Wis. Admin. Code Department of Natural Resources NR 440.675

Current through November 25, 2024

Section NR 440.675 - Volatile organic compound (VOC) emissions from the synthetic organic chemical manufacturing industry (SOCMI) air oxidation unit processes

(1) APPLICABILITY AND DESIGNATION OF AFFECTED FACILITY.

(a) The provisions of this section apply to each affected facility designated in par.

(b) that produces any of the chemicals listed in sub. (8) as a product, co-product, by-product or intermediate, except as provided in par. (c). (b) The affected facility is any of the following for which construction, modification or reconstruction commenced after October 21, 1983:

1. Each air oxidation reactor not discharging its vent stream into a recovery system.

2. Each combination of an air oxidation reactor and the recovery system into which its vent stream is discharged.

3. Each combination of 2 or more air oxidation reactors and the common recovery system into which their vent streams are discharged.

(c) Each affected facility that has a total resource effectiveness (TRE) index value greater than 4.0 is exempt from all provisions of this section except for subs. (3), (5) (f), (6) (h) and (L).

Note: The intent of these standards is to minimize the emissions of VOC through the application of best demonstrated technology (BDT). The numerical emission limits in these standards are expressed in terms of total organic compounds (TOC), measured as TOC minus methane and ethane. This emission limit reflects the performance of BDT.

(d)

1. Owners or operators of process vents that are subject to this section may choose to comply with the provisions of 40 CFR part 65, subpart D, as in effect on December 14, 2000, to satisfy the requirements of subs. (3) to (6). The provisions of 40 CFR part 65, subpart D, as in effect on December 14, 2000, also satisfy the criteria of par. (c). Other provisions applying to an owner or operator who chooses to comply with 40 CFR part 65, subpart D, as in effect on December 14, 2000, are provided in 40 CFR 65.1.

2. Owners or operators who choose to comply with 40 CFR part 65, subpart D, as in effect on December 14, 2000, shall also comply with ss. NR 440.01, 440.02, 440.05, 440.06, 440.07(1) (a) and (d), 440.14 and 440.15 for those process vents. All sections or subsections from ss. NR 440.01 to 440.19 not specified in this subdivision do not apply to owners or operators of process vents complying with 40 CFR part 65, subpart D, as in effect on December 14, 2000, except that provisions required to be met prior to implementing 40 CFR part 65 still apply. Owners or operators who choose to comply with 40 CFR part 65, subpart D, as in effect on December 14, 2000, shall comply with 40 CFR part 65, subpart A.

3. Owners or operators who choose to comply with 40 CFR part 65, subpart D, as in effect on December 14, 2000, at initial startup shall comply with subds. 1. and 2. for each vent stream on and after the date on which the initial performance test is completed, but not later than 60 days after achieving the maximum production rate at which the affected facility will be operated, or 180 days after the initial startup, whichever date comes first.

4. Each owner or operator subject to the provisions of this section that chooses to comply with 40 CFR part 65, subpart D, as in effect on December 14, 2000, at initial startup shall notify the administrator of the specific provisions of 40 CFR 65.63(a) (1), (2) or (3) with which the owner or operator has elected to comply. Notification shall be submitted with the notification of initial startup required by 40 CFR 65.5(b).

(2) DEFINITIONS. As used in this section, all terms not defined here shall have the meanings given them in s. NR 440.02 and the following terms shall have the specific meanings given them.

(a) "Air oxidation reactor" means any device or process vessel in which one or more organic reactants are combined with air or a combination of air and oxygen, to produce one or more organic compounds. Ammoxidation and oxychlorination reactions are included in this definition.

(b) "Air oxidation reactor recovery train" means an individual recovery system receiving the vent stream from at least one air oxidation reactor, along with all air oxidation reactors feeding vent streams into this system.

(c) "Air oxidation unit process" means a unit process, including ammoxidation and oxychlorination unit process, that uses air or a combination of air and oxygen, as an oxygen source in combination with one or more organic reactants to produce one or more organic compounds.

(d) "Boilers" means any enclosed combustion device that extracts useful energy in the form of steam.

(e) "By compound" means by individual stream components, not carbon equivalents.

(f) "Continuous recorder" means a data recording device recording an instantaneous data value at least once every 15 minutes.

(g) "Flame zone" means the portion of the combustion chamber in a boiler occupied by the flame envelope.

(h) "Flow indicator" means a device which indicates whether gas flow is present in a vent stream.

(i) "Halogenated vent stream" means any vent stream determined to have a total concentration, by volume, of compounds containing halogens of 20 ppmv by compound or greater.

(j) "Incinerator" means any enclosed combustion device that is used for destroying organic compounds and does not extract energy in the form of steam or process heat.

(k) "Process heater" means a device that transfers heat liberated by burning fuel to fluids contained in tubes, including all fluids except water that is heated to produce steam.

(L) "Process unit" means equipment assembled and connected by pipes or ducts to produce, as intermediate or final products, one or more of the chemicals in sub. (8). A process unit can operate independently if supplied with sufficient fuel or raw materials and sufficient product storage facilities.

(m) "Product" means any compound or chemical listed in sub. (8) that is produced for sale as a final product as that chemical or is produced for use in a process that needs that chemical for the production of other chemicals in another facility. By-products, co-products and intermediates are considered to be products.

(n) "Recovery device" means an individual unit of equipment, such as an absorber, condenser and carbon adsorber, capable of and used to recover chemicals for use, reuse or sale.

(o) "Recovery system" means an individual recovery device or series of such devices applied to the same process stream.

(p) "Total organic compounds" or "TOC" means those compounds measured according to the procedures in sub. (5) (b) 4. For the purposes of measuring molar composition as required in sub. (5) (e) 3. a., hourly emissions rate as required in sub. (5) (e) 6. and (f), and TOC concentration as required in sub. (6) (b) 4. and (g) 4., those compounds which the department has determined do not contribute appreciably to the formation of ozone are to be excluded. The compounds to be excluded are identified in s. NR 400.02(162).

(q) "Total resource effectiveness (TRE) index value" means a measure of the supplemental total resource requirement per unit reduction of TOC associated with an individual air oxidation vent stream, based on vent stream flow rate, emission rate of TOC, net heating value and corrosion properties, whether or not the vent stream is halogenated, as quantified by the equation given under sub. (5) (e).

(r) "Vent stream" means any gas stream, containing nitrogen which was introduced as air to the air oxidation reactor, released to the atmosphere directly from any air oxidation reactor recovery train or indirectly, after diversion through other process equipment. The vent stream excludes equipment leaks and relief valve discharges including, but not limited to, pumps, compressors and valves.

(3) STANDARDS. Each owner or operator of any affected facility shall comply with par. (a), (b) or (c) for each vent stream on and after the date on which the initial performance test required by s. NR 440.08 and sub. (5) is completed, but not later than 60 days after achieving the maximum production rate at which the affected facility will be operated or 180 days after the initial startup, whichever date comes first. Each owner or operator shall either:

(a) Reduce emissions of TOC (minus methane and ethane) by 98 weight- percent or to a TOC (minus methane and ethane) concentration of 20 ppmv on a dry basis corrected to 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

(b) Combust the emissions in a flare that meets the requirements of s. NR 440.18; or

(c) Maintain a TRE index value greater than 1.0 without use of VOC emission control devices.

(4) MONITORING OF EMISSIONS AND OPERATIONS.

(a) The owner or operator of an affected facility that uses an incinerator to seek to comply with the TOC emission limit specified under sub. (3) (a) shall install, calibrate, maintain and operate according to manufacturer's specifications the following equipment:

1. A temperature monitoring device equipped with a continuous recorder and having an accuracy of ± 1% of the temperature being monitored expressed in degrees Celsius or ± 0.5°C, whichever is greater.

a. Where an incinerator other than a catalytic incinerator is used, a temperature monitoring device shall be installed in the firebox.

b. Where a catalytic incinerator is used, temperature monitoring devices shall be installed in the gas stream immediately before and after the catalyst bed.

2. A flow indicator that provides a record of vent stream flow to the incinerator at least once every hour for each affected facility. The flow indicator shall be installed in the vent stream from each affected facility at a point closest to the inlet of each incinerator and before being joined with any other vent stream.

(b) The owner or operator of an affected facility that uses a flare to seek to comply with sub. (3) (b) shall install, calibrate, maintain and operate according to manufacturer's specifications the following equipment:

1. A heat sensing device, such as an ultra-violet sensor or thermocouple, at the pilot light to indicate the continuous presence of a flame.

2. A flow indicator that provides a record of vent stream flow to the flare at least once every hour for each affected facility. The flow indicator shall be installed in the vent stream from each affected facility at a point closest to the flare and before being joined with any other vent stream.

(c) The owner or operator of an affected facility that uses a boiler or process heater to seek to comply with sub. (3) (a) shall install, calibrate, maintain and operate according to the manufacturer's specifications the following equipment:

1. A flow indicator that provides a record of vent stream flow to the boiler or process heater at least once every hour for each affected facility. The flow indicator shall be installed in the vent stream from each air oxidation reactor within an affected facility at a point closest to the inlet of each boiler or process heater and before being joined with any other vent stream.

2. A temperature monitoring device in the firebox equipped with a continuous recorder and having an accuracy of " 1% of the temperature being measured expressed in degrees Celsius or " 0.5°C, whichever is greater, for boilers or process heaters of less than 44 MW (150 million Btu/hr) heat input design capacity.

(d) The owner or operator of an affected facility that uses a boiler or process heater to comply with sub. (3) (a) shall monitor and record the periods of operation of the boiler or process heater if the design input capacity of the boiler is 44 MW (150 million Btu/hr) or greater. The records shall be readily available for inspection.

(e) The owner or operator of an affected facility that seeks to demonstrate compliance with the TRE index value limit specified under sub. (3) (c) shall install, calibrate, maintain and operate according to manufacturer's specifications the following equipment, unless alternative monitoring procedures or requirements are approved for that facility by the department:

1. Where an absorber is the final recovery device in a recovery system:

a. A scrubbing liquid temperature monitoring device having an accuracy of " 1% of the temperature being monitored expressed in degrees Celsius or " 0.5°C, whichever is greater, and a specific gravity monitoring device having an accuracy of " 0.02 specific gravity units, each equipped with a continuous recorder;

b. An organic monitoring device used to indicate the concentration level of organic compounds exiting the recovery device based on a detection principle such as infra-red, photoionization or thermal conductivity, each equipped with a continuous recorder.

2. Where a condenser is the final recovery device in a recovery system:

a. A condenser exit or product side temperature monitoring device equipped with a continuous recorder and having an accuracy of " 1% of the temperature being monitoring expressed in degrees Celsius or "0.5°C, whichever is greater;

3. Where a carbon adsorber is the final recovery device in a recovery system:

a. An integrating steam flow monitoring device having an accuracy of " 10% and a carbon bed temperature monitoring device having an accuracy of " 1% of the temperature being monitored expressed in degrees Celsius or " 0.5°C, whichever is greater, both equipped with a continuous recorder;

(f) An owner or operator of an affected facility seeking to demonstrate compliance with the standards specified under sub. (3) with control devices other than an incinerator, boiler, process heater or flare; or recovery devices other than an absorber, condenser or carbon adsorber shall provide to the administrator information describing the operation of the control device or recovery device and the process parameters which would indicate proper operation and maintenance of the device. The administrator may request further information and will specify appropriate monitoring procedures or requirements.

(5) TEST METHODS AND PROCEDURES.

(a) For the purpose of demonstrating compliance with sub. (3), all affected facilities shall be run at full operating conditions and flow rates during any performance test.

(b) The following methods in Appendix A of 40 CFR part 60, incorporated by reference in s. NR 440.17, except as provided under s. NR 440.08(2) (b), shall be used as reference methods to determine compliance with the emission limit or percent reduction efficiency specific under sub. (3) (a):

1. Method 1 or 1A, as appropriate, 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 prior to the inlet of the control device and after the recovery system.

2. Method 2, 2A, 2C or 2D, as appropriate, for determination of the volumetric flow rates.

3. The emission rate correction factor, integrated sampling and analysis procedure of Method 3 shall be used to determine the oxygen concentration (%O2d) for the purposes of determining compliance with the 20 ppmv limit. The sampling site shall be the same as that of the TOC samples and the samples shall be taken during the same time that the TOC samples are taken.

The TOC concentration corrected to 3% O2 (Cc) shall be computed using the following equations:

C_c = C_TOC 17.9/20.9 - %0_2d

where:

Cc is the concentration of TOC corrected to 3% O2, dry basis, ppm by volume

CTOC is the concentration of TOC (minus methane and ethane), dry basis, ppm by volume

%O2d is the concentration of O2, dry basis, percent by volume

4. Method 18 to determine concentration of TOC in the control device outlet and the concentration of TOC in the inlet when the reduction efficiency of the control device is to be determined.

a. The sampling time for each run shall be 1 hour in which either an integrated sample or 4 grab samples shall be taken. If grab sampling is used then the samples shall be taken at 15-minute intervals.

b. The emission reduction (R) of TOC (minus methane and ethane) shall be determined using the following equation:

R = E_i-E_o/E_ix100

where:

R is the emission reduction, percent by weight

Ei is the mass rate of TOC entering the control device, kg/hr (lb/hr)

Eo is the mass rate of TOC discharged to the atmosphere, kg/hr (lb/hr)

c. The mass rates of TOC (Ei, Eo) shall be computed using the following equations:

See PDF for diagram

where:

Cij and Coj are the concentration of sample component "j" of the gas stream at the inlet and outlet of the control device, respectively, dry basis, ppm by volume

Mij and Moj are the molecular weight of sample component "j" of the gas stream at the inlet and outlet of the control device, respectively, g/g-mole (lb/lb-mole)

Qi and Qo are the flow rate of gas stream at the inlet and outlet of the control device, respectively, dscm/min (dscf/min)

K2 is a constant, 2.494 x 10-6 (1/ppm)(g-mole/scm)(kg/g)(min/hr) for metric units, where standard temperature for (g-mole/scm) is 20°C, and 1.557 x 10-7 (1/ppm)(lb-mole/scf)(min/hr) for English units, where standard temperature for (lb-mole/scf) is 68°F

d. The TOC concentration (CTOC) is the sum of the individual components and shall be computed for each run using the following equation:

where:

See PDF for diagram

CTOC is the concentration of TOC (minus methane and ethane), dry basis, ppm by volume

Cj is the concentration of sample components in the sample

n is the number of components in the sample

(c) When a boiler or process heater with a design heat input capacity of 44 MW (150 million Btu/hour) or greater is used to seek to comply with sub. (3) (a), the requirement for an initial performance test is waived, in accordance with s. NR 440.08(2). However, the department reserves the option to require testing at such other times as may be required.

(d) When a flare is used to seek to comply with sub. (3) (b), the flare shall comply with the requirements of s. NR 440.18.

(e) The following test methods in Appendix A of 40 CFR part 60, incorporated by reference in s. NR 440.17, except as provided under s. NR 440.08(2), shall be used for determining the net heating value of the gas combusted to determine compliance under sub. (3) (b) and for determining the process vent stream TRE index value to determine compliance under sub. (3) (c).

1. Method 1 or 1A, as appropriate, for selection of the sampling site. The sampling site for the vent stream flow rate and molar composition determination prescribed in subds. 3. and 4. shall be, except for the situations outlined in subd. 2., prior to the inlet of any control device, prior to any post-reactor dilution of the stream with air and prior to any post-reactor introduction of halogenated compounds into the vent stream. No transverse site selection method is needed for vents smaller than 10 centimeters (4 inches) in diameter.

2. If any gas stream other than the air oxidation vent stream from the affected facility is normally conducted through the final recovery device:

a. The sampling site for vent stream flow rate and molar composition shall be prior to the final recovery device and prior to the point at which the nonair oxidation stream is introduced.

b. The efficiency of the final recovery device is determined by measuring the TOC concentration using Method 18 at the inlet to the final recovery device after the introduction of any nonair oxidation vent stream and at the outlet of the final recovery device.

c. This efficiency is applied to the TOC concentration measured prior to the final recovery device and prior to the introduction of the nonair oxidation stream to determine the concentration of TOC in the air oxidation stream from the final recovery device. This concentration of TOC is then used to perform the calculations outlined in subds. 5. and 6.

3. The molar composition of the process vent stream shall be determined as follows:

a. Method 18 to measure the concentration of TOC including those containing halogens.

b. ASTM D1946-90 (reapproved 1994), incorporated by reference in s. NR 440.17(2) (a) 24., to measure the concentration of carbon monoxide and hydrogen.

c. Method 4 to measure the content of water vapor.

4. The volumetric flow rate shall be determined using Method 2, 2A, 2C or 2D, as appropriate.

5. The net heating value of the vent stream shall be calculated using the following equation:

See PDF for diagram

where:

HT is the net heating value of the sample, MJ/scm (Btu/scf), where the net enthalpy per mole of vent stream is based on combustion at 25°C and 760 mm Hg (77°F and 30 in Hg), but the standard temperature for determining the volume corresponding to one mole is 20°C (68°F)

K1 is a constant, 1.740 x 10-7 (1/ppm)(g-mole/scm)(MJ/kcal) for metric units where standard temperature for (g-mole/scm) is 20°C, and 1.03 x 10-11 (1/ppm)(lb-mole/scf)(Btu/kcal) for English units where standard temperature for (lb-mole/scf) is 68°F

Cj is the concentration on a wet basis of compound j in ppm, as measured for organics by Method 18 and measured for hydrogen and carbon monoxide by ASTM D1946-90 (reapproved 1994), incorporated by reference in s. NR 440.17(2) (a) 24., as indicated in subd 3.

Hj is the net heat of combustion of compound j, kcal/g-mole (kcal/lb-mole), based on combustion at 25°C and 760 mm Hg (77°F and 30 in Hg). The heats of combustion of vent stream components would be required to be determined using ASTM D2382-88 or D4809-95, incorporated by reference as specified in s. NR 440.17(2) (a) 30. and 61., if published values are not available or cannot be calculated

6. The emission rate of TOC in the process vent stream shall be calculated using the following equation:

See PDF for diagram

where:

ETOC is the emission rate of TOC in the sample, kg/hr (lb/hr)

K2 is the constant, 2.494 10-6 (1/ppm) (g-mole/scm) (kg/g) (min/hr) for metric units, where standard temperature for (g-mole/scm) is 20°C, and 1.557 x 10-7 (1/ppm)(lb-mole/scf)(min/hr) for English units, where standard temperature for (lb-mole/scf) is 68°F

Cj is the concentration on a wet basis of compound j in ppm as measured by Method 18 as indicated in subd. 3.

Mj is the molecular weight of sample j, g/g-mole (lb/lb-mole)

Qs is the vent stream flow rate (scm/min) (scf/hr) at a standard temperature of 20°C (68°F)

7. The total process vent stream concentration (by volume) of compounds containing halogens (ppmv, by compound) shall be summed from the individual concentrations of compounds containing halogens which were measured by Method 18.

(f) For purposes of complying with sub. (3) (c), the owner or operator of a facility affected by this section shall calculate the TRE index value of the vent stream using the equation for incineration in subd. 1. for halogenated vent streams. The owner or operator of an affected facility with a nonhalogenated vent stream shall determine the TRE index value by calculating values using both the incinerator equation in subd. 1. and the flare equation in subd. 2. and selecting the lower of the 2 values.

1. The TRE index value of the vent stream controlled by an incinerator shall be calculated using the following equation:

See PDF for diagram

a. Where for a vent stream flow rate that is greater than or equal to 14.2 scm/min (501 scf/min) at a standard temperature of 20°C (68°F):

TRE is the TRE index value

Qs is the vent stream flow rate scm/min (scf/min), at a standard temperature of 20°C (68°F)

HT is the vent stream net heating value, MJ/scm (Btu/scf), where the net enthalpy per mole of vent stream is based on combustion at 25°C and 760 mm Hg (68°F and 30 in Hg), but the standard temperature for determining the volume corresponding to one mole is 20°C (68°F), as in the definition of Qs

Ys = Qs for all vent stream categories listed in Table 1 except for Category E vent streams where Ys = (Qs) (HT)/3.6 for metric units and Ys = (Qs)(HT)/97 for English units

ETOC is the hourly emissions of TOC, kg/hr (lb/hr)

a, b, c, d, e and f are coefficients

The set of coefficients which apply to a vent stream shall be obtained from Table 1.

Design Category A1. For Halogenated Process Vent Streams, If 0 <= Net Heating Value (MJ/scm) <= 3.5 Or If 0 <= Net Heating Value (Btu/scf) <= 94:
Qs = Vent Stream Flow Rate scm/min (scf/min)	a	b	c	d	e	f
1)	14.2 <= Qs <= 18.8 (501 <= Qs <= 664)	19.18370 (42.29238)	0.27580 (0.017220)	0.75762 (0.072549)	-0.13064 (-0.00030361)	0 (0)	0.01025 (0.003803)
2)	18.8 < Qs <=699 (664 < Qs <= 24,700)	20.00563 (44.10441)	0.27580 (0.017220)	0.30387 (0.029098)	-0.13064 (-0.00030361)	0 (0)	0.01025 (0.003803)
3)	699 < Qs <=1400 (24,700 < Qs <= 49,000)	39.87022 (87.89789)	0.29973 (0.018714)	0.30387 (0.029098)	-0.13064 (-0.00030361)	0 (0)	0.01449 (0.005376)
4)	1400 < Qs <=2100 (49,000 < Qs <= 74000)	59.73481 (131.6914)	0.31467 (0.019647)	0.30387 (0.029098)	-0.13064 (-0.00030361)	0 (0)	0.01775 (0.006585)
5)	2100 < Qs <=2800 (74,000 < Qs <= 99,000)	79.59941 (175.4849)	0.32572 (0.020337)	0.30387 (0.029098)	-0.13064 (-0.00030361)	0 (0)	0.02049 (0.007602)
6)	2800 < Qs <=3500 (99,000 < Qs <= 120,000)	99.46400 (219.2783)	0.33456 (0.020888)	0.30387 (0.029098)	-0.13064 (-0.00030361)	0 (0)	0.02291 (0.008500)
Design Category A2. For Halogenated Process Vent Streams, If Net Heating Value > 3.5 MJ/scm Or If Net Heating Value > 94 (Btu/scf):
Qs = Vent Stream Flow Rate scm/min (scf/min)	a	b	c	d	e	f
7)	14.2 <= Qs <= 18.8	18.84466	0.26742	-0.20044	0	0	0.01025
(501 <= Qs <= 664)	(41.54494)	(0.016696)	(-0.019194)	(0)	(0)	(0.003803)
8)	18.8 < Qs <= 699	19.66658	0.26742	-0.25332	0	0	0.01025
(664 < Qs <= 24,700)	(43.35694)	(0.016696)	(-0.024258)	(0)	(0)	(0.003803)
9)	699 < Qs <=1400 (24,700 < Qs <= 49,000)	39.19213 (86.40297)	0.29062 (0.018145)	-0.25332 (-0.024258)	0 (0)	0 (0)	0.01449 (0.005376)
10)	1400 < Qs <=2100 (49,000 < Qs <= 74000)	58.71768 (129.4490)	0.30511 (0.019050)	-0.25332 (-0.024258)	0 (0)	0 (0)	0.01775 (0.006585)
11)	2100 < Qs <=2800 (74,000 < Qs <= 99,000)	78.24323 (172.4950)	0.31582 (0.019718)	-0.25332 (-0.024258)	0 (0)	0 (0)	0.02049 (0.007602)
12)	2800 < Qs <=3500 (99,000 < Qs = 120,000)	97.76879 (215.5411)	0.32439 (0.020253)	-0.25332 (-0.024258)	0 (0)	0 (0)	0.02291 (0.008500)
Design Category B. For Nonhalogenated Process Vent Streams, If 0 <= Net Heating Value (MJ/scm) <= 0.48 Or If 0 <= Net Heating Value (Btu/scf) <= 13:
Qs = Vent Stream Flow Rate scm/min (scf/min)		a	b	c	d	e	f
13)	14.2 < Qs <=1340 (501 < Qs <= 47,300)	8.54245 (18.83268)	0.10555 (0.0065901)	0.09030 (0.008647)	-0.17109 (-0.00039762)	0 (0)	0.01025 (0.003803)
14)	1340 < Qs <=2690 (47,300 < Qs <= 95,000)	16.94386 (37.35443)	0.11470 (0.0071614)	0.09030 (0.008647)	-0.17109 (-0.00039762)	0 (0)	0.01449 (0.005376)
15)	2690 < Qs <=4040 (95,000 < Qs <= 143,000)	25.34528 (55.87620)	0.12042 (0.0075185)	0.09030 (0.008647)	-0.17109 (-0.00039762)	0 (0)	0.01775 (0.00658)
16)	14.2 <= Qs <=1340 (501 <= Qs <= 47,300)	9.25233 (20.39769)	0.06105 (0.003812)	0.31937 (0.030582)	-0.16181 (-0.00037605)	0 (0)	0.01025 (0.003803)
17)	1,340< Qs <= 2,690	18.36363	0.06635	0.31937	-0.16181	0	0.01449
(47,300 < Qs <= 95,000)	(40.48446)	(0.004143)	(0.030582)	(-0.00037605)	(0)	(0.005376)
18)	2,690< Qs <= 4,040	27.47492	0.06965	0.31937	-0.16181	0	0.01775
(95,000 < Qs <= 143,000)	(60.57121)	(0.004349)	(0.030582)	(-0.00037605)	(0)	(0.006585)
Design Category D. For Nonhalogenated Process Vent Streams, If 1.9 < Net Heating Value (MJ/scm) <= 3.6: Or If 51 < Net Heating Value (Btu/scf) <= 97:
Qs = Vent Stream Flow Rate scm/min (scf/min)	a	b	c	d	e	f
19)	14.2 < Qs <= 1,180	6.67868	0.06943	0.02582	0	0	0.01025
(501 <= Qs <= 41,700)	(14.72382)	(0.004335)	(0.002472)	(0)	(0)	(0.003803)
20)	1,180 < Qs <= 2,370	13.21633	0.07546	0.02582	0	0	0.01449
(41,000 < Qs <= 83,700)	(29.13672)	(0.004711)	(0.002472)	(0)	(0)	(0.005376)
21)	2,370< Qs <= 3,550	19.75398	0.07922	0.02582	0	0	0.01755
(83,700 < Qs <= 125,000)	(43.54962)	(0.004946)	(0.002472)	(0)	(0)	(0.00658)
Design Category E. For Nonhalogenated Process Vent Streams, If Net Heating Value > 3.6 MJ/scm Or If Net Heating Value > 97 Btu/scf):
Ys = Dilution Flow Rate scm/min = (Qs)(HT)/3.6 (scf/min) = (Qs)(HT)/97	a	b	c	d	e	f
22)	14.2 <= Ys <=1,180	6.67868	0	0	-0.00707	0.02220	0.01025
(501 <= Ys <= 41,700)	(14.72382)	(0)	(0)	(-0.0000164)	(0.0001174)	(0.003803)
23)	1,180 < Ys <= 2,370	13.21633	0	0	-0.00707	0.02412	0.01449
(41,700 < Ys <= 83,700)	(29.13672)	(0)	(0)	(-0.0000164)	(0.0001276)	(0.005376)
24)	2,370< Ys <= 3,550	19.75398	0	0	-0.00707	0.02533	0.01755
(83,700 < Ys <= 125,000)	(43.54962)	(0)	(0)	(-0.0000164)	(0.0001340)	(0.006585)

b. Where for a vent stream flow rate that is less than 14.2 scm/min (501 scf/min) at a standard temperature of 20°C (68°F):

TRE is the TRE index value

Qs is 14.2 scm/min (501 scf/min)

HT is (FLOW) (HVAL) / Qs

where the following inputs are used:

FLOW is the vent stream flow rate (scm/min) (scf/min), at a standard temperature of 20°C (68°F)

HVAL is the vent stream net heating value MJ/scm (Btu/scf), where the net enthalpy per mole of vent stream is based on combustion at 25°C and 760 mm Hg (77°F and 30 in Hg), but the standard temperature for determining the volume corresponding to 1 mole is 20°C (68°F) as in the definition of Qs

Ys = Qs for all vent stream categories listed in Table 1 except for Category E vent streams, where Ys = QsHT/3.6 for metric units and Ys = QsHT/97 for English units.

ETOC is the hourly emissions of TOC reported in kg/hr (lb/hr)

a,b,c,d,e and f are coefficients

The set of coefficients that apply to a vent stream shall be obtained from Table 1.

2. The equation for calculating the TRE index value of a vent stream controlled by a flare is as follows:

See PDF for diagram

where:

TRE is the TRE index value

ETOC is the hourly emissions of TOC, kg/hr (lb/hr)

Qs is the vent stream flow rate, scm/min (scf/min) at a standard temperature of 20°C (68°F)

HT is the vent stream net heating value, MJ/scm (Btu/scf), where the net enthalpy per mole of vent stream is based on combustion at 25°C and 760 mm Hg (77°F and 30 in Hg), but the standard temperature for determining the volume corresponding to 1 mole is 20°C (68°F) as in the definition of Qs

a, b, c, d and e are coefficients

The set of coefficients that apply to a vent stream shall be obtained from Table 2.

Table 2. Air Oxidation Processes NSPS TRE Coefficients For Vent Streams Controlled By a Flare

a	b	c	d	e
a.	H_T < 11.2 MJ/scm	2.25	0.288	-0.193	-0.0051	2.08
(HT < 301 Btu/scf)	(0.140)	(0.0367)	(-0.000448)	(-0.0051)	(4.59)
b.	H_T >= 11.2 MJ/scm	0.309	0.0619	-0.0043	-0.0034	2.08
(HT >= 301 Btu/scf)	(0.0193)	(0.00788)	(-0.000010)	(-0.0034)	(4.59)

(g) Each owner or operator of an affected facility seeking to comply with sub. (1) (c) or (3) (c) shall recalculate the TRE index value for that affected facility whenever process changes are made. Some examples of process changes are changes in production capacity, feedstock type or catalyst type or whenever there is replacement, removal or addition of recovery equipment. The TRE index value shall be recalculated based on test data or on best engineering estimates of the effects of the change to the recovery system.

1. Where the recalculated TRE index value is less than or equal to 1.0, the owner or operator shall notify the department within 1 week of the recalculation and shall conduct a performance test according to the methods and procedures required by sub. (5) to determine compliance with sub. (3) (a). Performance tests shall be conducted as soon as possible after the process change but no later than 180 days from the time of the process change.

2. Where the initial TRE index value is greater than 4.0 and the recalculated TRE index value is less than or equal to 4.0, but greater than 1.0, the owner or operator shall conduct a performance test in accordance with s. NR 440.08 and this subsection, and shall comply with subs. (4) and (6) and this subsection. Performance tests shall be conducted as soon as possible after the process change but no later than 180 days from the time of the process change.

(6) REPORTING AND RECORDKEEPING REQUIREMENTS.

(a) Each owner or operator subject to sub. (3) shall notify the department of the specific provisions of sub. (3) with which the owner or operator has elected to comply. Notification shall be submitted with the notification of initial startup required by s. NR 440.07(1) (c). If an owner or operator elects at a later date to use an alternative provision of sub. (3) with which he or she will comply, then the department shall be notified by the owner or operator 90 days before implementing a change and, upon implementing the change, a performance test shall be performed as specified by sub. (5) within 180 days.

(b) Each owner or operator subject to the provisions of this section shall keep up-to-date, readily accessible records of the following data measured during each performance test and also include the following data in the report of the initial performance test required under s. NR 440.08. Where a boiler or process heater with a design heat input capacity of 44 MW (150 million Btu/hour) or greater is used to comply with sub. (3) (a), a report containing performance test data need not be submitted, but a report containing the information of subd. 2. a. is required. The same data specified in this subsection shall be submitted in the reports of all subsequently required performance tests where either the emission control efficiency of a control device, outlet concentration of TOC or the TRE index value of a vent stream from a recovery system is determined.

1. Where an owner or operator subject to this section seeks to demonstrate compliance with sub. (3) (a) through use of either a thermal or catalytic incinerator: a. The average firebox temperature of the incinerator, or the average temperature upstream and downstream of the catalyst bed for a catalytic incinerator, measured at least every 15 minutes and averaged over the same time period of the performance testing, and b. The percent reduction of TOC determined as specified in sub. (5) (b) achieved by the incinerator or the concentration of TOC (ppmv, by compound) determined as specified in sub. (5) (b) at the outlet of the control device on a dry basis corrected to 3% oxygen.

2. Where an owner or operator subject to the provisions of this section seeks to demonstrate compliance with sub. (3) (a) through use of a boiler or process heater:

a. A description of the location at which the vent stream is introduced into the boiler or process heater, and

b. The average combustion temperature of the boiler or process heater with a design heat input capacity of less than 44 MW (150 million Btu/hr) measured at least every 15 minutes and averaged over the same time period of the performance testing.

3. Where an owner or operator subject to the provisions of this section seeks to comply with sub. (3) (b) through the use of a smokeless flare, flare design, that is, steam-assisted, 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.

4. Where an owner or operator seeks to demonstrate compliance with sub. (3) (c).

a. Where an absorber is the final recovery device in a recovery system, the exit specific gravity, or alternative parameter which is a measure of the degree of absorbing liquid saturation, if approved by the department, and average exit temperature of the absorbing liquid, measured at least every 15 minutes and averaged over the same time period of the performance testing, both measured while the vent stream is normally routed and constituted; or

b. Where a condenser is the final recovery device in a recovery system, the average exit, that is, product side, temperature, measured at least every 15 minutes and average over the same time period of the performance testing while the vent stream is normally routed and constituted.

c. Where a carbon adsorber is the final recovery device in a recovery system, the total steam mass flow measured at least every 15 minutes and averaged over the same time period of the performance test, that is, full carbon bed cycle, temperature of the carbon bed after regeneration, and within 15 minutes of completion of any cooling cycle, and duration of the carbon bed steaming cycle, all measured while the vent stream is normally routed and constituted; or

d. As an alternative to subd. 4. a., b. or c., the concentration level or reading indicated by the organic monitoring device at the outlet of the absorber, condenser or carbon adsorber measured at least every 15 minutes and averaged over the same time period of the performance testing while the vent stream is normally routed and constituted.

e. All measurements and calculations performed to determine the TRE index value of the vent stream.

(c) Each owner or operator subject to the provisions of this section shall keep up-to-date, readily accessible continuous records of the equipment operating parameters specified to be monitored under sub. (4) (a) and (c) as well as up-to-date, readily accessible records of periods of operation during which the parameter boundaries established during the most recent performance test are exceeded. The department may at any time require a report of these data. Where a combustion device is used by an owner or operator seeking to demonstrate compliance with sub. (3) (a) or (c), periods of operation during which the parameter boundaries established during the most recent performance tests are exceeded are defined as follows:

1. For thermal incinerators, all 3-hour periods of operation during which the average combustion temperature was more than 28°C (50°F) below the average temperature of the vent stream during the most recent performance test at which compliance with sub. (3) (a) was determined.

2. For catalytic incinerators, all 3-hour periods of operation during which the average temperature of the vent stream immediately before the catalyst bed is more than 28°C (50°F) below the average temperature of the vent stream during the most recent performance test at which compliance with sub. (3) (a) was determined. The owner or operator also shall record all 3-hour periods of operation during which the average temperature difference across the catalyst bed is less than 80% of the average temperature difference of the device during the most recent performance test at which compliance with sub. (3) (a) was determined.

3. All 3-hour periods of operation during which the average combustion temperature was more than 28°C (50°F) below the average combustion temperature during the most recent performance test at which compliance with sub. (3) (a) was determined for boilers or process heaters with a design heat input capacity of less than 44 MW (150 million Btu/hr).

4. For boilers or process heaters, whenever there is a change in the location at which the vent stream is introduced into the flame zone as required under sub. (3) (a).

(d) Each owner or operator subject to the provisions of this section shall keep up-to-date, readily accessible continuous records of the flow indication specified under sub. (4) (a) 2., (b) 2. and (c) 1. as well as up-to-date, readily accessible records of all periods when the vent stream is diverted from the control device or has no flow rate.

(e) Each owner or operator subject to the provisions of this section who uses a boiler or process heater with a design heat input capacity of 44 MW (150 million Btu/hour) or greater to comply with sub. (3) (a) shall keep an up-to-date, readily accessible record of all periods of operation of the boiler or process heater.

Note: Examples of such records could include records of steam use, fuel use or monitoring data collected pursuant to other state or federal regulatory requirements.

(f) Each owner or operator subject to the provisions of this section shall keep up-to-date, readily accessible continuous records of the flare pilot flame monitoring specified in sub. (4) (b), as well as up-to-date, readily accessible records of all periods of operations in which the pilot flame is absent.

(g) Each owner or operator subject to the provisions of this section shall keep up-to-date, readily accessible continuous records of the equipment operating parameters specified to be monitored under sub. (4) (e) as well as up-to-date, readily accessible records of periods of operation during which the parameter boundaries established during the most recent performance test are exceeded. The department may at any time require a report of these data. Where the owner or operator seeks to demonstrate compliance with sub. (3) (c), periods of operation during which the parameter boundaries established during the most recent performance tests are exceeded are defined as follows:

1. Where an absorber is the final recovery device in a recovery system and where an organic monitoring device is not used:

a. All 3-hour periods of operation during which the average absorbing liquid temperature was more than 11°C (20 °F) above the average absorbing liquid temperature during the most recent performance test or

b. All 3-hour periods of operation during which the average absorbing liquid specific gravity was more than 0.1 unit above or more than 0.1 unit below, the average absorbing liquid specific gravity during the most recent performance test, unless monitoring of an alternative parameter, which is a measure of the degree of absorbing liquid saturation, is approved by the department, in which case the department will define appropriate parameter boundaries and periods of operation during which they are exceeded.

2. When a condenser is the final recovery device in a recovery system and where an organic monitoring device is not used, all 3-hour periods of operation during which the average exit or product side condenser operating temperature was more than 6°C (11°F) above the average exit (product side) operating temperature during the most recent performance test.

3. Where a carbon adsorber is the final recovery device in a recovery system and where an organic monitoring device is not used:

a. All carbon bed regeneration cycles during which the total mass steam flow was more than 10% below the total mass steam flow during the most recent performance test; or

b. All carbon bed regeneration cycles during which the temperature of the carbon bed after regeneration, and after completion of any cooling cycle, was more than 10% greater than the carbon bed temperature, in degrees Celsius, during the most recent performance test.

4. Where an absorber, condenser or carbon adsorber is the final recovery device in the recovery system and an organic monitoring device approved by the department is used, all 3-hour periods of operation during which the average concentration level or reading of organic compounds in the exhaust gases is more than 20% greater than the exhaust gas organic compound concentration level or reading measured by the monitoring device during the most recent performance test.

(h) Each owner or operator subject to the provisions of this section and seeking to demonstrate compliance with sub. (3) (c) shall keep up-to-date, readily accessible records of:

1. Any changes in production capacity, feedstock type or of any replacement, removal or addition of recovery equipment or air oxidation reactors;

2. Any recalculation of the TRE index value performed pursuant to sub. (5) (f);

3. The results of any performance test performed pursuant to the methods and procedures required by sub. (5) (d).

(i) Each owner and operator subject to the provisions of this section is exempt from the quarterly reporting requirements contained in s. NR 440.07(3).

(j) Each owner or operator that seeks to comply with the requirements of this section by complying with the requirements of sub. (3) shall submit to the department semiannual reports of the following information. The initial report shall be submitted within 6 months after the initial startup date.

1. Exceedances of monitored parameters recorded under pars. (c) and (g).

2. All periods recorded under par. (d) when the vent stream is diverted from the control device or has no flow rate.

3. All periods recorded under par. (e) when the boiler or process heater was not operating.

4. All periods recorded under par. (f) in which the pilot flame of the flare was absent.

5. Any recalculation of the TRE index value, as recorded under par. (h).

Note: The requirements of par. (j) remain in force until and unless EPA, in delegating enforcement authority to a state under section 111 (c) of the act, approves reporting requirements or an alternative means of compliance surveillance adopted by such state. In that event, affected sources within the state will be relieved of the obligation to comply with par. (j), provided that they comply with the requirements established by the state.

(L) The department will specify appropriate reporting and recordkeeping requirements where the owner or operator of an affected facility seeks to demonstrate compliance with the standards specified under sub. (3) other than as provided under sub. (4) (a) to (d).

(7) RECONSTRUCTION.

(a) For purposes of this section "fixed capital cost of the new components", as used in s. NR 440.15, includes the fixed capital cost of all depreciable components which are or will be replaced pursuant to all continuous programs of components which are commenced within any 2-year period following October 21, 1983. For purposes of this paragraph,"commenced" means that an owner or operator has undertaken a continuous program of component replacement or that an owner or operator has entered into a contractual obligation to undertake and complete, within a reasonable time, a continuous program of component replacement.

(8) CHEMICALS AFFECTED BY THIS SECTION.

Chemical Name	CAS No.*
(a)	Acetaldehyde ......................	75-07-0
(b)	Acetic acid ........................	64-19-7
(c)	Acetone ..........................	67-64-1
(d)	Acetonitrile........................	75-05-8
(e)	Acetophenone......................	98-86-2
(f)	Acrolein ..........................	107-02-8
(g)	Acrylic acid .......................	79-10-7
(h)	Acrylonitrile.......................	107-13-1
(i)	Anthraquinone .....................	84-65-1
(J)	Benzaldehyde......................	100-52-7
(k)	Benzoic acid, tech...................	65-85-0
(L)	1,3-Butadiene......................	106-99-0
(m)	p-t-Butyl benzoic acid...............	98-73-7
(n)	N-Butyric acid.....................	107-92-6
(o)	Crotonic acid ......................	3724-65-0
(P)	Cumene hydroperoxide ..............	80-15-9
(q)	Cyclohexanol ......................	108-93-0
(qm)	Cyclohexanone.....................	108-94-1
(r)	Dimethyl terephthalate...............	120-61-6
(rm)	Ethylene dichloride ..................	107-06-2
(s)	Ethylene oxide .....................	75-21-8
(sm)	Formaldehyde ......................	50-00-0
(t)	Formic acid ........................	64-18-6
(tm)	Glyoxal...........................	107-22-2
(u)	Hydrogen cyanide ..................	74-90-8
(um)	Isobutyric acid .....................	79-31-2-5
(v)	Isophthalic acid .....................	121-91
(vm)	Maleic anhydride ...................	108-31-6
(w)	Methyl ethyl ketone .................	78-93-3
(wm)	a-Methyl styrene...................	98-83-9
(x)	Phenol............................	108-95-2
(xm)	Phthalic anhydride ..................	85-44-9
(y)	Propionic acid ......................	79-09-4
(ym)	Propylene oxide ....................	75-56-9
(z)	Styrene ...........................	100-42-5
(zm)	Terephthalic acid ...................	100-21-0

*CAS numbers refer to the Chemical Abstracts Service Registry numbers assigned to specific isomers or mixtures of chemicals. Some isomers or mixtures that are covered by the standards do not have CAS numbers assigned to them. The standards apply to all of the chemicals listed, whether CAS numbers have been assigned or not.

Wis. Admin. Code Department of Natural Resources NR 440.675

Cr. Register, July, 1993, No. 451, eff. 8-1-93; am. (4) (a) 1. (intro.), (d) 1. a., 3. a., (5) (e) 1. a., Register, December, 1995, No. 480, eff. 1-1-96; renum. (2) (a) (intro.) and 1. to 18. to be (2) (intro.) and (a) to (r), am. (2) (p), Register, November, 1999, No. 527, eff. eff. 12-1-99; CR 06-109: cr. (1) (d), renum. (4) (c) 3. to be (4) (d) and am., renum. (4) (d) and (e) to be (4) (e) and (f), renum. (5) (b) 5., (c), (d), (e) and (f) to be (5) (c), (d), (e), (f) and (g) and am. (5) (e) 1., 3. b., 5. and 6. and (f) 1. a. and b., am. (5) (b) 4. b. and c., (6) (e) and (g) (intro.) and (8) Register May 2008 No. 629, eff. 6-1-08; corrections in (1) (d) 2. and (2) (p) made under s. 13.92(4) (b) 7, Stats., Register May 2008 No. 629.