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    Organic Odor Control With Chlorine Dioxide

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    Costas Aggelidis
    Chlorine dioxide is an effective disinfectant and oxidant that can be used to control odors in wastewater treatment by oxidizing compounds like mercaptans, amines, and sulfides that cause odors. It is more selective than chlorine and can work over a broad pH range. Feed rates vary by application but chlorine dioxide demand studies can determine the needed dosage. It is produced by activating sodium chlorite and feeding it as a dilute solution, which is then analyzed to measure residual levels.

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    Organic Odor Control With Chlorine Dioxide

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    Costas Aggelidis
    89 views3 pages
    Chlorine dioxide is an effective disinfectant and oxidant that can be used to control odors in wastewater treatment by oxidizing compounds like mercaptans, amines, and sulfides that cause odors. It is more selective than chlorine and can work over a broad pH range. Feed rates vary by application but chlorine dioxide demand studies can determine the needed dosage. It is produced by activating sodium chlorite and feeding it as a dilute solution, which is then analyzed to measure residual levels.

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    Organic Odor Control With Chlorine Dioxide

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    Chlorine dioxide is an effective disinfectant and oxidant that can be used to control odors in wastewater treatment by oxidizing compounds like mercaptans, amines, and sulfides that cause odors. It is more selective than chlorine and can work over a broad pH range. Feed rates vary by application but chlorine dioxide demand studies can determine the needed dosage. It is produced by activating sodium chlorite and feeding it as a dilute solution, which is then analyzed to measure residual levels.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    89 views3 pages

    Organic Odor Control With Chlorine Dioxide

    Uploaded by

    Costas Aggelidis
    Chlorine dioxide is an effective disinfectant and oxidant that can be used to control odors in wastewater treatment by oxidizing compounds like mercaptans, amines, and sulfides that cause odors. It is more selective than chlorine and can work over a broad pH range. Feed rates vary by application but chlorine dioxide demand studies can determine the needed dosage. It is produced by activating sodium chlorite and feeding it as a dilute solution, which is then analyzed to measure residual levels.

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    of 3

    OxyChem T

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    Daattaa S
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    A subsidiary of Occidental Petroleum Corp Technical Services 800-733-1165

    Organic Odor Control with Chlorine Dioxide


    mercaptan
    Introduction Phenyl C6H5SH 0.0003
    Chlorine dioxide (ClO2) is effective as both a disinfectant mercaptan
    and an oxidant in water and wastewater treatment. Its Propyl CH3(CH2)2SH 0.0005
    selective reactivity makes chlorine dioxide a powerful mercaptan
    non-chlorinating oxidizing agent useful in many water Skatole C9H9N 0.001
    treating applications for which chlorine and other Thiocresol CH3C6H4SH 0.0001
    oxidizing agents are unsuitable. Unlike most oxidants, tert-butyl (CH3)3CSH 0.00008
    chlorine dioxide may be used over a broad pH range to mercaptan
    oxidize industrial odor causing compounds. Trimethylamine (C H3)3N 0.0004

    The major sources of odorous substances such as


    Application Description mercaptans and substituted amines include the chemical
    A variety of odors are created or liberated in waste and petroleum industries, coking and sanitary
    treatment applications. Odor causing compounds include processes, animal feedlots and rendering plants.
    inorganic gases and organic gases and vapors
    generated as a result of biological activity. Organic Treatment Alternatives
    vapors may also originate from the direct discharge of A variety of technologies have been used for the control
    industrial chemical wastes. Industrial odors can be of odors. Three of the more effective technologies
    caused by a variety of compounds, including inorganic include carbon adsorption, chemical addition (including
    and organic sulfides, organic sulfur compounds including oxidants), and wet chemical scrubbing. The effective
    mercaptans (the sulfur analog of alcohols (RSH)), approach to controlling odor requires a good
    organic disulfides (RSSR), (intermediate oxidation understanding of the characteristics of the waste stream,
    products of mercaptans), various amines, aldehydes, the types of chemicals causing the odors and facility
    ketones, fatty acids, phenols and ammonia. constraints.

    Reduced sulfur compounds and nitrogen-bearing amines The pH of a waste stream has a major effect on both the
    tend to be the most odorous compounds because of generation of odors and the necessary treatment
    their relatively low threshold concentrations (Figure 1). protocol required. Some odor causing compounds are
    Figure 11 substantially more soluble in acidic media while others
    are more soluble in alkaline media (Figure 2). Thus, by
    Substance Formula Odor the proper choice of pH of operation, and oxidant, many
    Threshold odors can be minimized or eliminated.
    (mg/L)
    Allyl mercaptan 0.0001
    CH2:CHCH2S Figure 2: Effect of pH on Odor Generation
    H
    Ammonia NH3 17
    Amyl mercaptan 0.0003
    CH3(CH2)4SH
    Benzyl C6H5CH2SH 0.0002
    mercaptan
    Crotyl CH3(CH)2CH2 0.00003
    mercaptan SH
    Diphenyl sulfide (C6H5)2S 0.0001
    Ethyl mercaptan C2H5SH 0.0003
    Hydrogen H2S 0.0005
    sulfide
    Indole C6H4(CH2)NH 0.0001
    Methyl CH3SH 0.0005
    Chemical oxidation is best suited to moderate volume Chlorine dioxide does not require pH adjustment and
    waste streams containing moderate to high strength does not increase solids loading.
    pollutants and wastewaters with noxious odors, toxic Chlorine dioxide does not form THMs.
    compounds, and compounds which survive primary
    treatment processes. Feed Requirements
    For industrial applications dosages will vary depending
    To use oxidants, the odor must be dissolved, or be on the application. Dose rates may be determined by
    contained in a solid (sludge). In complex wastewater completing a chlorine dioxide demand study. For once-
    streams the odor causing compound may be absorbed through systems, or systems where treated water may
    in acidic or basic scrubbing solutions first which are then enter a US waterway, the concentration of residual
    treated by chemical oxidation. Alkaline scrubbing chlorite ion should be monitored such that it does not
    solutions are effective for sulfides mercaptans, exceed the requirements of the NPDES permit and is in
    aldehydes/ ketones. Acidic scrubbing solutions are compliance with local, state and federal regulations.
    effective for ammonia and amines.

    Chemical Oxidation with Chlorine Dioxide Method of Feed


    Chlorine dioxide is a powerful oxidant effective for the Chlorine dioxide is a gas produced by activating sodium
    control of reduced sulfur compounds and secondary and chlorite with an oxidizing agent or an acid source.
    tertiary amines. Sodium chlorite is converted to chlorine dioxide through
    a chlorine dioxide generator and applied as a dilute
    Between pH 5 and 9, 4.5 mg/L of chlorine dioxide solution. Chlorine dioxide solutions should be applied to
    instantaneously oxidizes 1 mg/L of a mercaptan the processing system at a point and in a manner which
    (expressed as sulfur) to the respective sulfonic acid permits adequate mixing and uniform distribution. The
    (RSO3H)/sulfonate compound, destroying the mercaptan feed point should be well below the water level to
    odor. Similarly, chlorine dioxide reacts with organic prevent volatilization of the chlorine dioxide.
    sulfides and disulfides, destroying the original odor.
    Organic disulfides are split at the sulfur atoms and Chlorine Dioxide Analysis
    oxidized to sulfonic acid. Residual chlorine dioxide concentrations should be
    determined by substantiated methods, which are specific
    The oxidation of amines with chlorine dioxide depends for chlorine dioxide. Chlorine dioxide solutions can be
    on the pH of the reaction mixture and the degree of analyzed by iodometric and amperometric titrations, and
    substitution of the amine. Between pH 5 and 9, an spectrophotometrically, with the standard DPD (N,N-
    average of 10 mg/L of chlorine dioxide oxidizes 1 mg/L diethyl-p-phenylenediamine) method. These methods
    of a tertiary aliphatic amine (expressed as nitrogen), are described in detail in Standard Methods for the
    destroying the amine odor. At pH above 7, an average Examination of Water and Wastewater3.
    of 5 mg/L of chlorine dioxide oxidizes 1 mg/L of a
    secondary aliphatic amine (expressed as nitrogen), 4500-ClO2 B Iodometric Method
    removing all traces of amine odor. The higher the pH of 4500-ClO2 D DPD-Glycine Method
    the reaction mixture (chlorine dioxide and tertiary and/or 4500-ClO2 E Amperometric Method II
    secondary aliphatic amines), the more rapidly oxidation
    proceeds.
    Further Information
    Alternative Oxidants
    Hydrogen Peroxide does not destroy mercaptans More detailed information on sodium chlorite is available

    and phenols unless catalyzed by ferrous sulfate. on request through the OxyChem Technical Service
    Hydrogen peroxide-ferrous sulfate, which requires Department. Call or write:
    acidic pH's, has the lowest chemical cost, but results
    in high solids loading and increased disposal costs. Technical Service Department
    Chlorine is the only oxidant that reacts with OxyChem

    ammonia, however, halogenated by-products restrict Post Office Box 12283


    use. Wichita, Kansas 67277-2283
    800-733-1165 option #1
    Potassium Permanganate is a strong oxidant,
    www.oxy.com
    which yields insoluble MnO2 as a byproduct. This
    results in high solids loading and significant disposal
    costs.

    Advantages of Chlorine Dioxide References


    Chlorine dioxide reacts more rapidly and completely 1. Odor Control in Wastewater Treatment Plants, WEF,
    than other available oxidizers. Manual of Practice No 22, ASCE Manuals of
    Reports on Engineering Practice No 82., Page 8, Wastewater, APHA, AWWA and WEF, Washington,
    (1995) D.C. (20th Ed. l998).

    2. Standard Methods for the Examination of Water and

    Important: The information presented herein, while not guaranteed, was prepared by technical personnel and is true and accurate to the best of our knowledge. NO WARRANTY OF
    MERCHANTABILITY OR OF FITNESS FOR A PARTICULAR PURPOSE, OR WARRANTY OR GUARANTY OF ANY OTHER KIND, EXPRESS OR IMPLIED, IS MADE REGARDING
    PERFORMANCE, SAFETY, SUITABILITY, STABILITY OR OTHERWISE. This information is not intended to be all-inclusive as to the manner and conditions of use, handling, storage,
    disposal and other factors that may involve other or additional legal, environmental, safety or performance considerations, and OxyChem assumes no liability whatsoever for the use of or
    reliance upon this information. While our technical personnel will be happy to respond to questions, safe handling and use of the product remains the responsibility of the customer. No
    suggestions for use are intended as, and nothing herein shall be construed as, a recommendation to infringe any existing patents or to violate any Federal, State, local or foreign laws.

    TDS 600-408 01/09

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