# Technical Memorandum

TO: Brenda Shine, Environmental Engineer Refining and Chemicals Group, SPPD (E143-01)

FROM: Eric Goehl, Environmental Protection Specialist Refining and Chemicals Group, SPPD (E143-01)

DATE: October 15, 2012

SUBJECT: Summary of Delayed Coking Un it Emission Source Test Reports

I. Purpose The objective of this document is to provide a summary of the Delayed Coking Unit (DCU) emission source test reports received by the EPA from the 2011 Information Collection Request (ICR) of the Petroleum Refinery industry.

II. Background On April 1, 2011, the EPA sent an ICR to facilities in the U.S. petroleum refining industry. The ICR was comprehensive and designed to collect information on processing characteristics, crude slate characteristics, emissi ons inventories and source testing to bolster our current data and fill known data gaps. The I CR had four components: (1) a questionnaire on processes and controls to be completed by all petroleum refineries (Component 1); (2) an emissions inventory to be developed by all petroleum refineries using the emissions estimation protocol developed for this effort (Component 2) ; (3) distillation feed sampling and analysis to be conducted by all petroleum refineries (Component3); and (4) emissions source testing to be completed in accordance with an EPA-approved protocol for specific sources at specific petroleum refineries(Component 4). Component 4 of the ICR required source testing for twelve different types of emission sources or units: fluid catalytic cracking units (FCCU), thermal catalytic cracking units, catalytic reforming units, sulfur recoveryunits, delayed coking units, fluid coking units, hydrocracking units, hydrogen plants, asphalt blowing units, fuelgas systems, cooling water systems, and wastewater treatment systems. This memorandum summarizes the results of the DCU sources tests. A similar memorandum is available for the other sources required to be tested as a result of

## this ICR. Facilities often claimed specific process information as CBI, and included that information in the CBI version of the emission source test report stored in the EPA’s CBI office in Research Triangle Park, NC. However, emi ssions data cannot be claimed as CBI. This memorandum summarizes and presents only non-CBI data.

III. Source-specific Testing Program Below is a list of facilities that submitted the required emission source test report for their DCU.

• BP Husky - Oregon, OH (OH2A0910)

• Houston Refining - Houston, TX (TX3B1200) This facility voluntary submitted an emission source test report.

• ExxonMobil - Baytown, TX (TX3B1160)

• Hovensa - Christiansted, VI (VI6A1530) This facility submitted an emission source te st report as part of ICR Component 1. This data was included in this summary b ecause the DCU was tested recently (MaySeptember 2010).

• Marathon Petroleum - Garyville, LA (LA3C0610) The following facilities did not submit the required emission source test report. (Note: The EPA was made aware that coke drums often do not vent for more than twenty minutes, this is not long enough to perform an emission source test. Therefore, the EPA granted an exemption to any facility that had a delayed coking operation that vented for less than twenty minutes.)

• Chevron Texaco Pascagoula, MS (MS3C0740) – Facility submitted data indicating the cycle vents for less than 20 minutes.

• ExxonMobil Joliet Refinery, Channahon, IL(IL2A0410) – Facility provided documentation that they use a unique feature to quench their drum and do not have a vent. Therefore they have little to no emissions from their DCU.

• Coffeyville Resources Refining, Coffeyville, KS (KS2C0460) – Facility submitted data indicating the cycle vents for less than 20 minutes.

• ConocoPhillips Company, Lake Charles Refinery, Westlake, LA (LA3C0570) - Facility submitted data indicating the cycle vents for less than 20 minutes.

2

## • BP Texas City Refinery, Texas City, TX (TX3B1110) - Facility submitted data indicating the cycle vents for less than 20 minutes.

• Giant Yorktown Refinery, Grafton, VA (VA1 A1390) - Facility was not operating at the time the ICR was sent out. Owners or operators of the DCU at these facilities were required to test for:

• Speciated volatile organic h azardous air pollutants (HAP)

• Speciated semi-volatile organic HAP

• Total hydrocarbons, methane, and ethane

• Aldehydes

• Carbon monoxide

• Hydrogen sulfide, carbonyl sulfide, and carbon disulfide

• Hydrogen chloride, chlorine, hydrog en fluoride, and hydrogen cyanide

• Total reduced sulfur compounds

• Mercury (speciated)

• Multiple metals

• Particulate matter (PM, PM 2.5 

## filterable, and PM condensable)

• NO X 

## , SO 2 

## , O 2 

## , CO 2 

## , moisture, and gas flow rate.

The EPA required that the data collected from the emission source testing to be reported using the EPA Electronic Reporting Tool (ERT). The ERT is a Microsoft® Access database application. If the facility c onducted testing using a method not currently supported by the ERT, the facility was required to report the results in the Refinery Testing Supplement, a Microsoft® Excel spreadsheet. After completing the Refinery Te sting Supplement, the refineries were also to submit an electronic copy of the emission te st report, preferably in PDF format.

IV. Results A summary of the emission results for the DCU are provided in attached spreadsheet. In order to better characterize the reported data from the emission test reports, detection level information was provided in the attached summar y spreadsheet. The following designations were used to describe the detection levels of the reported emissions data.

• DLL = Detection Level Limited = 1 or 2 runs below detection limit

3

## 4 • BDL = Below Detection Limit = All three runs are below detection limit

• No designation = All three r uns are above detection limit

### Summary of Delayed Coking Units Test Report Data

Detection Level (DL) lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle

75-07-0 Acetaldehyde BDL 7.10E-01 3.60E-03 2.75E-02 50-00-0 Formaldehyde BDL 1.20E-01 2.60E-04 1.83E-02 74-90-8 Hydrogen cyanide DLL 2.30E-03 BDL 1.81E-04 1.92E-03 Propanal BDL 1.30E+00 4.00E-03 7647-01-0 Hydrogen Chloride DLL 1.50E-01 DLL 3.24E-03 7782-41-4 Hydrogen Fluoride BDL 3.60E-03 BDL 3.18E-03 Hydrogen Sulfide 42.50 7.14E+00 3.72E+00 DLL 3.83E-02

1 Included 2nd run in this avg, facility wanted to exclude 2nd run from avg 67-64-1 Acetone BDL 8.20E-01 BDL 1.30E-03 3.02E-01 750-05-8 Acetonitrile BDL 1.60E+00 DLL 1.25E-02 DLL 4.87E-01 107-02-8 Acrolein BDL 6.60E-01 BDL 6.60E-04 BDL 5.91E-01 107-13-1 Acrylonitrile BDL 5.80E-01 BDL 1.75E-03 BDL 1.25E-03 71-43-2 Benzene DLL 0.76 DLL 1.90E+00 DLL 3.41E-01 DLL 1.20E-02 BDL 1.10E+01 106-99-0 1,3-Butadiene BDL 4.70E-01 BDL 6.50E-04 BDL 1.25E-03 75-15-0 Carbon Disulfide BDL 1.20E-01 BDL 1.58E-01 BDL 1.33E-02 Carbonyl Sulfide BDL 1.20E+00 BDL 3.69E-01 BDL 1.96E-02 108-90-7 Chlorobenzene DLL 2.90E-01 BDL 8.00E-04 BDL 1.25E-03 98-82-8 Cumene (Isopropylbenzene) DLL 1.60E-01 DLL 4.78E-03 BDL 1.34E-03 106-93-4 1,2-Dibromoethane BDL 1.70E+00 5.00E-01 BDL 1.25E-03 100-41-4 Ethylbenzene DLL 5.70E-01 1.21E-01 DLL 4.49E-03 110-54-3 Hexane DLL 7.00E-01 BDL 1.19E-01 BDL 1.47E-03 Isooctane 108-10-1 Methyl iso-Butyl Ketone DLL 1.00E-01 BDL 5.70E-04 BDL 3.18E-01 1634-04-4 Methyl t-Butyl Ether (MTBE) DLL 1.10E-01 9.50E-03 BDL 1.25E-03 75-09-2 Methylene Chloride DLL 4.40E+00 1.81E-03 1.54E-02 98-95-3 Nitrobenzene DLL 4.20E-01 BDL 7.86E-03 BDL 6.86E-03 79-46-9 2-Nitropropane DLL 4.30E-01 BDL 2.11E-02 BDL 4.00E-03 109-66-0 Pentane DLL 6.80E-01 DLL 2.92E-01 BDL 2.95E-03 100-42-5 Styrene DLL 1.80E-01 DLL 3.40E-03 BDL 1.35E-03 127-18-4 Tetrachloroethene BDL 1.70E+00 BDL 6.44E-03 BDL 1.25E-03 108-88-3 Toluene 2.66 DLL 6.80E+00 DLL 1.30E+00 DLL 1.28E-01 BDL 1.30E+01 Trichloroethene BDL 1.70E+00 BDL 7.54E-03 BDL 3.00E-01 540-84-1 2,2,4-Trimethylpentane DLL 1.00E-01 BDL 4.90E-04 BDL 1.26E-03 1330-20-7 Xylene o-Xylene DLL 1.30E+00 1.85E-01 DLL 7.16E-03 m&p-Xylenes 7.62E-01 DLL 3.45E-02 p-Xylene DLL 2.70E+00 VOLATILE ORGANIC HAP 1 TX3B1200 Houston Refining Houston, TX VI6A1530 Hovensa Christiansted, VI

CAS # Compound OH2A0910 BP-Husky Oregon, OH TX3B1160 ExxonMobil Baytown, TX LA3C0610 - Marathon Petroleum Garyville, LA

### Summary of Delayed Coking Units Test Report Data

Detection Level (DL) lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle TX3B1200 Houston Refining Houston, TX VI6A1530 Hovensa Christiansted, VI

CAS # Compound OH2A0910 BP-Husky Oregon, OH TX3B1160 ExxonMobil Baytown, TX LA3C0610 - Marathon Petroleum Garyville, LA

VOC

0.99 83-32-9 Acenaphthene 1.47E-02 6.10E-03 DLL 2.84E-04 6.99E-02 209-96-8 Acenaphthylene 2.88E-03 BDL 7.86E-03 BDL 2.20E-05 4.27E-03 62-53-3 Aniline BDL 1.30E-02 BDL 7.86E-03 DLL 2.34E-05 5.68E-02 120-12-7 Anthracene 6.00E-02 1.23E-02 9.81E-04 1.47E-01 92-87-5 Benzidine BDL 9.40E-02 BDL 7.86E-02 BDL 2.29E-04 56-55-3 Benzo(a)Anthracene 5.10E-03 DLL 6.44E-03 DLL 1.08E-04 3.10E-02 205-99-2 Benzo(b)Fluoranthene DLL 3.70E-03 BDL 7.86E-03 DLL 8.70E-06 6.60E-03 207-08-9 Benzo(k)Fluoranthene BDL 4.80E-03 BDL 7.86E-03 BDL 4.80E-06 5.32E-03 191-24-2 Benzo(ghi)Perylene 3.20E-03 BDL 7.86E-03 DLL 1.30E-05 1.44E-02 50-32-8 Benzo(a)Pyrene 4.99E-03 DLL 4.27E-03 2.18E-05 2.74E-02 192-97-2 Benzo(e)Pyrene 2.90E-03 DLL 2.64E-03 1.63E-05 92-52-4 Biphenyl 2.00E-02 4.06E-03 3.89E-04 1319-77-3 Cresols 4.54E-02 BDL 7.86E-03 218-01-9 Chrysene* 6.70E-03 DLL 7.86E-03 1.28E-04 3.21E-02 53-70-3 Dibenzo(a,h)Anthracene* DLL 1.20E-03 BDL 7.86E-03 DLL 5.90E-06 1.03E-02 132-64-9 Dibenzofuran 1.77E-02 3.07E-03 1.21E-04 3.74E-02 192-65-4 Dibenzo(a,e)pyrene DLL 1.90E-03 DLL 7.86E-03 BDL 3.60E-06 119-90-4 3,3'-Dimethoxybenzidine BDL 2.20E-02 DLL 2.91E-02 DLL 1.81E-04 60-11-7 Dimethylaminobenzene BDL 3.80E-03 BDL 7.86E-03 BDL 1.20E-05 57-97-6 7,12-Dimethybenz(a)anthracene DLL 6.00E-03 BDL 7.86E-03 BDL 3.60E-06 119-93-7 3,3'-Dimethylbenzidine BDL 2.80E-02 BDL 7.86E-03 BDL 1.74E-04 122-09-8 a,a-Dimethylphenethylamine BDL 1.30E-02 BDL 1.97E-02 BDL 7.22E-05 105-67-9 2,4-Dimethylphenol 2.04E-02 BDL 7.86E-03 1.14E-04 8.63E-02 206-44-0 Fluoranthene 7.30E-03 BDL 7.86E-03 1.75E-04 2.44E-02 86-73-7 Fluorene 4.96E-02 1.52E-02 9.04E-04 1.82E-01 193-39-5 Indeno(1,2,3-cd)Pyrene 9.12E-04 BDL 6.14E-03 DLL 4.60E-06 6.74E-03 78-59-1 Isophorone BDL 4.40E-03 BDL 6.14E-03 BDL 1.35E-05 56-49-5 3-Methylcholanthrene BDL 5.90E-03 BDL 6.14E-03 3.60E-06 91-57-6 2-Methylnaphthalene 7.27E-01 2.56E-01 1.32E-02 2.91E+00 91-20-3 Naphthalene 0.82 4.08E-01 1.46E-01 5.14E-03 1.74E+00 198-55-0 Perylene DLL 4.80E-04 BDL 7.86E-03 BDL 3.60E-06 85-01-8 Phenanthrene 1.46E-01 2.51E-02 2.95E-03 4.62E-01 108-95-2 Phenol 1.79E-02 BDL 7.86E-03 BDL 1.82E-05 1.21E-01 106-50-3 1,4-Phenylenediamine BDL 3.80E-02 BDL 7.86E-02 BDL 1.08E-04 129-00-0 Pyrene 2.74E-02 5.21E-03 7.96E-04 8.01E-02 95-53-4 o-Toluidine 6.70E-03 DLL 6.86E-03 BDL 2.37E-05 Total POM 1.49E+00 SVOC

### Summary of Delayed Coking Units Test Report Data

Detection Level (DL) lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle DL lb/cycle TX3B1200 Houston Refining Houston, TX VI6A1530 Hovensa Christiansted, VI

CAS # Compound OH2A0910 BP-Husky Oregon, OH TX3B1160 ExxonMobil Baytown, TX LA3C0610 - Marathon Petroleum Garyville, LA

7400-36-0 Antimony 2.20E-06 BDL 1.60E-05 BDL 2.87E-07 7440-38-2 Arsenic

. DLL 5.20E-06 BDL 9.65E-06 BDL 1.15E-06 7440-41-7 Beryllium DLL 3.20E-07 BDL 7.98E-07 BDL 2.87E-07 7440-43-9 Cadmium 1.10E-06 DLL 3.20E-05 5.79E-07 7440-47-3 Chromium 3.40E-05 1.40E-04 1.37E-05 7439-92-1 Lead 1.35E-04 1.23E-05 6.67E-07 7439-96-5 Manganese 9.69E-05 7.47E-04 8.50E-06 7440-02-0 Nickel 1.78E-04 3.31E-04 6.78E-06 7782-22-4 Selenium DLL 4.90E-05 DLL 9.22E-05 BDL 2.87E-06 7440-48-4 Cobalt 4.40E-06 BDL 9.88E-05 1.57E-06 7439-97-6 Elemental Mercury DLL 8.60E-07 BDL 3.03E-05 BDL 2.38E-06 Oxidized Mercury DLL 4.20E-06 BDL 1.41E-05 DLL 7.98E-07 Total Mercury DLL 5.00E-06 BDL 3.28E-06 18540-29-9 Hexavalent Chromium

7664-41-7 Ammonia 630-08-0 Carbon Monoxide 1.67E+00 2.78E-03 BDL 2.97E-04 7782-50-5 Chlorine BDL 4.00E-04 Chlorine gas DLL 1.13E-03 67-56-1 Methanol BDL 1.90E-01 DLL 8.90E-04 1.70E-05 74-82-8 Methane 263.00 3.21E+02 7.53E+01 5.13E+00 74-84-0 Ethane 67.20 5.49E+01 2.14E+01 7.70E-01 75-69-4 Trichlorofluoromethane 74-83-9 Bromomethane 10102-43-9 Nitric Oxide ND 9.38E-04 BDL 3.95E-04 Sulfur Dioxide ND 4.47E-02 DLL 7.65E-04 Total Reduced Sulfur 1.58E+01 DLL 1.34E-02

Condensible Particulate 3.96 4.94E-01 1.36E+00 3.23E-01 Filterable Particulate 0.34 9.99E-01 8.23E-01 3.97E-01 Filterable PM2.5 Total PM2.5 Total PM 4.29 2.38E+00 2.18E+00 7.21E-01 6.16E+01 METALS