agricultural applications”. Co-Project Director, $149,785, January 2017 to December 2019. • U.S. Department of Agriculture- Undergraduate Research and Extension Experiential Learning Fellowships. Co-Project Director, $299,367, September 2016 to August 2019.

Dr. Cabrales will lead the design concept to manufacturing and setup the experimental plan.

Julian Arellano

Julian will be the student project manager. He is a sophomore pursuing a B.S. in Engineering Sciences. He was selected due to his good grades, and academic performance in the course of Materials Science. He will prepare the methylene blue solutions and carry out the experiments under controlled conditions. He will conglomerate the data in graphs and tables. He will be in charge of disposing chemicals in a safe manner.

Jean Louis Kindler

Jean-Louis Kindler is President of OriginClear Technologies and leads the commercialization of OriginClear’s breakthrough water treatment technology. Mr. Kindler is a veteran of 25 years as both a top executive and engineer in environmental technologies. Before OriginClear, JL was co-founder and Chief Technology Officer of Ennesys, the company’s French joint venture, where he designed its patent-pending waste-to-energy system. Earlier, as founding CEO of MHS Equipment, a French nanotechnologies equipment manufacturing firm (42 M€, 360 employees in 2008), he led the development of a breakthrough fuel cell process. And earlier still, his twenty-year career in Japan gave him unique insight into fast-growing Asian markets. There, as principal of technology incubator Pacific Junction, Jean-Louis completed various assignments. These included technology sourcing for the French industrial group GEC-Altshom, building the first commercial unit of the Blue Tower, a breakthrough hydrogen production system using waste biomass feedstock, and market development for a fluids mixing technology that helped inspire early OriginClear inventions. Jean-Louis holds a Master’s in Economics and Public Policy from the Institute of Political Science in Lyon, France, and an MBA in International Management in Paris. Jean Louis will provide technical assistance and electrode supplier contacts. See attached letter of support. Schedule

Activity Dates

Participate College Expo Spring 2018 Sign contract and Agreement Summer 2018 Design of the fluidized electroxidation reactor May-June 2018 Building of fludizided bed electroxidation reactor July-Sept 2018 Experimental testing of reactor with Methylene blue September-November 2018 Experimental testing of reactor with Produced water. December 2018-January 2019 Data analysis and preparation of written report February- March 2019 Report and Expo Participation April 2019

In the next section, I am answering the questions related to the project description in case it was missed. Provide a detailed work plan identifying all project activities. It is required that the proposed work plan addresses each of the following:

1) Which water-related issue or challenge have you selected? Development on the implementation of water-use efficiency technology.

2) Is it a local or global focus per the RFP guidelines? Local, the project addresses an important issue in Kern County, California.

3) Which content strand (technology, policy or communications) have you chosen as the research focus for creating your project? The content strand is Technology.

4) Where will the research and data collection take place? The research and data collection will take place at CSU Bakersfield.

5) What is the anticipated outcome of your research? An outcome may be short-term (i.e., changes in knowledge or attitude) or long-term (i.e., changes in condition of natural resources). The anticipated outcome of this research is to obtain a more efficient water treatment process from what is on the current market.

6) Estimate of the Project Projection Benefits selected from the USBR Quantitative Benefits chart (see list below). See chart in the next section

7) Describe your team’s experience and technical capabilities (including in-house and/or outside hired individuals) to accomplish the project. List the roles and responsibilities of each team member.

See team members in project description above.

8) Provide a project schedule with key milestone dates and deliverables with measurable outcomes.

See schedule above

IDENTIFYING QUANTITATIVE BENEFIT PROJECTIONS

PERFORMANCE MEASURE QUANTITATIVE OUTCOME LOCAL / GLOBAL IMPACT

Makes More Water Available 7,500 Acre Feet/Year Local

Reduces Water Treatment Costs $1,164,000 / Year Local

Cost associated with each of the physical quantitative outcomes above

$155/AF/yr

Local

Notes: The calculated acre feet per year was based in a 5% of the 150,000 acre feet/year that could be available for reuse from produced water. This is based on the assumption that a more efficient oil removal technology will have an impact on the produced water which is lower in TDS and boron. The cost is based on 0.15 dollars per barrel, with a more efficient reactor, this could decrease the opoerating to around 0.13 cent per barrel. Thus, 0.02 dollars per barrel, times 7760 barrels in one acre feet times 7500 acre feet per year= 1,164,000

FINANCIAL CRITERIA

Matching funds

Dr. Cabrales will donate its time to this project, with a total of 37 hours for $2500.

BUDGET OVERVIEW

DESCRIPTION AMOUNT NOTES GRANT FUNDS REQUESTED $10,000

ADDITIONAL SOURCE OF FUNDS

(List all, if applicable) $2500 DATE ISSUED

(Iif applicable)

Matching funds from Faculty time

PROJECT TOTAL $12,500

Budget Breakdown BUDGET ITEM DESCRIPTION

PRICE/RATE UNIT QTY WWF College TOTAL COST

SALARIES AND WAGES

Consultant $0.00 hr 0.00 $0 $0 Professor $67.52 hr 17.18 $1,160 $0 $1,160 Professor - In kind Match

$67.52 hr 37.03 $0 $2500 $2,500

Student $11.00 hr 349.00 $3,839 $0 $3,839 SUBTOTAL $4,999 $2500 $7,499

TRAVEL

Mileage $0.55 mile 229.00 $126 $0.00 $126 Conference Registration

$250.00 each 2.00 $500 $0.00 $500

Airfare\Lodging (not allowed)

SUBTOTAL 0 626 0 $626.00 SUPPLIES/MATERIALS - Describe all major types of supplies/materials, unit price, # of units, etc., to be used on this assisted activity.

Pump $500.00 each 1.00 $500 $0.00 $500.00 Power supply $500.00 each 1.00 $500 $0.00 $500.00 Plexiglass tubes 3 sizes

$100.00 each 3.00 $300 $0.00 $300.00

Stainless steel 5 sizes

$14.00 each 5.00 $70 $0.00 $70.00

Electrodes $100.00 each 2.00 $200 $0.00 $200.00 COD heater reactor

$1000.00 each 1.00 $1,000 $0.00 $1,000.00

COD reaction vials

$201.25 each 4.00 $805 $0.00 $860.00

SUBTOTAL 3375 $0.00 $3,430.00 CONTRACTUAL/ CONSTRUCTION

College Overhead Fee

$1,000.00 each 1.00 $1,000.00 $0.00 $1,000.00

Note: Not to exceed $1,000

SUBTOTAL $1,000.00 $0.00 $1,000.00 TOTAL DIRECT COSTS:

$10,000.00 $2,500.00 $12,500.00

HR Benefits (Note: Ineligible Grant Expense)

0 0 0

TOTAL ESTIMATED PROJECT/ACTIVITY COSTS:

$10,000.00 $2,500.00 $12,500.00

CSU Bakersfield - Cabrales

BUDGET ITEM DESCRIPTION PRICE/RATE UNIT QTY WWF College TOTAL COST

Consultant $0.00 hr 0.00 $0 $0Professor $67.52 hr 17.18 $1,160 $0 $1,160Professor ‐ In kind Match $67.52 hr 37.03 $0 $2500 $2,500Student $11.00 hr 349.00 $3,839 $0 $3,839SUBTOTAL $4,999 $2500 $7,499

Mileage $0.55 mile 229.00 $126 $0.00 $126Conference Registration $250.00 each 2.00 $500 $0.00 $500Airfare\Lodging (not allowed)SUBTOTAL 0 626 0 $626.00

Pump $500.00 each 1.00 $500 $0.00 $500.00Power supply $500.00 each 1.00 $500 $0.00 $500.00Plexiglass tubes 3 sizes $100.00 each 3.00 $300 $0.00 $300.00Stainless steel 5 sizes $14.00 each 5.00 $70 $0.00 $70.00Electrodes $100.00 each 2.00 $200 $0.00 $200.00COD heater reactor $1000.00 each 1.00 $1,000 $0.00 $1,000.00COD reaction vials $201.25 each 4.00 $805 $0.00 $860.00SUBTOTAL 3375 $0.00 $3,430.00

College Overhead Fee $1,000.00 each 1.00 $1,000.00 $0.00 $1,000.00Note: Not to exceed $1,000SUBTOTAL $1,000.00 $0.00 $1,000.00

TOTAL DIRECT COSTS: $10,000.00 $2,500.00 $12,500.00

HR Benefits(Note: Ineligible Grant Expense) 0 0 0TOTAL ESTIMATED PROJECT/ACTIVITY COSTS:

$10,000.00 $2,500.00 $12,500.00

Faculty Salary per month  11,694.00$      Faculty Salary per year (X8 Monthly) 93,555.00$      *Faculty Hourly Calculation 67.52$             *An approximation, Faculty are not paid hourly wage.  (11694 Monthly Salary /4.33 Weeks per month average) / 40 hours

COMPUTATION

SALARIES AND WAGES

TRAVEL

SUPPLIES/MATERIALS ‐ Describe all major types of supplies/materials, unit price, # of units, etc., to be used on 

CONTRACTUAL/ CONSTRUCTION