Review of Municipal Effluent Chlorination/ Dechlorination Principles, Technologies and Practices

David Forgie, Ph.D., P.Eng. - Associated Engineering Phil Wong, P.Eng. - Environment Canada Jennifer Tennant - Environment Canada

Background Most wastewater discharges need to be disinfected to protect public health and/or shellfish from pathogens Chlorination is still popular despite in-roads made by UV disinfection:
UV needs a very clear effluent Cost (capital and O&M) is still a factor

Background - Continued
Chlorination leaves some chlorine residual (either as free or combined chlorine) Chlorine residuals as low as 0.026 mg/L can be toxic to fish Such chlorine residuals would be deleterious substances under the Federal Fisheries Act (Section 36(3)) The 1999 BC Municipal Sewage Regulation requires chlorine residuals be less than 0.010 mg/L (10 ppb)

Background - Continued
There were an estimated 40 wastewater treatment plants in BC that chlorinate Of these, 20 were thought to dechlorinate It was not known how chlorination was being accomplished and controlled Likewise, it was not known how dechlorination was being accomplished or controlled

The Georgia Basin Ecosystem Initiative

Joint Canada US initiative The GBEI is focused on stopping and reversing pollution Wastewater treatment is important Chlorination is both good and bad news

Genesis of the Document

There were questions about chlorination and dechlorination practices in BC The needs of GBEI needed to be fulfilled Environment Canada is a partner in the GBEI Environment Canada wanted to develop a document that would: Provide a technology resource to those who were chlorinating and dechlorinating Document the current chlorination and dechlorination practices

Link to the summary document at: http://www.pyr.ec.gc.ca/georgiabasin/reports/ chlorination/summary_e.htm

Link to the document at: http:www.pyr.ec.gc.ca/GeorgiaBasin/reports/ chlorination/EC-GB-03-73.pdf

Contents of the Document

The chemistry of chlorination Chlorination chemicals Chlorination chemical dosing equipment Measurement of chlorine residuals Dechlorination technology and measurement Results of a survey of current B.C. chlorination/dechlorination practices

Chlorination Chemistry
Cl2 + H 2O HOCl + H+ + ClChlorine gas to hypochlorous acid

HOCL OCl- + H+
Hypochlorous acid to hypochlorite ion

HOCl + NH3 NH2Cl + H2O

Hypochlorous acid to monochloramine

Chlorine effectiveness (by species, concentration, and time)

Hypochlorous Acid fraction as a function of pH

Chlorination Chemistry
Influences on the reactions: pH (higher = less HOCl; less disinfection) Temperature (affects reaction rates) Presence of nitrogen compounds, e.g. ammonia (results in chloramines) Influences on effectiveness: Concentration/Time Mixing Resistant microorganisms (e.g. Giardia, Cryptosporidium, staphylococcus aureus, viruses, etc.)

Chlorination Chemicals
Chlorine Gas, Cl2 Chlorine dioxide (ClO2 ) Sodium Hypochlorite (NaOCl) Calcium Hypochlorite (puck systems) Cost Equivalent to Chlorine Gas: Chlorine Gas = 1 Sodium Hypochlorite = 2.5 Calcium Hypochlorite = 8.75

Chlorination Elemental gas or Sodium Hypochlorite most common

gas handling facilities more complex

Small Sodium Hypochlorite feed system Large (180 ML/d) Gas Chlorine feed system

Gaseous Chlorine Basics

Chlorine Gas Provided in 150 lb or 1 ton cylinders Significant safety provisions required
A

Typical 1 Ton Chlorine cylinder (tonners) storage

150 lb Chlorine cylinder

Sodium Hypochlorite Liquid provided in drum, tote, bulk or generated on site Safer, easier but more expensive than gas
A Small Sodium Hypochlorite tote system
A

An example Sodium Hypochlorite generator

Measurement of Chlorine Residuals

Orthotolodine Method (OTA) Diethyl phenylene diamine (DPD) Method Iodometric Method Amperometric Method Syringaldazine (FACTS) Method Oxidation Reduction Potential (ORP) High Pressure Liquid Chromatography

Most Common Methods

DPD Colourimetric Method Amperometric Method Oxidation Reduction Potential (ORP) Problems: DPD method does not go low enough Amperometric Method requires training ORP more suited to on-line measurement

Example Residual Measurement Devices

On-line Measurement Devices

Dechlorination
Conversion of HOCl or OCl- to ClCommon Dechlorination Chemicals: Sulphur dioxide, SO2 Sodium sulphite, NaSO3 Sodium bisulphite, NaHSO3 Sodium metabisulphite, Na2S2O5 Sodium thiosulphate, Na2S2O3 Hydrogen Peroxide, H 2O2

Comparison of Dechlorination Chemicals

Chemical
Sulphur Dioxide

Advantages
Significant use history Inexpensive for large installations Injection equipment similar to that for chlorine gas can be used

Disadvantages
Corrosive and hazardous to use Initial capital costs are high May increase hazard liability insurance Requires special storage and handling equipment Expensive for small installations

Comparison of Dechlorination Chemicals

Chemical
Sodium Thiosulphate

Advantages
Significant use history Non-toxic, noncorrosive, easy to use Low initial capital costs Easy to inject

Disadvantages
Solutions subject to freezing in cold weather

Comparison of Dechlorination Chemicals

Chemical
Sodium Bisulphite

Advantages
Significant use history Easy to inject Low use ratio

Disadvantages
Expensive chemical Sodium bisulphite is corrosive Solutions subject to freezing in cold weather

Comparison of Dechlorination Chemicals

Chemical
Sodium Sulphite

Advantages
Significant use history Non-toxic, noncorrosive, easy to use

Disadvantages
High use ratio Solutions subject to freezing in cold weather

Comparison of Dechlorination Chemicals

Chemical
Hydrogen Peroxide

Advantages
Easy to inject Inexpensive chemical cost

Disadvantages
Does not remove chloramines at a useful rate Highly unstable and subject to deterioration

Measurement of Dechlorination
Common practice is to over dechlorinate (slightly) Measurement and control is important to save money and not end up with a problem Measurement includes:
Amperometric back-titration ORP Probe-based sulphite measurement methods DPD-type portable methods

Current Practices Survey (2003)

A questionnaire was developed and circulated to 56 BC wastewater treatment plants (44 were in the Georgia Basin) Of these, 20 plants disinfect with chlorine Chlorination = gaseous chlorine or sodium hypochlorite (NaOCl) No chlorine dioxide or calcium hypochlorite (at the time of the survey) Trend is away from gas to NaOCl due to safety concerns

Current Practices Survey (continued)

Some plants dont dechlorinate (ground disposal) Dechlorination is typically by sulphur dioxide gas Plants that use gaseous chlorine typically use sulphur dioxide gas to dechlorinate One small plant used sodium sulphite There was some interest in sodium bisulphite and sodium thiosulphite Cost is an issue (sulphur dioxide is relatively inexpensive and very effective)

Current Practices Survey ( continued)

Only the larger plants use on-line measurement and control of chlorination and dechlorination The smaller plants typically use hand-held DPD colorimeters (and over dose (slightly) on dechlorination) New equipment may make automatic control more affordable

Conclusions
Chlorination of wastewater effluent in B.C. will continue for some time in the future. The trend in chlorination/dechlorination in B.C. will be towards safer to handle and easier to use chemicals, despite increases in costs. While the amperometric titration method is the most accurate means of measuring chlorine and sulphite residuals, the test requires time and operator skill that is often beyond the plant resources available.

Conclusions (continued)
The DPD method of manual chlorine residual measurement is easy to use, but it isnt accurate enough to actually measure a 10 :g/L (10 ppb) chlorine residual. Operators tend to slightly overdose dechlorination chemicals to ensure that the chlorine residual is zero. New automated amperometric titration systems may permit easy measurements of low chlorine residual levels. Selection of on-line residual monitoring is dependent on effluent quality and plant size