Odour control in a municipal waste water treatment plant

application note

8810 analyzer

8350/8351 probe 9135 transmitter

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1 - WHAT IS THE PROBLEM ?

Industrial unpleasant odours Industries Cement works, lime kilns Origin of odours Acrolein, amines, mercaptans, ammonia, dibutyl sulphide, H2S, SO2, etc. Fermentation products Fermentation products Amines, sulphides, mercaptans Sulphide, mercaptans Phenolic compounds H2S, SO2 Ammonia, sulphur compounds

Pharmaceutical industries Food industries Food industries (fish) Rubber industries Textile industries Paper pulp industries Organic compost

Odour treatments Odours emanating from water treatment plants are due to gases or fumes given off by some of the components of waste water. They are also caused by compounds formed during the various stages of treatment. The list of pollutants to be encountered in the atmosphere of a treatment plant includes many families of compounds based on nitrogen, sulphur, hydrocarbons etc.

Gas pollutants in waste water treatment plant Nitrogen compounds Ammonia Amines Amines oxides NH3 R-NH2, R2-NH, R3-N RH-NO, R2H-NO, R3-NO

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Nitrogen Sulphur compounds Hydrogen sulphide Mercaptans Hydrocarbons Saturated and/or unsaturated Aromatic Chlorine derivatives Other compounds Aldehydes Acrolein Alcohols Saturated and.or unsaturated fatty acids Skatole Diamino sulphides

NOx

H2S R-S-H, R-S-R

R-CHO CH2-CHCHO R-CH2OH

R2=N-S-N=R2

2 - ODOUR TREATMENT PROCESS

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Figure 1
Odour treatment necessitates a few pre-treatment techniques (reducing emissions, ventilation etc) before the chemical treatment in a gas scrubber occurs. The first step of the gas scrubber is to transfer pollutants from the gas phase to the liquid phase, sometimes enhanced by the second stage oxidation of the components in the liquid phase. This single second stage often proves itself insufficient to remove a wide spectrum of odours. The solution lies in providing several stages in series. Major characteristics for this gas treatment are: . a "stage column" filled with sulphuric acid solution, operates against the dust, cools gases and reduces ammonia and amine exhaust. a 'packed column' filled with sodium hypochlorite and caustic soda solution realises the oxidation of the compounds based on sulphur, nitrogen, oxygen and dissolved acid derivatives created previously.

Examples of chlorine oxidation reactions: 1) explained by NH3 + HCIO NH3 + H2O NH4+ + HCIO 2) 3) H2S + 4ClO2 => => => => NH2Cl (Chloramine) NH4+ + OH
-

NH2Cl + H3O+ 4Cl- + H2S04 CHH3S03 + 3Cl (Methylsulphonic acid)

CH3SH + 3ClO => (Mercaptan)

the "packed column" is replenished thanks to a source of chlorine adapted to the consumption of chlorine per hour. For example, concentrated sodium hypochlorite, industrial sodium hypochlorite solution or electochlorinator. (See Figure 1)

In the "packed column", the content of chlorine (in its form ClO - ) corresponds with the oxidation reagent's reservoir against pollutants. The level of chlorine is dependent on: . . . the average concentration of pollutant volume of air through the tower response time analysis - because with only one analysis per day, carried out by the laboratory, the user will be obliged to increase the injection of chlorine. This is why the level of chlorine sometimes ends up at 2g/l. Therefore, it will take at least one night to consume all the chlorine in the tower.

As a consequence, the consumption of chlorine per week becomes tremendous. This causes financial, transportation and stock problems.
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If the waste water plant is small (below 50,000 m3/h of treated toxic air), these problems of cost, stock and transport cannot be solved. However, costs can be reduced by using low-cost sodium hypochlorite, which is released, for example, by industrial manufacturing cleaning solutions. In this case, the source of chlorine is mixed with soap-like compounds which change the composition of the sample. If the waste water plant is large, the source of chlorine becomes an electrochlorinator. Sodium hypochlorite is produced on site by electroxidation of chloride (Cl - ) in the gas chlorine (Cl 2 ) and electroreduction of water (H2O)in hydrogen gas, mixed with hydroxyl ion (OH - ). This technique means the customer has to deal with electrochlorination, but reduces the cost of the raw product (sodium chloride salt and electricity). In this case, together with chlorine comes small graphite (carbon) particles from electrode decomposition. These particles also change the sample composition.

3 - ON-LINE CHLORINE MEASUREMENT

Maintaining the correct content of chlorine in the water is the key to a good process. Optimizing the injection of chlorine will reduce the cost and will guarantee at any moment that the process is within specifications for pollutant-free exhaust. 3.2 Chemical description of the sample: 100-2000 mg/l depending on the NaClO injection 8<pH<11 depending on the NaOH injection TH<10 French Degree if make up water is decarbonated

Chlorine Alkalinity Hardness 3.3

Review of the available measurement technologies * Potentiometric measurement

The oxidoreduction potential measurement of the solution is sometimes proposed because its cheap. We must insist that redox potentials have nothing to do with the concentration of chlorine in the water. At most, it indicates if one oxidizing reagent is in excess or not, according to the formula: E = E0 + K + log (oxidized form) n (Reduced form) E is then dependent on all the different species combined in the solution, and reflects only the ratio between the oxidized and the reduced form. Therefore, operating with the redox or RH measurement will be risky if there is not a large excess of chlorine in the bath. Oxidizing towers equiped with redox measurement will consume a lot of concentrated chlorine solution. The bigger the station, the more the chlorine waste will increase costs, stock and transport problems. This therefore is not the ideal solution to control the process.

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* UV Measurement: Today, there are no industrial analysers based on this principle for this application, because complex sample contents cause too much interference on the UV detection. * Amperometric measurement: Amperometry analysis follows the reduction current between the two electrodes which is proportional to the concentration of the oxidizing reagent. This is the principle of the CHLOROMAT for drinking water. Three years ago Polymetron released a high concentration chlorine system on the French market with: a dilution of the sample to reduce the reduction wave an acidification of the diluted sample a CHLOROMAT cell and the transmitter

Its use on the site has shown this is a good solution but with the following drawbacks: concentration of NAOH can change a lot in a very short time, taking away the pH buffered value source of chlorine e.g. electrochlorinator will bring particles which require maintenance on the analyser itself or on a filtration unit source of chlorine e.g. industrial cleaning solution is mixed with foam and detergent which are not suitable for the analysis

3.4 - Potentiometric titration

3.4.1

Measurement principle

This measurement determines the chlorine concentration by the quantity of thiosulphate oxidized by the chlorine present in the sample.

In principle (equation N1l): Cl2 + 2(S 2032 ) Chlorine gas Thiosulphate => 2Cl+ Chloride S4O62Tetrathiorate

But in the water at pH=5, chlorine gas produces (equation number 2): Cl2 + H2O => Chlorine HCIO + Hypochlorous acid HCl Hydrochloric acid

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(Equation N1 +Equation N2) leads to thiosulphate oxidation in water at pH3 Equation N3: 2HCIO + 2H+ + 2(S 2O3 2- ) => 3.4.2 Laboratory measurement 2Cl - + S4O62- + 2H3O+

Potential changes in the manual titration can be observed on a platinum electrode or with changes in the colour of an indicator. The common indicator is named thiodene and corresponds with a soluble amidon version. (Equation no4): 2HCIO + (Equation no5): I2 + iodine Tetrathionate 2H+ + KI 2 => Thiodene thiosulphate I2 + KCI + H20 + S4O22liodide

Thus every single molecule of chlorine is transferred into iodine (equation N4). The iodine molecules react as an oxidant over the thiosulphate (equation N5). When the blue colour of the indicator disappears, it means that all iodine has disappeared in the reaction with the thiosulphate. Thus, the volume of thiosulphate added to the solution is proportional with the original chlorine concentration.

3.4.3

8810 Analyser for chlorine measurement in that application

* Methodology Titration as follows: . . . Sample taken: 70ml pH sample conditioning with 4ml of acetic acid buffer solution Thiosulphate solution added until redox potential shows that chlorine has disappeared. Proper working time of the titration pump is related to the original chlorine concentration by a calibration curve. Chemical cleaning phase programmable in frequency, length and strength.

In other words, the principle and operations of the 8810 titration are exactly the same as the principle and operations of laboratory titration. In fact, for many people, this likeness between the laboratory and 8810 titrations creates a strong feeling of confidence. This is one of our major sales argument. * 8810 analyser installation . . Insert 8810 after the circulating pump of the bath Request a fast loop for the sample line
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Freely programmable alarm for low and high concentrations

* System configuration . or 368810,50xxx . or 368810,71050 . 368810,56000 Additional piston pump for conditioning instead of a peristaltic pump Chemical cleaning complete with 10 l canister and level detector
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368810,20xxx

8810 ORP analyser complete with platinum and reference electrode and one peristaltic pump for titration with sodium thiosulfate Same analyser with a piston pump instead of a peristaltic pump Additional peristaltic pump for conditioning with acetic acid / acetate buffer

368810,700xx

A company of the Zellweger Luwa Group

OPTIONS : . . 368810,40000 368810,45000 Polyester wall mounting cabinet Free standing cabinet

N.B. Automatic calibration doesnt exist for this application. Chlorine solutions are not stable enough in time (NaClO slowly transformed to Cl2 under oxygen activity). * Main sales arguments / benefits of this solution . . . 8810 measurement principle is the same as laboratory one 8810 measurement operation is the same as laboratory one Continuous measurement of the residual chlorine guarantees the correct oxidation of the gas pollutant. Its then possible to reduce the residual chlorine average concentration. Chlorine chemical product consumption can be reduced by more than factor 3 ! If the addition of the chlorine is controlled, the amount added, stocked and transported is reduced. Regarding chlorine, you are immediately on the road to a safer world.

4. pH AND REDOX MEASUREMENT

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