Chemical Oxidation Oxidizing agents

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1 Chemical Oxidation CENG 4710 Environmental Control Chemical oxidation is used to detoxify waste by adding an oxidizing agent to chemically transform waste compounds. It is capable of destroying a wide range of organic compounds, including chlorinated VOCs, phenols, and inorganics such as cyanide. Oxidizing agents Ozone (commonly used) Hydrogen peroxide (commonly used) Chlorine (may result in chlorine substitution rather than destruction of the organic; the resulting chlorinated hydrocarbon may be more toxic) Ultraviolet (UV) light is usually added along with ozone and/or hydrogen peroxide to accelerate the oxidation of VOCs 98

2 99 CENG 4710 Environmental Control

3 Measurement of Organic Content determines the approximate quantity of oxygen required to biologically stabilize the organic matter determines the size of waste treatment facilities measures the efficiency of some treatment processes determines compliance with wastewater discharge limits Chemical Oxygen Demand (COD) The oxygen equivalent of the organic matter that can be oxidized is measured by using a strong chemical oxidizing agent in an acidic medium. Potassium dichromate is excellent for this purpose. Test is performed at elevated temperature Catalyst (silver sulfate) is required in some cases The principle reaction is Organic matter (C a HbOc ) Cr2O7 2 H catalyst 3 Cr CO2 H2O heat Some inorganic compounds may interfere with the test 100

4 Total Organic Carbon (TOC) A known quantity of sample is injected into a high temperature furnace or chemicallyoxidizing environment The organic carbon is oxidized to carbon dioxide in the presence of a catalyst The carbon dioxide produced is measured by an infrared analyser The test is very quick so it becomes popular Biochemical oxygen demand (BOD) measurement of the dissolved oxygen used by microorganisms in the biochemical oxidation of organic matter 5-day or 10-day BOD (BOD5 or BOD10) is most used 101

5 Theoretical Oxygen Demand (ThOD) Organic compounds in wastewater is a combination of carbon, hydrogen, oxygen, and nitrogen The ThOD can be computed if the chemical formula of the organic matter is known Its usage is limited because the organic matter in wastewater is usually a mixture of many unknown substances Example: Determine the ThOD for glycine (CH2( NH2 ) COOH ) using the following assumptions: 1. In the first step, the organic carbon and nitrogen are converted to carbon dioxide and ammonia. 2. In the second and third steps, the ammonia is oxidized sequentially to nitrite and nitrate. 3. The ThOD is the sum of the oxygen required for all three steps. 102

6 Solution 1. Write the balanced reaction for the carbonaceous oxygen demand: 3 CH2( NH2 ) COOH O2 NH3 2CO2 H2O 2 2. Write the balanced reaction for the nitrogenous oxygen demand: (a) NH3 3 O2 HNO2 H2O 2 (b) HNO2 1 O2 HNO NH3 2O2 HNO3 H2O 3. Determine the ThOD: ThOD = (3/2+2) mol O2/mol glycine = 3.5 mol O2/mol glycine 32 g/mol O2 = 112 g O2/mol glycine 103

7 Process Description Conducted in completely mixed tanks or plug flow reactors Contaminated water is introduced at one side of the tank and the treated water exits at the other side Oxidizing agent is dosed into the tank Complete mixing is necessary to prevent shortcircuiting in the tank, so the contaminants can contact with the oxidizing agent for a minimum period of time and the chemical dosage is reduced Design Considerations Ozone Produced from oxygen using electrical energy to split the oxygen into two oxygen radicals (O ) The radicals combine with other oxygen molecules (O2) to form ozone (O3) Ozone is a unstable (disadvantage), blue gas at normal temperature and pressure Ozone is a powerful oxidant The reaction products are less toxic and many are biodegradable 104

8 105 CENG 4710 Environmental Control

9 Reactions between ozone and organic molecules include the insertion of oxygen into a benzene ring, the breaking of double bonds, and the oxidation of alcohol. Ozonolysis of the C=C bond produces aldehydes and ketones: Alcohols react with ozone to form organic acids: 3RCH 2OH 2O3 3RCOOH 3H2O Using UV light with ozone can dramatically reduce the reaction time required. 106

10 107 CENG 4710 Environmental Control

11 Figure 9-30 Reactions of ozone in aqueous solution 108

12 Fig Degradation of phenol by ozone 109

13 Example: Determine the amount of ozone required to treat 760 L/min of ground water contaminated with trichloroethylene at 150 g/l. Assume 90% removal is required. Solution: From the figure, select the highest ozone dosage rate (1.4 mg/l min), 90% removal requires about 1 hour of contact at 1.4 mg/l min. Required dose: 1.4 mg/l min 60 min = 84 mg/l Mass of ozone required daily: (760 L/min)(1440 min/day)(84 mg/l) = mg/day = 91.9 kg/day Note that using ozone combined with UV light at 0.42 watts/l, the contact time is reduced to approximately one minute. 110

14 Hydrogen peroxide In the presence of an iron catalyst (Fenton s reagent), hydrogen peroxide produces the hydroxyl radical ( OH). This radical reacts with organic compounds to produce a reactive organic radical, which can again react with hydrogen peroxide to produce an additional hydroxyl radical: OH RH R H 2 O R H O OH ROH 2 2 Schmitt reported on the use of hydrogen peroxide to treat a paint stripping liquid waste containing the following contaminants: Methylene Chloride: 50-1,000 mg/l Phenol: 500-6,000 mg/l Chromium (VI): mg/l It was shown that 99% of the phenol could be destroyed following Cr 6+ reduction and precipitation, at a dosage of 2.5 g H 2 O 2 per g phenol, with an iron catalyst level of 0.05 mg Fe 2+ /mg H 2 O

15 The effectiveness of H2O2 may be greatly enhanced by UV light, as seen in Fig The application of H2O2 +UV light is a well established technology with operating costs ranging from US$1 to US$10 per thousand gallons treated. When UV is used to catalyze peroxide reactions, the ability of the water to transmit light becomes important, and information must be obtained on light transmissibility. Pre-treatment to remove color, iron, or suspended solids may be required. Fig Decomposition of trichlorethylene (TCE) with H2O2, UV and H2O2 +UV. 112

16 Example: Calculate the amount of H2O2 and iron catalyst (as Fe 2+ ) to remove 99% of the phenol in a 10,000 L/day waste stream containing 6,000 mg/l of phenol. Solution: The required dosage for 99% removal are 2.5 g H2O2 per g phenol and 0.05 mg Fe 2+ /mg H2O2. Mass of phenol to be treated per day: 10,000 L/d 6,000 mg/l= mg/d=60kg/day Mass of H2O2 required daily: 60 kg/day 2.5 g H2O2 /g phenol = 150 kg/day Mass of Fe 2+ required daily: 150 kg/day 0.05 mg Fe 2+ /mg H2O2 =7.5 kg/day 113

17 Chlorine For aqueous waste treatment, chlorine is evaporated to a gas and mixed with water to provide a hypochlorous acid (HOCl) solution: Cl2( aq) H2O HOCl H Cl Hypochlorous acid ionizes as follows: HOCl H OCl This is ph dependent, the dissociation constant is around 7.6 at ambient temperature. The oxidizing power of chlorine tends to increase with ph. A classical application of oxidation with chlorine is the destruction of cyanide. Under alkaline conditions cyanide is converted to the less toxic cyanate: CN OCl CNO Cl Caution must be exercised to maintain ph above 10 to prevent cyanogen chloride, a toxic gas, from being produced: NaCN Cl2 CNCl NaCl Under caustic conditions, cyanogen chloride is converted to sodium cyanate: CNCl + 2NaOH NaCNO + H2O + NaCl 114

18 Cyanate is destroyed by further alkaline reaction with chlorine: 2NaCNO Cl 4NaOH N 2CO 6NaCl 2H O In practice, excess chlorine must be added to ensure that cyanogen chloride is not produced. The above reactions provide information to determine the stoichiometric amount of chlorine needed. However, the actual amounts required depend on other constituents in the waste such as metals and reducing agents that create a chemical demand for chlorine. Additionally, chlorine is not stable in aqueous solutions and some will be lost to decomposition. 115

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