Innovative Biological Emissions Treatment

Technology to Reduce Air Pollution for

Petroleum and Petrochemical Operations

Kim Jones, David Ramirez , Shooka Khoramfar

Department of Environmental Engineering, Texas A&M

University-Kingsville, Kingsville, TX 78363, USA

Project consultant:

James Boswell, Boswell Environmental, Montgomery, Texas

Project Sponsor:

Carolyn LaFleur , Houston Advanced Research Center (HARC)

Project partners:

George King, Sam Pittman, Cody Garcia, Apache Resources

Production Facility

1/31/2017

Potential opportunities for biological air emission control

2

Waste Water during Drilling, Fracturing and Natural Gas

Production

Process equipment such as Compressors and motors on the

drilling and production sites Condensate storage tanks

Based on Occupational Safety and Health Administration (OSHA), permissible exposure limit (PEL) (8 hTWA) of benzene for general industry = 1.0 ppm

Why biological treatment?• Biological treatment of air emissions offers a cost-effective and sustainable control

technology for industrial facilities facing increasingly stringent air emissions limits.

• This system uses the capacity of microorganisms to degrade air toxins (HAPs,Hazardous Air Pollutants), like benzene without the use of natural gas as fuel or thecreation of secondary pollutants.

• The replacement of conventional thermal oxidizers with biofilters will yield naturalgas savings alone in the range of thousands of dollars to over $1 million per year perunit.

• Any new technology that could replace a single thermal oxidizer (100,000cfm size)could provide a savings of more than 4,166 MM BTUs of natural gas annually (basedon 8,760 hrs of operation and 0.475 MM BTU per hour of usage). That representsenough natural gas to comfortably heat or cool approximately 120 homes annuallyfor each thermal oxidizer or flare replaced.

• Water vapor, carbon dioxide and biomass are the products of aerobic biodegradationof organic pollutants. However, the carbon emissions in biologically based units ismuch less than incinerators and flares.

3(Source: Boswell, 2008)

Successful pilot scale sequential treatment for VOC emissions at different industries

4

Forest product plant,

Stimson Lumber Co. Gaston,

Oregon

Paint & Coatings Eugene,

Oregon

Process description• The goal of this project is to demonstrate a novel sequential treatment technology that integrates two

types of bio-oxidation systems biotrickling filter and fixed bed biofilter for controlling petrochemicalindustries air emissions.

• This coupled design can be optimized to maximize the conditions for microbial degradation of VOCvapors.

• The first bed takes the highest inlet VOC loadings, to remove the more water soluble organics, whilethe secondary bed acts as an overload and polishing stage to remove more complex organiccompounds.

• The first unit also controls the incoming air stream temperature and regulates humidity and dampens fluctuations in contaminant loadings.

• Less hydrophobic pollutants can be removed in the first stage Bio-trickling Chamber by the biofilm on the surfaces of the X-Flow media and microbes in the sump and more hydrophobic compounds should be removed within the Bio-Matrix Chamber periodically sprayed with sump water to maintain proper moisture for best biofilm development.

• Water entering the biotrickling filter is collected in a sump, monitored for water quality parameters, and continuously sprayed onto the top of the X-flow media bed in the BTF.

• The flowing water phase benefits the biotrickling filter by providing a continuous supply of nutrients, removing possible degradation by-products, suspending biomass for continual reseeding of the system, and aiding in the transfer of hydrophilic pollutants onto the biofilm. 5

Objectives for the Apache (TAMU #2 tank battery) field test

Sampling and characterization of some field VOCs emissions1Design, build, process test and implementation of a field scale sequential treatment unit in 12 months2 Demonstrate the ability of bio-oxidation systems to treat variable loadings of VOC emissions as experienced in refineries and production facilities during routine operations, process turnarounds or upsets3Optimize the process for the ability to efficiently degrade mixtures of hydrophobic compounds typically encountered in refinery and oil and gas production facility emissions4

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Characterization of VOCs

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GC-FID PID

GC-MS

Biotrickle filter media (First vessel)

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Biofilter media (Second vessel)

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Key design and operational parameters

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Key design and

operational parameters

Air flow rate

Water flow rate

Temperature

pH and Conductivity

Nutrient concentration

Pressure

Biofilter bed moisture

Field scale unit start up at Apache TAMU #2 tank battery-10 May 2016 to 1 August 2016

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The field unit consists of a skid mounted two vessel system (100 cubic feet of total treatment volume) made of fiberglass with corrosion resistant schedule 80 PVC piping (Diamond Fiberglass Fabricator, Victoria, TX).

Field scale unit start up at Apache TAMU #2 tank battery- 6 May 2016

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Date Completed task

04/28/16 Load the BF media to the second vessel

05/05/16- 05/25/16

Safety meeting, Generator set up, Sampled of the headspace for GC-MS analysis, Loaded the BTF media to the first vessel, Checked the immediate area around the

system for hydrocarbon content with a photoionization detector (PID),

Inoculation of the system with oily water and compost tea,

Checked the water pump and blower performance

05/30/16 Inoculation of the system with the CITGO’s Corpus Christi Refinery wastewater

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Field scale unit start up at Apache TAMU #2 tank battery- 28 April 2016 to 30 May 2016-

Main dimensions and characteristics of the two tanks

BTF BFBed height (ft) 4 4

Diameter (ft) 4 4

Ratio height to diameter 1 1

Recirculation tank volume (gal) 100 100

Water make-up tank volume (gal)

300

Air flow rate (ft3/min) 25 25

Recirculation flow rate (gal/min)

3.5 (optimization possible) 3.5 (optimization possible)

Spraying frequency 24/7 2 min every 8 hr (optimizationpossible)

Gas velocity, (ft/min) 300 300

EBRT (min) 2 (optimization possible) 2 (optimization possible)

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GC-MS characterization from the headspace of the Apache TAMU #2 tank battery

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Peak # Component Retention Time Conc. (ppm)

1 Butane 9.51 6709

2 Isobutane 9.21 5118

3 Pentane 10.88 4233

4 Butane, 2-methyl- 10.45 4189

5 Hexane 13.03 1553

6 Pentane, 2-methyl- 12.29 1497

7 Cyclohexane, methyl- 16.16 896

8 Heptane 15.50 649

9 Cyclopentane, methyl- 13.75 534

10 Toluene 16.93 282

11 Octane 17.83 218

12 Benzene 14.32 197

13 Nonane 19.90 110

14 p-Xylene 19.22 87

Fluctuation in VOC concentration at inlet of the bio-oxidation unit – 1 August 2016- Apache TAMU #2 tank battery

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8:24 AM 9:36 AM 10:48 AM 12:00 PM 1:12 PM 2:24 PM 3:36 PM

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PID measurements from the inlet and outlet of the bio-oxidation unit-10 May 2016 to 29 July 2016- Apache TAMU #2 tank battery

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10-May 20-May 30-May 9-Jun 19-Jun 29-Jun 9-Jul 19-Jul 29-Jul

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Removal efficiency of the biooxidation unit- 10 May 2016 to 29 July 2016- Apache TAMU #2 tank battery

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10-May 20-May 30-May 9-Jun 19-Jun 29-Jun 9-Jul 19-Jul 29-Jul

RE

(%)

TimeBTF removal efficiency Overall removal efficiency BF removal efficiency

Average RE of the system (July month): 53%Average RE of the BTF (July month): 40%Average RE of the BF (July month): 23%

Performance characteristics of the BTF unit using GC-FID- Sampling at 28 July using 3 tedlar bags

CompoundRetention time

(min)

Inlet

concentration

(ppm)

Outlet

concentration

(ppm)

RE (%)

p-Xylene 1.57 587 228 61%

o-Xylene 4.44 498 322 35%

Benzene 6.41 44 31 30%

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Biofiltration Summary

• In spite of the hydrophobic nature of the pollutants, a relatively highVOC removal was observed in the BTF unit probably due to high biofilmgrowth and continuous spraying of water and nutrients.

• BF watering is an important operational parameter since it directlyinfluences the water content and the pH value on the filter media. At theApache site, given the very warm temperatures during the fieldbiofiltration test, increased irrigation of the BF unit was probablyneeded.

• The surprisingly high VOC removal capabilities of the BTF unit suggeststhat a combination of both suspended growth and attached growthbiofilms may provide an important new approach toward biotreatmentoptimization of VOCs for the oil and gas and petrochemical industries

• The bio-technology employed in this project may be a cost-effectivetreatment technique to mitigate VOC emissions from oil and gas facilitiesand should be evaluated as a possible MACT (Maximum AchievableControl Technology) to control HAPs.

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Next steps…• To improve the removal efficiency in the bio-oxidation unit, water

addition to the system (BTF and BF) should be optimized along withthe nutrients concentration.

1. Collecting media samples periodically in order to measure moisture andnutrient concentration of the compost media according to standardmethods.

2. Periodically, monitoring pH, conductivity and nutrient (ammonia, nitratenitrogen, total phosphorus) concentration of the sump.

• Since the air flow rate or empty bed residence time (e.g. the size ofthe unit, etc.) will obviously affect the treatment costs, the bio-oxidation performance will be optimized under various operationconditions.

• To improve the removal efficiency in the BTF unit for hydrophobicpollutants, addition of surfactants may be tested.

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Implementation of Air Quality Technology for the Oil and Gas Industry in Coastal Areas: Air Emission Measurements and Control

Contract No. CITP0910-TAMUK0513B

Coastal Impact Assistance Program

Investigator: Dr. David Ramirez

Current Practice

Proposed TSA System

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Project GoalThe development and testing of a thermal-swing adsorption (TSA) system to capture and recover toxic air emissions from point sources (storage condensate tanks)

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Design and Development of TSA System:

Phase I – Bench Scale

Summary Benzene Toluene Ethyl

benzene

m, p-

Xylene

o-Xylene

Average 138 136 0.440 31.8 4.73

Maximum 575 306 11.9 95.0 10.6

Minimum 112 109 1.17 3.31 4.32

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Summary of BTEX Concentrations (ppm) from Bench Scale

Condensate Tank with Sample API, 54.2

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

Benzene Toluene Ethylbenzene m, p-Xylene o-Xylene Xylene (m, pand o)

BT

EX

Em

iss

ion

Ra

te (

lb/y

r)

Experiment Tank 4.09d Promax 3.2

Comparison of Experimental BTEX Emissions with Simulations

from Promax 3.2 and Tanks 4.09D

Recovered liquid hydrocarbons at regeneration temperatures between 80-125°C

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(80-90)°C (105-125)°C

Effect of Regeneration Temperature on the

Liquid Recovery

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Phase II of the TSA System: Pilot Scale

Schematic of the 100 sLpm-Capacity Pilot Scale TSA System

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Phase III of the TSA System:

the 3,000 sLpm Pilot Scale Unit

Pilot Scale TSA System for Continuous Operation

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Phase III of the TSA System: Field Deployment

of the 3,000 sLpm Pilot Scale Unit

Field testing at the Apache site for capturing vapor emissions from the tank battery

Operation Conditions and Removal Efficiencies for the Pilot-Scale TSA Unit During the Field Test

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Adsorption Column 1

Parameter Value

Gas stream temperature 110°F

Gas volumetric flow rate 142 sLpm

Amount of granular

activated carbon in

adsorption column 1

5 kg

Amount of granular

activated carbon in

adsorption column 2

8 kg

Removal efficiency of total

hydrocarbons before

breakthrough

99.6%

Removal efficiency of H2S 100%

Removal efficiency of CO2 96.3%

Adsorption Breakthrough for the Pilot-Scale TSA Unit During the Field Test: Adsorption Column 2

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Next steps…

• The field deployable GC-FID will be used along with the PIDs in order to continuously monitor the concentration of BTEX compounds in the gas phase.

• We would welcome more opportunities to work with Apache/HARC to optimize our field scale unit for removal of BTEX compounds.

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Subsequent phases of this project would be optimization of air flow, water flow and residence time for the most effective BTEX degradation for remote oil and gas facilities, and the deployment of more telemetry and modem communication, with a Programmable Logic Controller (PLC) to remotely monitor unit performance and operating conditions.

Acknowledgements

• This project was funded by the Houston Advanced Research Center’s (HARC) Environmentally Friendly Drilling - Coastal Impacts Technology Program GLO Contract #M11AF00005

• Apache Corporation, Houston and Bryan/College Station, Texas

• Institute for Sustainable Energy and the Environment

• Texas A&M University-Kingsville (TAMUK)

• TAMUK team of students • Shooka Khoramfar• Joshua Robbins• Fasae Olusola• Erich Potthast• Josie Rios

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The environmental crisis is a global problem, and only global action will resolve it.~ Barry Commoner, biologist

Thank you for your attention!

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Mitigation of Vapor Emissions

• Source reduction

• Modifying process

• Thermal combustion

• Flaring

• Catalytic incineration

• Biofiltration

• Condensation

• Membrane separation

• Absorption

• Adsorption

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DestructiveMethods

RecoveryMethods

PreventiveMethods

Storage Tank Emissions

• Oil and condensate tanks are used to store produced liquid at individual well sites.

• Two primary emission loss are:

• Flashing loss, condensate brought from down hole pressure to atmospheric pressure may experience a sudden volatilization of some of the condensate

• Working and breathing losses, whereby some volatilization of stored product occurs through valves and other openings in the tank battery over time. (TCEQ,2010)

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Oil and Condensate Tank Battery at Eagle

Ford Shale

Alamo Area Council of Governments Report, 2014

VOC Emission Inventory at the Eagle Ford Shale

Source Category,

Moderate Scenario

38Source: AACOG,2014

Acknowledgment

We would like to thank the Houston Advanced Research Centre for their grant support for this research.

Thank you !

Recommended exposure limit guidelines for benzene in ambient air

Name of agency Parameter Concentration

American Conference ofGovernmental IndustrialHygienists (ACGIH)

Threshold limit values (TLV) 0.5 ppm

Short-term exposure limit (STEL) 2.5 ppm

National Institute for Occupational Safety and Health (NIOSH)

Recommended exposure limit (REL) based on 10-h time weighted average (TWA)

0.1 ppm

STEL 1.0 ppm

Immediately dangerous to life or health (IDLH)

500 ppm

Occupational Safety andHealth Administration (OSHA)

Permissible exposure limit (PEL) (8 h TWA) for general industry

1.0 ppm

Environmental Protection Agency (EPA)

Inhalation reference concentration (RfC)

0.03 mg m-3

Inhalation unit risk 2.2x10 -6- 7.8xl0-6 μg m-3

40(Source: www.atsdr.cdc.gov)

Available technologies for removal of VOCs

Many processes and technologies have been developed to control VOCs emission. There are six main processes by which a gaseous pollutant may be removed from an air stream.

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Biotreatment

Absorption (wet scrubbing)

Carbon Adsorption

Condensation

Thermal incineration

Flares

In the case of absorption, the target pollutant is transferred to the scrubbing solution. Recovery ofthe solvent might be undertaken by distillation or by stripping the absorbed materials from thesolvent.

Adsorption is an efficient technique for the treatment of low concentration of VOCs wherepollutants get adsorbed onto the surface of activated carbon or zeolites which are used asadsorbents. Adsorption can provide the means for the materials to be more readily recovered.

Condensation is preferable at high pollutant concentration where waste gas treatment involvesrecovery of some valuable solvents from the concentrated waste streams. The VOCs are partiallyrecovered by simultaneous cooling and compressing the gaseous vapors.

For organic pollutants when the concentration is low or recovering the material is not desired,incineration at high temperatures (700-1400 °C) or in the presence of a catalytic such as platinum(300-700 °C) can be used to convert the pollutant to carbon dioxide and water.

For large emissions such as those found in petroleum refineries the pollutant may be flared.

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Description of available technologies for removal of VOCs

Technology Advantages Disadvantages

Biotreatment

Simple and low cost (capitol, operational and maintenance) technologyLow energy requirement, no fuelneededEffective removal of odours and VOCsEnvironmentally friendly without production of by-productsLow carbon emissions

Difficulty in control of pH and moisture in biofiltersRelatively large footprintClogging and pressure drop due to extensive growing of biomass

Absorption(Wet Scrubbing)

Medium capital costsRelatively small footprint Ability to handle particulate and variable loads of the gas stream

Very high operating costsNot effective for most of the VOCsToxic and complex chemicals requirement

Carbon Adsorption

Medium capital costsSmall footprintReliable operation

High operating costsReduced carbon life due to the moisture of the gas streamCreates secondary waste stream due to spent carbon

Incineration

Small footprintReliable and uniform performance for relatively all compounds irrespective of nature and concentration

High operating and capital costsHuge amount of investment in fuel costCreates secondary waste stream (Nox)

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How it works?• In the biofiltration process, contaminated air is moistened and is pumped into the

biofilter. While the air slowly flows upward through the filter media, thecontaminants in the air stream are absorbed and metabolized by themicroorganisms. The purified air passes out of the top of the biofilter and into theatmosphere. Most biofilters that are in operation today can treat odor and VOCs atefficiencies greater that 90%. The technology is best suited to treat relatively lowconcentrations of pollutants (<1000 ppm) and loading rates between 300-500ft3/ft2-hr.

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Schematic of the unit

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Sampling of VOCs

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Tedlar bag sampling

Elimination capacity vs. pollutant loading rate- Apache TAMU #2 tank battery

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Optimization of the BTF-BF unit for removal of hydrophobic pollutants

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Application of fungi

Cont…

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Application of surfactants

Controlling instruments

Water flow rateAir flow rate and Temperature Pressure gauges

pH and Conductivity Biofilter bed moisture Nutrient concentration

50