73-CHO-1 (REPORT NUMBER) AIR POLLUTION EMISSION TEST TENNECO CHEMICALS (PLANT NAME; Fords, New Jersey (PLANT ADDRESS) U. S. ENVIRONMENTAL PROTECTION AGENCY Office of Air and Water Programs Office of Air Quality Planning and Standards Emission Standards and Engineering Division Emission Measurement Branch Research Triangle Park, N. C. 27711 ------- Emission Testing Report EMB Test No.: 73-CHO-l TENNECO CHEMICALS Fords, New Jersey Roger 0, Pfaff Project Officer Environmental Protection Agency Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 ------- ftni r or- ^miTrm- I r\UL.L- \JI V/UM I 1-IY I Page Number(s) I. INTRODUCTION 1-2 TABLE 1 - Summary o.f Results ; . . . . 2 • II. DISCUSSION OF RESULTS 3 III. PROCESS DESCRIPTION 4-6 Figure 1 - Process Flow Diagram 5 Figure 2 - Location of Sampling Point .... 6 IV. SAMPLING AND ANALYTICAL PROCEDURES 7 ------- INTRODUCTION Under the Clean Air Act, as amended, the Environmental Protection Agency is responsible for establishing Federal performance standards for new stationary sources which contribute significantly to air pollution or cause or contribute to the endangerment of public health or welfare. Petrochemical manufacturing plants have been included in a listing of such sources. The Office of Air Quality Planning and Standards establishes performance standards from emission data gathered from the best emission control systems which have been shown to be operable and economically feasible. . The Industrial Studies Branch performs a study of all aspects of the industry which are pertinent to the development of emission standards. As part of the industry study for formaldehyde, one of the petrochemicals for which a standard may be established, emission rates from well-controlled plants were desired. TRW, Inc., under contract to the Emission Measurement Branch, performed source tests at Tenneco Chemicals, Inc., in Fords, New Jersey, during the week of July 30, 1973. Measurements were made of formaldehyde, methanol, dimethyl ether, carbon monoxide, and total hydrocarbons emitted from the process. Six test runs were performed under normal process .conditions. A sample of scrubber water for each test run was analyzed for formaldehyde. The iron-oxide process for manufacture of formaldehyde is used at this plant. Emissions are controlled by a five tray bubble cap water absorber. 1 ------- Table 1. Summary of Results Run Number Stack Flow Rate, DSCFMa(Nm3/min)b 16,298(461.3) 16,380(463.6) 16,699(472.6)16,192(458.2)15,037(425.5) 16,151(457,1) Stack Temperature, °F (°C) 80(27) 80(27) 80(27) 80(27) 80(27) 80(27) THC as methanol', Ib/hr (Kg/hr) 235.2(106.8) 278.8(126.6) 288.2(130.8) 315.1(143.1) 279.0(126.7) 395.6(181,4) THC as carbon, Ib/hr (Kg/hr) 88.2(40.0) 104.6(47.5) 108.1(49.1) 118.2(53.7) 104.6(47.5) 105.0(49.5) Formaldehyde, Ib/hr (Kg/hr) ' 33.35(15.1) 35.39(16.1) 36.05(16.4) 32.56(14.8) 29.43(13.4) 34.13(15.5) Methanol, Ib/hr (Kg/hr) 40.52(18.4) 30.04(13.6) 30.59(13.9) 32.52(14.8) 50,16(22.8) • 38.51(17.5) Dimethyl ether, Ib/hr (Kg/hr) 10.80(4.90) 13.45(6.11) 10.68(4.85) 10.93(4.96) 11.51(5.231 Carbon monoxide, Ib/hr (Kg/hr) 258.5(117.4) 245.4(111.4) 249.7(113.4) 239.1(108.6) 228.8(103.9) 245.3(111.4) Formaldehyde in scrubber water, mg/ml 5.08 4.2 , 5.35 5.2 "5.65 6.25 3 Dry standard cubic feet per minute at 70°F and 29.92 in. Hg. b Dry normal cubic meters per minute at 21.1°C and 760 mm. Hg. • ------- DISCUSSION OF RESULTS Results of the six test runs compare favorably. Run 1 for dimethyl ether was lost because of a bad bag sample. Runs 2 and 4 were slightly, below percent isokinetic limits (89.9 and 88.9). This was caused by difficulty in pulling the high sampling rate required. Preliminary test results were higher .than expected, so before Run 5 was started the scrubber water flow rate was decreased. This was an attempt to decrease pollutant-containing mist emissions. The reductions had no effect on the emissions. However, after the tests were completed, a change was made in plant operational procedure which is expected to decrease emissions. ------- PROCESS DESCRIPTION The chemistry of the formation of formaldehyde from methanol, via the mixed (metal) oxide catalyst process may be shown as follows: CH3OH + 1/2 02 f CH20' + H20 + 38 Kcal. This differs from the classical silver-catalyzed process in that (apparently) no hydrogen is produced, and the methanol molecule itself, rather than the produced hydrogen, is oxidized. Methanol is mixed with air and heated to between 220 and 350°F in a steam jacketed vaporizer. The methanol will normally comprise about 7.5% (vol.) of the converter feed. The super-heated vapors from the vaporizer pass into the converter, where the oxidation reaction takes place, in tubes filled with a mixed oxide catalyst, between 650°F and 800°F. The heat of reaction is removed by the circulating Dowtherm fluid surrounding the catalyst tubes and is used to produce steam. The converter effluent gases are cooled from approximately 500°F to about 220°F in a heat exchanger prior to being quenched to near 100°F in the absorber. The converter effluent vapors are introduced into the bottom section of the column and flow counter-current to the dilution/scrubbing water, which is pumped onto the top tray and flows downward\ through the tower. The formaldehyde vapors are absorbed by the water, forming a 46 to 53% solution. This exits from the bottom of the tower. The exit gases leave the absorber and pass through a demister pad into the water scrubber. - 4 ------- Vent Water c -5 -a o n n> o CD U3 -I OJ 3 Gas Sample Point Scrubbe Water Air Flow Air Methanol Reactor Air Reactor ->- Waste Water t/) o ~l CT n> -s Temperature of top tray Product Methanol Meter gallons Air Flow ------- Distance to nearest upstream disturbance: 4 feet Type of disturbance: Demister Distance to nearest downstream disturbance: Type of disturbance: End of stack Inside diameter of duct:' 23.5 inches Number'of traverse points: 32 6 feet PoRT A Figure 2 Location of Sampling Point ------- SAMPLING AND ANALYTICAL PROCEDURES Formaldehyde and methanol were collected in water using a modified EPA Method 5 participate train. Formaldehyde was analyzed .by colorimetry after reacting the impinger solution with a chromatropic-sulfuric acid reagent. Methanol. was analyzed by gas chromatography. Details are in Appendix D. Dimethyl ether was collected in an integrated bag sample and analyzed by gas chromatography. Carbon monoxide was collected by drawing a sample from the rear of the probe on the test train. The sample was routed around the THC combustor and to a non-dispersive infrared analyzer (NDIR) after being passed through ascerite to remove CCu. Details are in Appendix D. Total hydrocarbon sample was drawn from the same point as the CO sample but passed through a catalytic combustor to combust all hydrocarbons and CO to C0?. The sample then traveled through the same tubing as the CO sample, but was routed to a second NDIR instead of through the ascerite and CO analyzer. Background CO^ was measured (and subtracted) by bypassing the combustor. It was also during the bypass stage that the CO concentration was determined. Details are in Appendix D. Problems with heating of equipment occurred throughout the test. During half of runs 1 and 5, no heat was applied to the probe or the sample box. During run 6, heat was applied to the probe only, and only during the first half of the test. During the last portion of run 6, the heated Teflon line from the probe to the combustor did not function. ------- |