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.
NR 440.684(9)(d)(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. NR 440.684(9)(e)(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, NR 440.684(9)(f)(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.
Figure 1. Tutwiler burette (lettered items mentioned in text).
NR 440.684 HistoryHistory: 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. NR 440.686NR 440.686 Volatile organic compound (VOC) emissions from synthetic organic chemical manufacturing industry (SOCMI) distillation operations. NR 440.686(1)(1) Applicability and designation of affected facility. NR 440.686(1)(a)(a) The provisions of this section apply to each affected facility designated in par. (b) that is part of a process unit 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). NR 440.686(1)(b)(b) The affected facility is any of the following for which construction, modification or reconstruction commenced after December 30, 1983: NR 440.686(1)(b)1.1. Each distillation unit not discharging its vent stream into a recovery system. NR 440.686(1)(b)2.2. Each combination of a distillation unit and the common recovery system into which its vent stream is discharged. NR 440.686(1)(b)3.3. Each combination of 2 or more distillation units and the common recovery system into which their vent streams are discharged. NR 440.686(1)(c)1.1. Any distillation unit operating a part of a process unit which produces coal tar or beverage alcohols or which uses, contains and produces no VOC is not an affected facility. NR 440.686(1)(c)3.3. Any distillation unit that is designed and operates as a batch operation is not an affected facility. NR 440.686(1)(c)4.4. Each affected facility that has a total resource effectiveness (TRE) index value greater than 8.0 is exempt from all provisions of this section except for subs. (3), (5) (d), (e) and (f) and (6) (h) and (L). NR 440.686(1)(c)5.5. Each affected facility in a process unit with a total design capacity for all chemicals produced within that unit of less than one gigagram per year is exempt from all provisions of this section except for the recordkeeping and reporting requirements in sub. (6) (j), (L) 6. and (n). NR 440.686(1)(c)6.6. Each affected facility operated with a vent stream flow rate less than 0.008 scm/min is exempt from all provisions of this section except for the test method and procedure and the recordkeeping and reporting requirements in subs. (5) (g) and (6) (i), (L) 5. and (o). NR 440.686 NoteNote: 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 less methane and ethane. This emission limit reflects the performance of BDT.
NR 440.686(1)(d)1.1. 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) 4. and 6. 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. NR 440.686(1)(d)2.2. 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. NR 440.686(1)(d)3.3. 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. NR 440.686(1)(d)4.4. 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), as in effect on December 14, 2000, 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). NR 440.686(2)(2) Definitions. As used in this section, all terms not defined here shall have the meaning given them in s. NR 440.02 and the following terms shall have the specific meanings given them: NR 440.686(2)(a)(a) “Batch distillation operation” means a noncontinuous distillation operation in which a discrete quantity or batch of liquid feed is charged into a distillation unit and distilled at one time. After the initial charging of the liquid feed, no additional liquid is added during the distillation operation. NR 440.686(2)(b)(b) “Boiler” means any enclosed combustion device that extracts useful energy in the form of steam. NR 440.686(2)(c)(c) “By compound” means by individual steam components, not carbon equivalents. NR 440.686(2)(d)(d) “Continuous recorder” means a data recording device recording an instantaneous data value at least once every 15 minutes. NR 440.686(2)(e)(e) “Distillation operation” means an operation separating one or more feed streams into 2 or more exit streams, each exit stream having component concentrations different from those in the feed streams. The separation is achieved by the redistribution of the components between the liquid and vapor- phase as they approach equilibrium within the distillation unit. NR 440.686(2)(f)(f) “Distillation unit” means a device or vessel in which distillation operations occur, including all associated internals, such as trays or packing, and accessories, such as reboiler, condenser, vacuum pump, steam jet or other similar device, plus any associated recovery system. NR 440.686(2)(g)(g) “Flame zone” means the portion of the combustion chamber in a boiler occupied by the flame envelope. NR 440.686(2)(h)(h) “Flow indicator” means a device which indicates whether gas flow is present in a vent stream. NR 440.686(2)(i)(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. NR 440.686(2)(j)(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. NR 440.686(2)(k)(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. NR 440.686(2)(L)(L) “Process unit” means equipment assembled and connected by pipes or ducts to produce, as intermediates 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. NR 440.686(2)(m)(m) “Product” means any compound or chemical listed in sub. (8) that is produced for sale as a final product as that chemical or for use in the production of other chemicals or compounds. By-products, co-products and intermediates are considered to be products. NR 440.686(2)(n)(n) “Recovery device” means an individual unit of equipment, such as an absorber, carbon adsorber or condenser, capable of and used for the purpose of recovering chemicals for use, reuse or sale. NR 440.686(2)(o)(o) “Recovery system” means an individual recovery device or series of such devices applied to the same vent stream. NR 440.686(2)(p)(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) 2. a., hourly emissions rate as required in sub. (5) (e) 5. 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). NR 440.686(2)(q)(q) “TRE index value” means a measure of supplemental total resource requirement per unit reduction of TOC associated with an individual distillation 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). NR 440.686(2)(r)(r) “Vent stream” means any gas stream discharged directly from a distillation facility to the atmosphere or indirectly to the atmosphere after diversion through other process equipment. The vent stream excludes relief valve discharges and equipment leaks including, but not limited to, pumps, compressors and valves. NR 440.686(3)(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: NR 440.686(3)(a)(a) Reduce emission of TOC, less methane and ethane, by 98 weight-percent or to a TOC, less 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 NR 440.686(3)(c)(c) Maintain a TRE index value greater than 1.0 without use of VOC emission control devices. NR 440.686(4)(a)(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) shall install, calibrate, maintain and operate according to manufacturer’s specifications the following equipment: NR 440.686(4)(a)1.1. 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. NR 440.686(4)(a)1.a.a. Where an incinerator other than a catalytic incinerator is used, a temperature monitoring device shall be installed in the firebox. NR 440.686(4)(a)1.b.b. Where a catalytic incinerator is used, temperature monitoring devices shall be installed in the gas stream immediately before and after the catalyst bed. NR 440.686(4)(a)2.2. 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. NR 440.686(4)(b)(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: NR 440.686(4)(b)1.1. A heat sensing device, such as a ultra-violet beam sensor or thermocouple, at the pilot light to indicate the continuous presence of a flame. NR 440.686(4)(b)2.2. 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. NR 440.686(4)(c)(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: NR 440.686(4)(c)1.1. 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 distillation unit 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. NR 440.686(4)(c)2.2. 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. NR 440.686(4)(d)(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 heat input capacity of the boiler or process heater is 44 MW (150 million Btu/hr) or greater. The records shall be readily available for inspection. NR 440.686(4)(e)(e) The owner or operator of an affected facility that seeks to comply 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: NR 440.686(4)(e)1.1. Where an absorber is the final recovery device in the recovery system: NR 440.686(4)(e)1.a.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; or NR 440.686(4)(e)1.b.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 infrared, photoionization or thermal conductivity, each quipped with a continuous recorder. NR 440.686(4)(e)2.2. Where a condenser is the final recovery device in the recovery system: NR 440.686(4)(e)2.a.a. The condenser exit (product side) 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; or NR 440.686(4)(e)2.b.b. An organic monitoring device used to monitor 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. NR 440.686(4)(e)3.3. Where a carbon adsorber is the final recovery device unit in the recovery system: NR 440.686(4)(e)3.a.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; or NR 440.686(4)(e)3.b.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. NR 440.686(4)(f)(f) An owner or operator or an affected facility seeking to demonstrate compliance with the standards specified under sub. (3) with control devices other than incinerator, boiler, process heater or flare; or recovery device 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. NR 440.686(5)(a)(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. NR 440.686(5)(b)(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), shall be used as reference methods to determine compliance with the emission limit or percent reduction efficiency specified under sub. (3) (a). NR 440.686(5)(b)1.1. 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. NR 440.686(5)(b)2.2. Method 2, 2A, 2C or 2D, as appropriate, for determination of the gas volumetric flow rates. NR 440.686(5)(b)3.3. 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 completed using the following equation: 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
NR 440.686(5)(b)4.4. Method 18 to determine the 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. NR 440.686(5)(b)4.a.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. NR 440.686(5)(b)4.b.b. The emission reduction (R) of TOC (minus methane and ethane) shall be determined using the following equation: where:
