Mo. Code Regs. Ann. tit. 10, § 10-5.550
PURPOSE: This rule limits volatile organic compound emissions from reactor processes and distillation operations in the St. Louis 1997 eight (8)-hour ozone nonattainment area.
PUBLISHER’S NOTE: The secretary of state has determined that the publication of the entire text of the material which is incorporated by reference as a portion of this rule would be unduly cumbersome or expensive. This material as incorporated by reference in this rule shall be maintained by the agency at its headquarters and shall be made available to the public for inspection and copying at no more than the actual cost of reproduction. This note applies only to the reference material. The entire text of the rule is printed here.
(1) Applicability.
(B) Exemptions from the provisions of this rule are as follows:
operation that is designed and operated in a batch mode is not subject to the provisions of this rule;
operation that is part of a polymer manufacturing operation is not subject to the provisions of this rule;
operation operating in a process unit with a total design capacity of less than one (1) gigagram (1,100 tons) per year for all chemicals produced within that unit is not subject to the provisions of this rule except for the reporting and record keeping requirements listed in subsection (4)(D) of this rule; and
or distillation operation with a flow rate less than 0.0085 standard cubic meter per minute or a total volatile organic compound (VOC) concentration less than five hundred (500) parts per million by volume is not subject to the provisions of this rule except for the performance testing requirement listed in subparagraph (3)(B)3.B., paragraph (3)(B)9. and the reporting and record keeping requirements listed in subsection (4)(C) of this rule.
(2) Definitions.
Volatile Organic Compound Emissions from Reactor Processes and Distillation Operations Processes in the Synthetic Organic Chemical Manufacturing Industry, EPA-450/4-91-031, as incorporated by reference in subsection (2)(M) of this rule) that is produced as that chemical for sales as a product, by-product, co-product, or intermediate or for use in the production of other chemicals or compounds.
(3) General Provisions.
(A) Control Requirements.
process unit with a TRE index value less than or equal to one (1.0), the owner or operator shall—
methane and ethane) by ninety-eight (98) weight-percent, or to twenty (20) parts per million by volume, on a dry basis corrected to three percent (3%) oxygen, whichever is less stringent. If a boiler or process heater is used to comply with this paragraph, then the vent stream shall be introduced into the flame zone of the boiler or process heater; or
Flares used to comply with this paragraph shall comply with the requirements of 40 CFR 60.18. 40 CFR 60.18 promulgated as of July 1, 2018 is hereby incorporated by reference in this rule, as published by the Office of the Federal Register. Copies can be obtained from the U.S. Publishing Office Bookstore, 710 N. Capitol Street NW, Washington DC 20401. The flare operation requirement does not apply if a process, not subject to this rule, vents an emergency relief discharge into a common flare header and causes the flare servicing the process subject to this rule to be out of compliance with one (1) or more of the provisions of the flare operation rule.
within a process unit with a TRE index value greater than one (1.0), the owner or operator shall maintain vent stream parameters that result in a calculated total resource effectiveness greater than one (1.0) without the use of a volatile organic compound control device. The TRE index shall be calculated at the outlet of the final recovery device.
(B) Total Resource Effectiveness Determination, Performance Testing, and Exemption Testing.
compliance with the TRE index value in paragraph (3)(A)2. of this rule, engineering assessment may be used to determine process vent stream flow rate, net heating value, and TOC emission rate for the representative operating condition expected to yield the lowest TRE index value.
such engineering assessment and the TRE equation in subparagraph (3)(B)6.A. of this rule is greater than four (4.0), then it is not recommended that the owner or operator perform the measures specified in paragraph (3)(B)5. of this rule.
such engineering assessment and the TRE equation in subparagraph (3)(B)6.A. of this rule is less than or equal to four (4.0), then it is recommended that the owner or operator perform the measurements specified in paragraph (3)(B)5. of this rule.
but is not limited to, the following:
test is representative of current operating practices at the process unit;
data representative of the process under representative operating conditions;
or implied within a permit limit applicable to the process vent;
accepted chemical engineering principles, measurable process parameters, or physical or chemical laws or properties. Examples for analytical methods include, but are not limited to:
based on process stoichiometry to estimate maximum VOC concentration;
rate based on physical equipment design such as pump or blower capacities;
trations based on saturation conditions; and
expected net heating value based on the stream concentration of each organic compound, or, alternatively, as if all TOC in the stream were the compound with the highest heating value; and
cedures used in the engineering assessment shall be documented.
pliance with the control requirements of this rule, the process unit shall be run at representative operating conditions and flow rates during any performance test.
part 60, Appendix A, as specified in 10 CSR 10-6.030(22), shall be used to demonstrate compliance with the emission limit or percent reduction efficiency requirement listed in subparagraph (3)(A)1.A. of this rule:
for selection of the sampling sites. The control device inlet sampling site for determination of vent stream molar composition or TOC (less methane and ethane) reduction efficiency shall be located after the last recovery device but prior to the inlet of the control device, prior to any dilution of the process vent stream, and prior to release to the atmosphere;
appropriate, for determination of gas stream volumetric flow rate;
tor, integrated sampling, and analysis procedure of Method 3 to determine the oxygen concentration (%O2d) for the purpose of determining compliance with the twenty (20) parts per million by volume limit. The sampling site shall be the same as that of the TOC samples, and samples shall be taken during the same time that the TOC samples are taken. The TOC concentration corrected to three percent (3%) oxygen (Cc) shall be computed using the following equation:
17.9
Cc = CTOC × ( ) 20.9 – %O2d
where: Cc = Concentration of TOC (minus methane and ethane) corrected to three percent (3%) O2, dry basis, parts per million by volume; CTOC = Concentration of TOC (minus methane and ethane), dry basis, parts per million by volume; and %O2d = Concentration of oxygen, dry basis, percent by volume;
centration of TOC (less methane and ethane) at the outlet of the control device when determining compliance with the twenty (20) parts per million by volume limit, or at both the control device inlet and outlet when the reduction efficiency of the control device is to be determined.
each run shall be one (1) hour in which either an integrated sample or four (4) grab samples shall be taken. If grab sampling is used then the samples shall be taken at fifteen (15)- minute intervals.
TOC (less methane and ethane) shall be determined using the following equation:
Ei – Eo R = × 100 Ei
where: R = Emission reduction, percent by weight. Ei = Mass rate of TOC (minus methane and ethane) entering the control device, kilogram TOC per hour. Eo = Mass rate of TOC (minus methane and ethane) discharged to the atmosphere, kilogram TOC per hour.
shall be computed using the following equations: n Ei = K2 (∑ CijMij) Qi j=1 ; and n Eo = K2 (∑ CojMoj) Qo j=1
where: Cij, Coj = Concentration of sample component “j” of the gas stream at the inlet and outlet of the control device, respectively, dry basis, parts per million by volume; Mij, Moj = Molecular weight of sample component “j” of the gas stream at the inlet and outlet of the control device, respectively, grams per gram-mole; Qi, Qo = Flow rate of gas stream at the inlet and outlet of the control device, respectively, dry standard cubic meters per minute; K2 = 2.494 × 10-6 (liters per minute) (gram-mole per standard cubic meter)(kilogram per gram)(minute per hour), where standard temperature for (gram-mole per standard cubic meter) is twenty degrees Celsius (20 °C); and n = Number of components in the sample.
the sum of the individual components and shall be computed for each run using the following equation: n CTOC = ∑ Cj j=1
where: CTOC = Concentration of TOC (minus methane and ethane), dry basis, parts per million by volume; Cj = Concentration of sample component “j”, dry basis, parts per million by volume; and n = Number of components in the sample; and
with a design heat input capacity of forty-four (44) megawatts or greater, or a boiler or process heater into which the process vent stream is introduced with the primary fuel, is used to comply with the control requirements, an initial performance test is not required.
the control requirements of this rule, the flare shall comply with the requirements of 40 CFR part 60.18.
used to determine compliance with the TRE index value:
for selection of the sampling site.
stream molar composition determination and flow rate prescribed in subparagraph (3)(B)5.B. and subparagraph (3)(B)5.C. of this rule shall be, except for the situations outlined in part (3)(B)5.A.(II) of this rule, after the final recovery device, if a recovery system is present, prior to the inlet of any control device, and prior to any post-reactor or post-distillation unit introduction of halogenated compounds into the process vent stream. No traverse site selection method is needed for vents smaller than ten (10) centimeters in diameter.
reactor or distillation vent stream is normally conducted through the final recovery device—
stream flow rate and molar composition shall be prior to the final recovery device and prior to the point at which any nonreactor or nondistillation stream or stream from a nonaffected reactor or distillation unit is introduced. Method 18 shall be used to measure organic compound concentrations at this site;
recovery device shall be determined by measuring the organic compound concentrations using Method 18 at the inlet to the final recovery device after the introduction of all vent streams and at the outlet of the final recovery device; and
recovery device determined according to subpart (3)(B)5.A.(II)(b) of this rule shall be applied to the organic compound concentrations measured according to subpart (3)(B)5.A.(II)(a) of this rule to determine the concentrations of organic compounds from the final recovery device attributable to the reactor or distillation vent stream. The resulting organic compound concentrations are then used to perform the calculations outlined in subparagraph (3)(B)5.D. of this rule;
stream shall be determined as follows:
centration of organic compounds including those containing halogens; and
specified in 10 CSR 10-6.040(16), to measure the concentration of carbon monoxide and hydrogen;
determined using Method 2, 2A, 2C, or 2D, as appropriate;
methane and ethane), (ETOC), in the vent stream shall be calculated using the following equation:
n
ETOC = K2 ∑ CjMjQs j=1
where: ETOC = Emission rate of TOC (minus methane and ethane) in the sample, kilograms per hour; K2 = Constant, 2.494 × 10-6 (liters per parts per million)(gram-moles per standard cubic meter)(kilogram per gram)(minute per hour), where standard temperature for (grammole per standard cubic meter)(g-mole/scm) is twenty degrees Celsius (20 °C); Cj = Concentration of compound “j”, on a dry basis, in parts per million as measured by Method 18, as indicated in subparagraph (3)(B)3.C. of this rule; Mj = Molecular weight of sample “j”, grams per gram-mole; Qs = Vent stream flow rate (standard cubic meters per minute) at a temperature of twenty degrees Celsius (20 °C); and n = Number of components in the sample;
centration (by volume) of compounds containing halogens (parts per million by volume, by compound) shall be summed from the individual concentrations of compounds containing halogens which were measured by Method 18; and
stream shall be calculated using the equation:
n
HT = K1 ∑ CjHj (1 – Bws) j=1
where: HT = Net heating value of the sample (megajoule per standard cubic meter), where the net enthalpy per mole of vent stream is based on combustion at twenty-five degrees Celsius (25 °C) and seven hundred sixty (760) millimeters of mercury, but the standard temperature for determining the volume corresponding to one mole is twenty degrees Celsius (20 °C), as in the definition of Qs (vent stream flow rate); K1 = Constant, 1.740 × 10-7 (parts per million)-1 (gram-mole per standard cubic meter), (megajoule per kilocalorie), where standard temperature for (gram-mole per standard cubic meter) is twenty degrees Celsius (20 °C); 10 CSR 10-5
Bws = Water vapor content of the vent stream, proportion by volume: except that if the vent stream passes through a final stream jet and is not condensed, it shall be assumed that Bws =0.023 in order to correct to 2.3 percent moisture; Cj = Concentration on a dry basis of compound “j” in parts per million, as measured for all organic compounds by Method 18 and measured for hydrogen and carbon monoxide by the American Society for Testing and Materials D1946-90(2015)e1, as specified in 10 CSR 10-6.040(16); Hj = Net heat of combustion of compound “j”, kilocalorie per gram-mole, based on combustion at twenty-five degrees Celsius (25°C) and seven hundred sixty (760) millimeters of mercury. The heat of combustion of vent stream components shall be determined using ASTM D4809-13, as specified in 10 CSR 10-6.040(25), if published values are not available or cannot be calculated; and n = Number of components in the sample.
(TRE) index.
shall be calculated using the following equation:
TRE = [a + b (Qs) + c (Ht) + d (ETOC)] ETOC where: TRE = TRE index value; ETOC = Hourly emission rate of TOC (minus methane and ethane), (kilograms per hour) as calculated in subparagraph (3)(B)5.D. of this rule; Qs = Vent stream flow rate standard cubic meters per minute at a standard temperature of twenty degrees Celsius (20 °C); HT = Vent stream net heating value (megajoules per standard cubic meter), as calculated in subparagraph (3)(B)5.F. of this rule; and a,b,c,d = Coefficients presented in Table 1. Effectiveness for Nonhalogenated and Coefficients for Total Resource Effectiveness for Nonhalogenated and Halogenated Vent Streams
Values of Coefficients
Type of Stream
Values of Coefficients Nonhalogenated
Halogenated
Values of Coefficients
stream shall use the applicable coefficients in Table 1 to calculate the TRE index value based on a flare, a thermal incinerator with zero percent (0%) heat recovery, and a thermal incinerator with seventy percent (70%) heat recovery, and select the lowest TRE index value.
with a halogenated vent stream, determined as any stream with a total concentration of halogen atoms contained in organic compounds of two hundred (200) parts per million by volume or greater, shall use the applicable coefficients in Table 1 to calculate the total resource effectiveness index value based on a thermal incinerator and scrubber.
facility seeking to comply with paragraph (3)(A)2. of this rule shall recalculate the flow rate and TOC concentration for that affected facility whenever process changes are made. Examples of process changes include changes in production capacity, feedstock type, or catalyst type, or whenever there is replacement, removal, or addition of recovery equipment. The flow rate and VOC concentration shall be recalculated based on test data, or on best engineering estimates of the effects of the change to the recovery system.
TRE index <1.0, the owner or operator shall notify the state Air Pollution Control Coefficients for Total Resource Table 1 Halogenated Vent Streams
Control Device Basis
Flare
Thermal incinerator 0 percent heat recovery
Thermal incinerator 70 Percent heat recovery
Thermal incinerator and scrubber Values of Coefficients
a b c d
2.129 0.183 -0.005 0.359
3.075 0.021 -0.037 0.018
3.803 0.032 -0.042 0.007
5.470 0.181 -0.040 0.004
Program within one (1) week of the recalculation and conduct a performance test according to the methods and procedures required by subsection (3)(B) of this rule.
a process vent stream has a VOC concentration below five hundred (500) parts per million by volume, the following procedures shall be followed:
as specified in subparagraph (3)(B)3.A. of this rule;
CFR part 60, Appendix A, as specified in 10 CSR 10-6.030(22), shall be used to measure concentration; alternatively, any other method or data that has been validated according to the protocol in Method 301 of 40 CFR part 63, Appendix A may be used.
following procedures shall be used to calculate parts per million by volume concentration:
for each run shall be one (1) hour in which either an integrated sample or four (4) grab samples shall be taken. If grab sampling is used, then the samples shall be taken at approximately equal intervals in time, such as fifteen (15)-minute intervals during the run; and
(minus methane and ethane) shall be calculated using Method 18 according to subparagraph (3)(B)3.D. of this rule.
the following procedures shall be used to calculate parts per million by volume TOC concentration:
only if a single VOC is greater than fifty percent (50%) of total VOC, by volume, in the process vent stream;
composition may be determined by either process knowledge, test data collected using an appropriate EPA method or a method of data collection validated according to the protocol in Method 301 of 40 CFR part 63, Appendix A. Examples of information that could constitute process knowledge include calculations based on material balances, process stoichiometry, or previous test results provided the results are still relevant to the current process vent stream conditions;
tion gas for Method 25A shall be the single VOC present at greater than fifty percent (50%) of the total VOC by volume;
25A shall be fifty (50) parts per million by volume;
acceptable if the response from the high-level calibration gas is at least twenty (20) times the standard deviation of the response from the zero calibration gas when the instrument is zeroed on the most sensitive scale; and
shall be corrected to three percent (3%) oxygen using the procedures and equation in subparagraph (3)(B)3.C. of this rule; and
demonstrate that the concentration of TOC including methane and ethane measured by Method 25A is below two hundred fifty (250) parts per million by volume with VOC concentration below five hundred (500) parts per million by volume to qualify for the low concentration exclusion.
(C) Monitoring Requirements.
facility that uses an incinerator to seek to comply with the TOC emission limit specified under subparagraph (3)(A)1.A. of this rule shall install, calibrate, maintain, and operate according to manufacturer’s specifications: a temperature monitoring device equipped with a continuous recorder and having a minimum accuracy of plus or minus one percent (± 1%) of the temperature being measured expressed in degrees Celsius or plus or minus (±) 0.5 °C, whichever is more accurate.
catalytic incinerator is used, a temperature monitoring device shall be installed in the firebox.
used, temperature monitoring devices shall be installed in the gas stream immediately before and after the catalyst bed.
facility that uses a flare to seek to comply with subparagraph (3)(A)1.B. of this rule shall install, calibrate, maintain, and operate according to manufacturer’s specifications, a heat-sensing device, such as an ultraviolet beam sensor or thermocouple, at the pilot light to indicate continuous presence of a flame.
facility that uses a boiler or process heater with a design heat input capacity less than forty-four (44) megawatts to seek to comply with subparagraph (3)(A)1.A. of this rule shall install, calibrate, maintain, and operate according to the manufacturer’s specifications, a temperature monitoring device in the firebox. The monitoring device should be equipped with a continuous recorder and have a minimum accuracy of plus or minus one percent (± 1%) of the temperature being measured expressed in degrees Celsius or plus or minus (±) 0.5 °C, whichever is more accurate. Any boiler or process heater in which all vent streams are introduced with primary fuel is exempt from this requirement.
facility that seeks to demonstrate compliance with the total resource effectiveness index limit specified under paragraph (3)(A)2. of this rule shall install, calibrate, maintain, and operate according to manufacturer’s specifications the following equipment:
recovery device in the recovery system—
monitor equipped with a continuous recorder; and
ped with continuous recorders;
recovery device in the recovery system, a condenser exit (product side) temperature monitoring device equipped with a continuous recorder and having a minimum accuracy of plus or minus one percent (± 1%) of the temperature being monitored expressed in degrees Celsius or plus or minus (±) 0.5 °C, whichever is more accurate;
final recovery device unit in the recovery system, in integrating regeneration stream flow monitoring device having a minimum accuracy of plus or minus ten percent (± 10%), capable of recording the total regeneration stream mass flow for each regeneration cycle; and a carbon bed temperature monitoring device having a minimum accuracy of plus or minus one percent (± 1%) of the temperature being monitored expressed in degrees Celsius or plus or minus (±) 0.5 °C, whichever is more accurate, and capable of recording the carbon bed temperature after each regeneration and within fifteen (15) minutes of completing any cooling cycle; or
genated streams after an incinerator, boiler, or process heater, the following monitoring equipment is required for the scrubber—
ped with a continuous recorder; and
continuous recorders to be located at the scrubber influent for liquid flow and the scrubber inlet for gas stream flow.
vent using a vent system that contains bypass lines that could divert a vent stream away from the combustion device used shall either—
operate a flow indicator that provides a record of vent stream flow at least once every fifteen (15) minutes. The flow indicator shall be installed at the entrance to any bypass line that could divert the vent stream away from the combustion device to the atmosphere; or
closed position with a car-seal or a lock-andkey type configuration. A visual inspection of the seal or closure mechanism shall be performed at least once every month to ensure that the valve is maintained in the closed position and the vent stream is not diverted through the bypass line.
(4) Reporting and Record Keeping.
(A) Each reactor process or distillation operation subject to this rule shall keep records of the following parameters measured during a performance test or TRE determination required under subsection (3)(B) of this rule and required to be monitored under subsection (3)(C) of this rule.
to the provisions of this rule seeks to demonstrate compliance with subparagraph (3)(A)1.A. of this rule through the use of either a thermal or catalytic incinerator—
the incinerator (or the average temperature upstream and downstream of the catalyst bed for a catalytic incinerator), measured at least every fifteen (15) minutes and averaged over the same time period of the performance testing; and 10 CSR 10-5
determined as specified in paragraph (3)(B)3. of this rule achieved by the incinerator, or the concentration of TOC (parts per million by volume, by compound) determined as specified in paragraph (3)(B)3. of this rule at the outlet of the control device on a dry basis corrected to three percent (3%) oxygen.
to the provisions of this rule seeks to demonstrate compliance with subparagraph (3)(A)1.A. of this rule through the use of a boiler or process heater and the boiler or process heater is not exempt from these requirements due to all vent streams being introduced with primary fuel—
which the vent stream is introduced into the boiler or process heater; and
ture of the boiler or process heater with a design heat input capacity of less than fortyfour (44) megawatts measured at least every fifteen (15) minutes and averaged over the same time period of the performance test.
to the provisions of this rule seeks to demonstrate compliance with subparagraph (3)(A)1.B. of this rule through the use of a smokeless flare; flare design (i.e., steamassisted, air-assisted, or nonassisted), all visible emission readings, heat content determinations, flow rate measurements, and exit velocity determinations made during the performance test, continuous records of the flare pilot flame monitoring, and records of all periods of operations during which the pilot flame is absent.
to the provisions of this rule seeks to demonstrate compliance with paragraph (3)(A)2. of this rule—
performed to determine the flow rate, and volatile organic compound concentration, heating value, and TRE index value of the vent stream; and
ing final recovery device parameters:
recovery device in the recovery system, the exit specific gravity (or alternative parameter which is a measure of the degree of absorbing liquid saturation, if approved, by the permitting authority), and average exit temperature of the absorbing liquid measured at least fifteen (15) minutes and averaged over the same time period of the performance testing (both measured while the vent stream is normally routed and constituted);
recovery device in the recovery system, the average exit (product side) temperature measured at least every fifteen (15) minutes and averaged over the same time period of the performance testing while the vent stream is routed and constituted normally; or
the final recovery device in the recovery system, the total stream mass or volumetric flow measured at least every fifteen (15) minutes and averaged over the same time period of the performance test (full carbon bed cycle), temperature of the carbon bed after regeneration (and within fifteen (15) minutes of completion of any cooling cycle(s)), and duration of the carbon bed steaming cycle (all measured while the vent stream is routed and constituted normally).
(4)(A)4.A. or (4)(A)4.B. of this rule, the concentration level or reading indicated by the organics monitoring device at the outlet of the absorber, condenser, or carbon adsorber, measured at least every fifteen (15) minutes and averaged over the same time period as the performance testing while the vent stream is normally routed and constituted.
(B) Each reactor process or distillation operation seeking to comply with paragraph (3)(A)2. of this rule shall also keep records of the following information:
feedstock type, or catalyst type, or of any replacement, removal, and addition of recovery equipment or reactors and distillation units; and
TOC concentration, or TRE value performed according to paragraph (3)(B)7. of this rule.
(500) parts per million by volume.
AUTHORITY: section 643.050, RSMo 2016.* Original rule filed July 15, 1999, effective Feb. 29, 2000. Amended: Filed March 20, 2019, effective Jan. 30, 2020. *Original authority: 643.050, RSMo 1965, amended 1972, 1992, 1993, 1995, 2011.