Section NR 440.684 - Onshore natural gas processing: SO2 emissions(1) APPLICABILITY AND DESIGNATION OF AFFECTED FACILITIES. (a) The provisions of this section are applicable to the following affected facilities that process natural gas: each sweetening unit, and each sweetening unit followed by a sulfur recovery unit.(b) Facilities that have a design capacity less than 2 long tons per day (LT/D) of hydrogen sulfide (H2S) in the acid gas (expressed as sulfur) are required to comply with sub. (8) (c) but are not required to comply with subs. (3) to (7).(c) The provisions of this section are applicable to facilities located on land and include facilities located onshore which process natural gas produced from either onshore or offshore wells.(d) The provisions of this section apply to each affected facility identified in par. (a) which commences construction or modification after January 20, 1984. (e) The provisions of this section do not apply to sweetening facilities producing acid gas that is completely reinjected into oil-or-gas-bearing geologic strata or that is otherwise not released to the atmosphere.(2) DEFINITIONS AND SYMBOLS. (a) As used in this section, terms not defined in this subsection have the meanings given in s. NR 440.02. 1. "Acid gas" means a gas stream of hydrogen sulfide (H2S) and carbon dioxide (CO2) that has been separated from sour natural gas by a sweetening unit.2. "Natural gas" means a naturally occurring mixture of a hydrocarbon and nonhydrocarbon gases found in geologic formations beneath the earth's surface. The principal hydrocarbon constituent is methane.3. "Onshore" means all facilities except those that are located in the territorial seas or on the outercontinental shelf.4. "Reduced sulfur compounds" means hydrogen sulfide (H2S), carbonyl sulfide (COS), and carbon disulfide (CS2).5. "Sulfur production rate" means the rate of liquid sulfur accumulation from the sulfur recovery unit.6. "Sulfur recovery unit" means a process device that recovers element sulfur from acid gas.7. "Sweetening unit" means a process device that separates the H2S and CO2 contents from the sour natural gas stream.8. "Total SO2 equivalents" means the sum of volumetric or mass concentrations of the sulfur compounds obtained by adding the quantity existing as SO2 to the quantity of SO2 that would be obtained if all reduced sulfur compounds were converted to SO2, ppmv or kg/dscm (lb/dscf).(b) As used in this section, all symbols not defined in this subsection have the meanings given them in s. NR 440.03. 1. "E" is the sulfur emission rate expressed as elemental sulfur in kg/hr (lb/hr), rounded to one decimal place.2. "R" is the sulfur emission reduction efficiency achieved in percent carried to one decimal place.3. "S" is the sulfur production rate in kg/hr (lb/hr), rounded to one decimal place.4. "X" is the sulfur feed rate from the sweetening unit, that is, the H2S in the acid gas, expressed as sulfur, Mg/d (long ton/day), rounded to one decimal place.5. "Y" is the sulfur content of the acid gas from the sweetening unit, expressed as mole percent H2S (dry basis) rounded to one decimal place.6. "Z" is the minimum required sulfur dioxide (SO2) emission reduction efficiency, expressed as percent carried to one decimal place. Zi refers to the reduction efficiency required at the initial performance test. Zc refers to the reduction efficiency required on a continual basis after compliance with Zi has been demonstrated.(3) STANDARDS FOR SULFUR DIOXIDE. (a) During the initial performance test required by s. NR 440.08(2), each owner or operator shall achieve, at a minimum, an SO2 emission reduction efficiency (Zi) to be determined from Table 1 based on the sulfur feed rate (X) and the sulfur content of the acid gas (Y) of the affected facility.(b) After demonstrating compliance with the provisions of par. (a), the owner or operator shall achieve, at a minimum, an SO2 emission reduction efficiency (Zc) to be determined from Table 2 based on the sulfur feed rate (X) and the sulfur content of the acid gas (Y) of the affected facility. (4) COMPLIANCE PROVISIONS. (a)1. To determine compliance with the standards for sulfur dioxide specified in sub. (3) (a), during the initial performance test as required by s. NR 440.08, the minimum required sulfur dioxide emissions reduction efficiency (Z) is compared to the emission reduction efficiency (R) achieved by the sulfur recovery technology. a. If R is greater than or equal to Zi, the affected facility is in compliance.b. If R is less than Zi, the affected facility is not in compliance.2. Following the initial determination of compliance as required by s. NR 440.08, any subsequent compliance determinations that may be required by the department shall compare R to Zc.(b) The emission reduction efficiency (R) achieved by the sulfur recovery technology shall be determined using the procedures in sub. (5) (c) 1. Table 1. - Required Minimum Initial SO2 Emission Reduction Efficiency (Zi)
| H2S content of | Sulfur feed rate (X), LT/D |
| acid gas (Y), % | 2.0<=X<=5.0 | 5.0<X<=15.0 15.0<X<=300.0 | X> 300.0 |
| 1. | Y>=50 | 79.0 | ..........88.51X0.0101Y0.0125 or 99.8, whichever is smaller...... |
| 2. | 20<=Y<50 | 79.0 | ..........88.51X0.0101Y0.0125 or 97.9, whichever is smaller . . | 97.9 |
| 3. | 10<=Y<20 | 79.0 | 88.51X0.0101Y0.0125 93.5 or 93.5, whichever is smaller | 93.5 |
| 4. | Y<10 | 79.0 | 79.0 79.0 | 79.0 |
Table 2. - Required Minimum SO2 Emission Reduction Efficiency (Zc)
| H2S content of | Sulfur feed rate (X), LT/D |
| acid gas (Y), % | 2.0<= X<= 5.0 | 5.0<X<=15.0 15.0<X<=300.0 | X> 300.0 |
| 1. | Y>= 50 | 74.0 | .......... 85.35X0.0144Y0.0128 or 99.8, whichever is smaller...... |
| 2. | 20<= Y<50 | 74.0 | ..... 85.35X0.0144Y0.0128 or 97.5, whichever is smaller....... | 97.5 |
| 3. | 10<=Y<20 | 74.0 | 85.35X0.0144Y0.0128 90.8 | 90.8 |
| or 90.8, whichever is smaller |
| 4. | Y<10 | 74.0 | 74.0 74.0 | 74.0 |
(5) TEST METHODS AND PROCEDURES. (a) In conducting the performance tests required in s. NR 440.08, the owner or operator shall use as reference methods and procedures the test methods in Appendix A of 40 CFR part 60, incorporated by reference in s. NR 440.17, or other methods and procedures as specified in this subsection, except as provided in s. NR 440.08(2).(b) During a performance test required by s. NR 440.08, the owner or operator shall determine the minimum required reduction efficiencies (Z) of SO2 emissions as required in sub. (3) (a) and (b) as follows: 1. The average sulfur feed rate (X) shall be computed as follows: X = K Qa Y
where:
X is the average sulfur feed rate, Mg/d (long ton/day)
Qa is the average volumetric flow rate of acid gas from sweetening unit, dscm/day (dscf/day)
Y is the average H2S concentration in acid gas feed from sweetening unit, percent by volume, expressed as a decimal
K is (32kg S/kg-mole)/((24.04 dscm/kg-mole)(1000kg S/Mg)) = 1.331 x 10-3 Mg/dscm for metric units, and is (32 lb S/lb-mole)/((385.36 dscf/lb-mole)(2240 lb S/long ton)) = 3.707 x 10-5 long ton/dscf for English units
2. The continuous readings from the process flowmeter shall be used to determine the average volumetric flow rate (Qa) in dscm/day (dscf/day) of the acid gas from the sweetening unit for each run.3. The Tutwiler procedure in sub. (9) or a chromatographic procedure following ASTM E260-96, incorporated by reference in s. NR 440.17(2) (a) 75., shall be used to determine the H2S concentration in the acid gas feed from the sweetening unit. At least one sample per hour, at equally spaced intervals, shall be taken during each 4-hour run. The arithmetic mean of all samples shall be the average H2S concentration (Y) on a dry basis for the run. By multiplying the result from the Tutwiler procedure by 1.62 10-3, the units gr/100 scf are converted to volume percent.4. Using the information from par. (b) 1. and 3., Tables 1 and 2 shall be used to determine the required initial (Zi) and continuous (Zc) reduction efficiencies of SO2 emissions.(c) The owner or operator shall determine compliance with the SO2 standards in sub. (3) (a) or (b) as follows: 1. The emission reduction efficiency (R) achieved by the sulfur recovery technology shall be computed for each run using the following equation: R = (100 S)/(S + E)
2. The level indicators or manual soundings shall be used to measure the liquid sulfur accumulation rate in the product storage tanks. Readings taken at the beginning and end of each run, the tank geometry, sulfur density at the storage temperature and sample duration shall be used to determine the sulfur production rate (S) in kg/hr (lb/hr) for each run.3. The emission rate of sulfur shall be computed for each run as follows: E = Ce Qsd/ K1
where:
E is the emission rate of sulfur per run, kg/hr (lb/hr)
Ce is the concentration of sulfur equivalent (SO2 + reduced sulfur), g/dscm (lb/dscf)
Qsd is the volumetric flow rate of effluent gas, dscm/hr (dscf/hr)
K1 is a conversion factor, 1000 g/kg (7000 gr/lb)
4. The concentration (Ce) of sulfur equivalent shall be the sum of the SO2 and TRS concentrations, after being converted to sulfur equivalents. For each run and each of the test methods specified in this paragraph, the sampling time shall be at least 4 hours. Method 1 shall be used to select the sampling site. The sampling point in the duct shall be at the centroid of the cross- section if the area is less than 5 m2 (54 ft2) or at a point no closer to the walls than 1 m (39 in.) if the cross-sectional area is 5 m2 (54 ft2) or more and the centroid is more than 1 m (39 in.) from the wall. a. Method 6 shall be used to determine the SO2 concentration. Eight samples of 20 minutes each shall be taken at 30-minute intervals. The arithmetic average shall be the concentration for the run. The concentration shall be multiplied by 0.5 10-3 to convert the results to sulfur equivalent.b. Method 15 shall be used to determine the TRS concentration from reduction-type devices or where the oxygen content of the effluent gas is less than 1.0 % by volume. The sampling rate shall be at least 3 liters/min (0.1 ft3/min) to insure minimum residence time in the sample line. Sixteen samples shall be taken at 15-minute intervals. The arithmetic average of all the samples shall be the concentration for the run. The concentration in ppm reduced sulfur as sulfur shall be multiplied by 1.333 10-3 to convert the results to sulfur equivalent.c. Method 16A or 15 shall be used to determine the reduced sulfur concentration from oxidation-type devices or where the oxygen content of the effluent gas is greater than 1.0 % by volume. Eight samples of 20 minutes each shall be taken at 30-minute intervals. The arithmetic average shall be the concentration for the run. The concentration in ppm reduced sulfur as sulfur shall be multiplied by 1.333 10-3 to convert the results to sulfur equivalent.d. Method 2 shall be used to determine the volumetric flow rate of the effluent gas. A velocity traverse shall be conducted at the beginning and end of each run. The arithmetic average of the 2 measurements shall be used to calculate the volumetric flow rate (Qsd) for the run. For the determination of the effluent gas molecular weight, a single integrated sample over the 4-hour period may be taken and analyzed or grab samples at 1-hour intervals may be taken, analyzed and averaged. For the moisture content, 2 samples of at least 0.10 dscm (3.5 dscf) and 10 minutes shall be taken at the beginning of the 4-hour run and near the end of the time period. The arithmetic average of the 2 runs shall be the moisture content for the run.(d) To comply with sub. (7) (d), the owner or operator shall obtain the information required by using the monitoring devices in par. (b) or (c).(7) MONITORING OF EMISSIONS AND OPERATIONS. (a) The owner or operator subject to the provisions of sub. (3) (a) or (b) shall install, calibrate, maintain and operate monitoring devices or perform measurements to determine the following operations information on a daily basis: 1. The accumulation of sulfur product over each 24-hour period: The monitoring method may incorporate the use of an instrument to measure and record the liquid sulfur production rate, or may be a procedure for measuring and recording the sulfur liquid levels in the storage tanks with a level indicator or by manual soundings with subsequent calculation of the sulfur production rate based on the tank geometry, stored sulfur density, and elapsed time between readings. The method shall be designed to be accurate with " 2% of the 24-hour sulfur accumulation.2. The H2S concentration in the acid gas from the sweetening unit for each 24-hour period: At least one sample per 24-hour period shall be collected and analyzed using the method specified in sub. (5) (b) 3. The department may require the owner or operator to demonstrate that the H2S concentration obtained from one or more samples over a 24-hour period is within " 20% of the average of 12 samples collected at equally spaced intervals during the 24-hour period. In instances where the H2S concentration of a single sample is not within " 20% of the average of the 12 equally spaced samples, the department may require a more frequent sampling schedule.3. The average acid gas flow rate from the sweetening unit: The owner or operator shall install and operate a monitoring device to continuously measure the flow rate of acid gas. The monitoring device reading shall be recorded at least once per hour during each 24-hour period. The average acid gas flow rate shall be computed from the individual readings.4. The sulfur feed rate (X): For each 24-hour period, X shall be computed using the equation in sub. (5) (b) 1.5. The required sulfur dioxide emission reduction efficiency for the 24-hour period. The sulfur feed rate and the H2S concentration in the acid gas for the 24-hour period as applicable, shall be used to determine the required efficiency in accordance with the provisions of sub. (3) (b).(b) Where compliance is achieved through the use of an oxidation control system or a reduction control system followed by a continually operated incineration device, the owner or operator shall install, calibrate, maintain, and operate monitoring devices and continuous emission monitors as follows: 1. A continuous monitoring system to measure the total sulfur emission rate (E) of SO2 in the gases discharged to the atmosphere. The SO2 emission rate shall be expressed in terms of equivalent sulfur mass flow rates kg/hr (lb/hr). The span of this monitoring system shall be set so that the equivalent emission limit of sub. (3) (b) will be between 30% and 70% of the measurement range of the instrument system.2. Except as provided in subd. 3.: A monitoring device to measure the temperature of the gas leaving the combustion zone of the incinerator, if compliance with sub. (3) (a) is achieved through the use of an oxidation control system or a reduction control system followed by a continually operated incineration device. The monitoring device shall be certified by the manufacturer to be accurate to within " 1% of the temperature being measured. When performance tests are conducted under the provision of s. NR 440.08 to demonstrate compliance with the standards under sub. (3), the temperature of the gas leaving the incinerator combustion zone shall be determined using the monitoring device. If the volumetric ratio of sulfur dioxide to sulfur dioxide plus total reduced sulfur (expressed as SO2) in the gas leaving the incinerator is w 0.98, then temperature monitoring may be used to demonstrate that sulfur dioxide emission monitoring is sufficient to determine total sulfur emissions. At all times during the operation of the facility, the owner or operator shall maintain the average temperature of the gas leaving the combustion zone of the incinerator at or above the appropriate level determined during the most recent performance test to ensure the sulfur compound oxidation criteria are met. Operation at lower average temperatures may be considered by the department to be unacceptable operation and maintenance of the affected facility. The owner or operator may request that the minimum incinerator temperature be reestablished by conducting new performance tests under s. NR 440.08.3. The owner or operator may, as an alternative to subd. 2., install, calibrate, maintain, and operate a continuous emission monitoring system for total reduced sulfur compounds as required in par. (d) in addition to a sulfur dioxide emission monitoring system. The sum of the equivalent sulfur mass emission rates from the 2 monitoring systems shall be used to compute the total sulfur emission rate (E).(c) Where compliance is achieved through the use of a reduction control system not followed by a continually operated incineration device, the owner or operator shall install, calibrate, maintain, and operate a continuous monitoring system to measure the emission rate of reduced sulfur compounds as SO2 equivalent in the gases discharged to the atmosphere. The SO2 equivalent compound emission rate shall be expressed in terms of equivalent sulfur mass flow rates kg/hr (lb/hr). The span of this monitoring system shall be set so that the equivalent emission limit of sub. (3) (b) will be between 30 and 70% of the measurement range of the system.(d) For those sources required to comply with pars. (b) and (c), the average sulfur emission reduction efficiency achieved (R) shall be calculated for each 24-hour clock interval. The 24-hour interval may begin and end at any selected clock time but shall be consistent. The 24-hour average reduction efficiency (R) shall be computed based on the 24-hour average sulfur production rate (S) and sulfur emission rate (E) using the equation in sub. (5) (c) 1. 1. Data obtained from the sulfur production rate monitoring device specified in par. (a) shall be used to determine S. 2. Data obtained from the sulfur emission rate monitoring systems specified in par. (b) or (c) shall be used to calculate a 24-hour average for the sulfur emission rate (E). The monitoring system shall provide at least one data point in each successive 15-minute interval. At least 2 data points shall be used to calculate each 1-hour average. A minimum of 18 1-hour averages shall be used to compute each 24-hour average. NR 440.684(e) In lieu of complying with par. (b) or (c), those sources with a design capacity of less than 152 Mg/d (150 long ton/day) of H2S expressed as sulfur may calculate the sulfur emission reduction efficiency achieved for each 24-hour period by using the following equation: R = K2S/X
where:
R is the sulfur dioxide removal efficiency achieved during the 24-hour period, percent
K2 is a conversion factor, 0.02400 Mg/d per kg/hr (0.01071 long ton/day per lb/hr)
S is the sulfur production rate during the 24-hour period, kg/hr (lb/hr)
X is the sulfur feed rate in the acid gas, Mg/d (long ton/day)
(f) The monitoring devices required in sub. (7) (b) 1., (b) 3., and (c) shall be calibrated at least annually according to the manufacturer's specifications as required by s. NR 440.13(2).(g) The continuous emission monitoring systems required in sub. (7) (b) 1., (b) 3., and (c) shall be subject to the emission monitoring requirements of s. NR 440.13. For conducting the continuous emission monitoring system performance evaluation required by s. NR 440.13(3), Performance Specification 2 of 40 CFR part 60, Appendix B, incorporated by reference in s. NR 440.17, shall apply, and Method 6 of 40 CFR part 60, Appendix A, incorporated by reference in s. NR 440.17, shall be used for systems required by par. (b).(8) RECORDKEEPING AND REPORTING REQUIREMENTS. (a) Records of the calculations and measurements required in subs. (3) (a) and (b) and (7) (a) to (g) shall be retained for at least 2 years following the date of the measurements by owners and operators subject to this section. This requirement is included under s. NR 440.07(5).(b) Each owner or operator shall submit a written report of excess emissions to the department semiannually. For the purpose of these reports, excess emissions are defined as: 1. Any 24-hour period (at consistent intervals) during which the average sulfur emission reduction efficiency (R) is less than the minimum required efficiency (Z).2. For any affected facility electing to comply with the provisions of sub. (7) (b) 2., any 24-hour period during which the average temperature of the gases leaving the combustion zone of an incinerator is less than the appropriate operating temperatures determined during the most recent performance test in accordance with the provisions of sub. (7) (b) 2. Each 24-hour period shall consist of at least 96 temperature measurements equally spaced over the 24 hours.(c) To certify that a facility is exempt from the control requirements of these standards, each owner or operator of a facility with a design capacity less than 2 LT/D of H2S in the acid gas (expressed as sulfur) shall keep, for the life of the facility, an analysis demonstrating that the facility's design capacity is less than 2 LT/D of H2S expressed as sulfur.(d) Each owner or operator who elects to comply with sub. (7) (e) shall keep, for the life of the facility, a record demonstrating that the facility's design capacity is less than 150 LT/D of H2S expressed as sulfur.(9) OPTIONAL PROCEDURE FOR MEASURING HYDROGEN SULFIDE IN ACID GAS-TUTWILER PROCEDURE. (a)General. The Tutwiler procedure may be used to measure hydrogen sulfide in acid gas in accordance with the Gas Engineer's Handbook, first edition, second printing, Fuel Gas Engineering Practices, page 6/25, incorporated by reference in s. NR 440.17. When an instantaneous sample is desired and H2S concentration is 10 grains per 1000 cubic foot or more, a 100 ml Tutwiler burette is used. For concentrations less than 10 grains, a 500 ml Tutwiler burette and more dilute solutions are used. In principle this method consists of titrating hydrogen sulfide in a gas sample directly with a standard solution of iodine.(b)Apparatus. (See Figure 1.) A 100 or 500 ml capacity Tutwiler burette with 2-way glass stopcock at the bottom and 3-way stopcock at the top is connected either with inlet tubulature or a glass-stoppered cylinder, 10 ml capacity, graduated i n 0.1 ml subdivisions, with rubber tubing connecting the burette with a leveling bottle.(c)Reagents.1. Iodine stock solution, 0.1N. Weigh out 12.7 g of iodine and 20 to 25 g cp potassium iodide for each liter of solution. Dissolve the KI in as little water as necessary and then dissolve the iodine in the concentrated KI solution, make up to proper volume, and store in a glass-stoppered brown glass bottle.2. Standard iodine solution, 1 ml " 0.001771 g I. Transfer 33.7 ml of the 0.1N stock solution into a 250 ml volumetric flask, add water to the mark and mix well. Then, for a 100 ml sample of gas, 1 ml of standard iodine solution is equivalent to 100 grains of H2S per cubic foot of gas. Starch solution. Rub into a thin paste about one teaspoonful of wheat starch with a little water, pour it into about a pint of boiling water and stir. After it has cooled, decant off the clear solution. Make fresh solution every few days.
(d)Procedure. Fill the leveling bulb with starch solution. Raise (L), open cock (G), open (F) to (A), and close (F) when the solution starts to run out of the gas inlet. Close (G). Purge the gas sampling line and connect it with (A). Lower (L) and open (F) and (G). When the liquid level is several ml past the 100 ml mark, close (G) and (F), and disconnect the sampling tube. Open (G) and bring the starch solution to the 100 ml mark by raising (L), then close (G). Open (F) momentarily, to bring the gas in the burette to atmospheric pressure, and close (F). Open (G) and bring the liquid level down to the 10 ml mark by lowering (L). Close (G), clamp the rubber tubing near (E) and disconnect it from the burette. Rinse the graduated cylinder with a standard iodine solution (0.00171 g I per ml), fill the cylinder and record the reading. Introduce successive small amounts of iodine thru (F), shaking well after each addition, and continue until a faint permanent blue color is obtained. Record the reading, subtract it from the previous reading and call the difference D.(e)Reagent test. With every fresh stock of starch solution, perform a blank test as follows: introduce fresh starch solution into the burette up to the 100 ml mark. Close (F) and (G). Lower (L) and open (G). When the liquid level reaches the 10 ml mark, close (G). With air in the burette titrate as during a test and up to the same end point. Call the ml of iodine used C. Then, Grains H2S per 100 cubic foot of gas = 100 (D - C)
(f)Sensitivity enhancement. Greater sensitivity can be attained if a 500 ml capacity Tutwiler burette is used with a more dilute (0.001N) iodine solution. Concentrations less than 1.0 grains per 100 cubic foot can be determined in this way. Usually the starch-iodine end point is much less distinct and a blank determination of end point, with H2S-free gas or air, is required. See PDF for diagram
Figure 1. Tutwiler burette (lettered items mentioned in text).
Wis. Admin. Code Department of Natural Resources NR 440.684
Cr. Register, September, 1990, No. 417, eff. 10-1-90; am. (2) (a) 4., (4) (b), (7) (a) 2. and 4., (b) 3., (c), (d) (intro.), (e) and (8) (a), renum. (2) (b) 4. to 6. to be (2) (b) 5. to 7., cr. (2) (b) 4., r. and recr. (5), r. (6), Register, July, 1993, No. 451, eff. 8-1-93; am. (5) (c) 3., Register, December, 1995, No. 480, eff. 1-1-96; CR 06-109: am. (2) (a) 8. and (b) 1. to 3., (4) (b), (5) (b) 1. to 3., (c) 2. and 4. and (7) (b) 1. and (c), r. (2) (b) 4., renum. (2) (b) 5. to 7. to be (2) (b) 4. to 5. and am., r. and recr. (5) (c) 3. and (7) (e) Register May 2008 No. 629, eff. 6-1-08.