2,3,7,8-TCDD Equivalent Emissions from Cement Kilns Burning Hazardous Waste
Presented at the AWMA International Specialty Conference on Waste Combustion in Boilers and Industrial Furnaces April, 1994
ABSTRACT
Effective August 21, 1991 the United States Environmental Protection Agency (USEPA) adopted the Boiler and Industrial Furnace (BIF) rules which govern cement kiln operations burning hazardous waste fuel and set limits on cement kiln emissions of metals, HCL/chlorine and organics.
Dioxin testing was required to address the concerns of the USEPA arising from the review of stack test data from municipal waste combustion units. Dioxin emissions tests were developed and designed to meet EPA criteria under worst-case conditions and performed at 15 cement plants. Upon compilation of this data, an evaluation was performed for a correlation between HCl and Cl2 emissions and dioxin emissions. When no correlation was found, additional data analysis revealed a trend between the kiln exit temperature and dioxin emissions.
Additional data was gathered from selected cement plants and the available individual run data was plotted against temperatures at APCD device inlets. The dioxin emissions show a decrease in concentration as a function of decreasing temperature. This corresponds with EPA's concerns about dioxin emissions increasing as a function of stack or APCD temperatures.
In conclusion, temperature seems to be a primary factor for dioxin
formation.
If temperatures can be controlled below 400oF, there may be
a reduction in dioxin emissions from cement kilns whether or not they
burn
hazardous waste fuels.
INTRODUCTION
Effective August 21, 1991 the United States Environmental Protection Agency (USEPA) adopted the Boiler and Industrial Furnace (BIF) rules which govern cement kiln operations burning hazardous waste as fuel. BIF set limits on cement kiln emissions of metals, chloride and organics. Testing was required by August 21, 1992, and if, during the course of testing, the air pollution control device (APCD) in use at the cement kiln recorded temperatures between 450oF and 750oF, then dioxin emission testing was necessary. The dioxin testing was mandated due to a lack of data available from cement kilns for these emissions and USEPA concerns arising in the review of stack test data from municipal waste combustion units.
Approximately fifteen dioxin emissions tests were performed at cement plants. Many of the emissions tests were developed to meet EPA criteria and were designed to be under worst case conditions. A worst case scenario would be defined as maximum waste fuel being burned with the highest allowable chlorine content in addition to the maximum temperature that would be encountered in the APCD. Table 1 lists the results of the emissions tests.
Upon compilation of this data, an evaluation was performed for a correlation between HCl and Cl2 emissions and dioxin emissions. Wide variation in the HCl and Cl2 emissions was observed. No correlation could be obtained between chlorine and dioxin emissions. However, a trend was observed between the kiln exit temperature and dioxin emissions. Higher temperatures were associated with the higher dioxin emissions.
The database was sorted by descending temperatures (Table 2.) and
corrected
to 7% oxygen. Subsequent to the sort, the data was plotted (Plot 1).
The
dioxin emissions appear as a function of stack exit temperature. The
dioxin
emissions show a corresponding decrease in concentration as a function
of temperature when it drops below approximately 585oF with
significant dioxin emissions occurring at temperatures in the 600oF
to 750oF range. This corresponds with EPA's concerns about
dioxin
emissions increasing as a function of stack or APCD temperature
increase.
Subsequent to this finding, we chose one plant in the U.S. that had
eleven
tests performed under varying conditions yielding results exhibiting a
range of temperatures vs. dioxin emissions. Table 3 outlines the
results
for that particular test facility. The corresponding dioxin emissions
are
presented for those emissions tests, during which a similar type of
curve
is observed (Plot 2). Higher dioxin emissions occur during the higher
temperatures
(greater than 450oF and increasing to 495oF) with
a significant decrease in dioxin emissions occurring below 420oF.
CONCLUSION
In conclusion, temperature seems to be a contributing factor to
dioxin
formation. The lower temperature in the APCD may result in lower dioxin
emissions being formed with subsequent lower emissions exiting the
stack.
However, it was noted that hydrocarbon content, alkali content and
chlorine
loading may also be contributing factors in addition to temperature and
need to be investigated further. If temperatures can be controlled
below
450oF, there may be a reduction in dioxin emissions both
from
cement kilns burning and not burning hazardous waste fuels.
| Table 1. Cement kiln dioxin data and corrected values for 7% Oxygen. | ||||||||||||||
|
|
|
|
|
TEQ |
NGDSCM |
TEMP |
TEMP |
|
(dscmm) |
USED |
7% 02 |
DIOXIN at 7% 02 |
7% 02 |
TEMP |
| ASH GROVE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Chanute |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| ASH GROVE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Chanute |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| ASH GROVE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Foreman |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| ASH GROVE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Foreman |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| ASH GROVE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Louisville |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| CONTINENTAL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Hannibal |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| ESSROC |
|
|
|
|
|
|
|
|
|
|
|
|||
| Logansport |
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|||||
| HOLNAM |
|
|
|
|
|
|
|
|
|
|
|
|
||
| Clarksville |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| HOLNAM |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Holly Hill |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| KOSMOS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| LAFARGE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| Alpena |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| LAFARGE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Fredonia |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| LONESTAR |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Greencastle |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| MEDUSA |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Wampum |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| N. TEXAS CEM. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| N. TEXAS CEM. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
||||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| RIVER CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Festus |
|
|
|
|
|
|
|
|
|
|
|
|
||
|
|
|
|
|
|
|
|
|
|
|
|
|
|||
| SOUTHDOWN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Fairborn |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| SOUTHDOWN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Fairborn |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| SOUTHDOWN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Dixie |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| SOUTHDOWN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Dixie |
|
|
|
|
|
|
|
|
|
|
|
|||
|
|
|
|
|
|
|
|
|
|
|
|
||||
| Table 2. Cement kiln dioxin data - temperatures sorted by descending value. | ||||||||||||||
| NAME |
|
|
|
TEQ |
NGD SCM |
TEMP |
|
|
(dscmm) |
USED |
7% O2 |
at 7% 02 |
7% 02 |
TEMP |
| CCC-HANNIBAL |
|
|
2 |
|
|
|
|
|
|
|
|
|
|
|
| CCC-HANNIBAL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-CLARKSVILLE |
|
|
|
|
|
|
|
|
|
|
|
|||
| CCC-HANNIBAL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-CLARKSVILLE |
|
|
|
|
|
|
|
|
|
|
|
|||
| HOLNAM-CLARKSVILLE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|||
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|||
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|||
| LONESTAR-GREENCSTL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| LONESTAR-GREENCSTL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LONESTAR-GREENCSTL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LAFARGE-ALPENA |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LAFARGE-ALPENA |
|
|
|
|
|
|
|
|
|
|
|
|||
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|||
| LAFARGE-ALPENA |
|
|
|
|
|
|
|
|
|
|
|
|||
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| LAFARGE-FRDNIA |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| RIVER CEMENT-FESTUS |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
||
| RIVER CEMENT-FESTUS |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| RIVER CEMENT-FESTUS |
|
|
|
|
|
|
|
|
|
|
|
|
||
| MEDUSA-WAMPUM |
|
|
|
|
|
|
|
|
|
|
|
|||
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| MEDUSA-WAMPUM |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-FOREMAN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| MEDUSA-WAMPUM |
|
|
|
|
|
|
|
|
|
|
|
|||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| N. TEXAS CEMENT |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-DIXIE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-LOUISVILLE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-LOUISVILLE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-LOUISVILLE |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| ASHG-LOUISVILLE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ASHG-CHANUTE |
|
|
|
|
|
|
|
|
|
|
|
|
||
| ESSROC-LOGANSPORT |
|
|
|
|
|
|
|
|
|
|
||||
| ESSROC-LOGANSPORT |
|
|
|
|
|
|
|
|
|
|
|
|||
| ESSROC-LOGANSPORT |
|
|
|
|
|
|
|
|
|
|
||||
| KOSMOS CEMENT CO. |
|
|
|
|
|
|
|
|
|
|
|
|||
| KOSMOS CEMENT CO. |
|
|
|
|
|
|
|
|
|
|
|
|||
| KOSMOS CEMENT CO. |
|
|
|
|
|
|
|
|
|
|
|
|||
| KOSMOS CEMENT CO. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
||
| STHDOWN-FRBRN |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 3. Cement kiln dioxin data - Holnam Holly Hill. | ||||||||||||||
| NAME |
|
|
|
TEQ |
NGDSCM |
TEMP |
TEMP |
|
(dscmm) |
USED |
7% O2 |
at 7% O2 |
7% 02 |
TEMP |
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| HOLNAM-HHILL |
|
|
|
|
|
|
|
|
|
|
|
|
||


BIBLIOGRAPHY
Gossman Consulting. Commercial BIF compliance test results. Hampshire, Illinois. 1993.
Gossman Consulting. Trial burn and certification of compliance test report. Holly Hill, South Carolina. August 1992.
Gossman Consulting. Trial burn and certification of compliance test report. Clarksville, Missouri. July 1992.
Mittelhauser Corporation. Boiler and industrial furnace regulations: certification of compliance for National Cement Company. Lebec, California. August 1992.
Radian Corporation. Boiler and industrial furnace regulations: certification of compliance for Lafarge Corporation. Alpena, Michigan. August 1992.
Radian Corporation. Boiler and industrial furnace regulations: certification of compliance for Lafarge Corporation. Fredonia, Kansas. August 1992.
USEPA. Boiler and industrial furnace regulations: certification of compliance for Southdown, Inc. Knoxville, Tennessee. June 25, 1992.
USEPA. 40 CFR 266: Burning of hazardous waste in boilers and industrial furnaces. Federal Register 1991;56:35