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Mirrico Seminar, Kazan, September 2011 Paul Wood and Anna Vatsurina.

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Presentation on theme: "Mirrico Seminar, Kazan, September 2011 Paul Wood and Anna Vatsurina."— Presentation transcript:

1 Mirrico Seminar, Kazan, September 2011 Paul Wood and Anna Vatsurina

2 Outline  Learnings from an incident  Review Risk, Hazard and Exposure  Exposure issues  Examples of how Dow Microbial Control, controls exposure to biocides  Packaging  Labelling  Safe Removal  Transport  Lab Safety  Storage  Dosing  Suggestions  Conclusions

3 Everyone Learns from an Incident Biocides are not dangerous when handled correctly

4 Chemical Handling: Level of Risk Hazard Type or Consequence of Exposure  Corrosive = will cause burns (contact may not be detected immediately)  Toxic = a poison  Respiratory irritant = like household bleach or ammonia  Skin sensitizers = cause “skin allergy” Exposure Potential or Likelihood of Event  How much product ?  Probability of an exposure ? Two factors to determine the risk when handling a chemical

5 Hazard x Exposure Potential = Risk Level of Risk Priority in hazard management reduces the exposure potential Hazard = HIGH LOW LOW Hazard = HIGH HIGH HIGH Safe Ethanol = x Unsafe Ethanol= x

6  There are many routes to exposure Exposure Potential InhalationSkin Ingestion How do we come into contact with a chemical ?

7 Types of Workplace Exposure  Gloves left lying on the floor  Water collecting on top of a drum  Contaminated cleaning cloth left in a bin  Opening, moving, connecting / disconnecting, emptying apparently “Empty” drums  Containers used for hazardous materials without labels  Cleaning / repair of contaminated installations  Door handles / Doors opened by someone wearing gloves Exposure to biocide residues

8 Types of Workplace Exposure  Spills from damaged packaging, or pipe work  Dosing from drums, or pails manually  Decanting from drums, or pails into smaller vessels  Using samples  Collecting samples from the production process  Taking samples for Quality Control of raw materials  Samples shipped to customers  Handling samples in the lab. Exposure to liquid biocides

9 Exposure Control  Perform a hazard- and safety analysis of the intended task according to your internal rules ( EHS review )  Follow the recommendations on MSDS* and Labels  Installations and tools you intend to use for the planned task  PPE (Personal Protective Equipment): type and control intervals  Appropriate ventilation of the working place / area  Safety installations: Safety Showers / Eye rinsing stations  Industrial Hygiene / Cleanliness and Housekeeping  Working Instruction  Spill-/Leakage Handling  Emergency Procedures  Training !!! If there is the potential for exposure

10 Biocide Packaging  Containers  Have to be UN approved  3H1/Y1.4/150/** GB/3380  Stringent testing  Drop tested  Are fitted with tamper evident seals for security reasons  Are palletised to prevent damage  The number of drums are limited on a pallet to prevent overhang and restrict weight  Packaging ergonomics Packaging has to be designed to be safe

11 On Site Signs & Labelling  Signs placed around the workplace inform operators on which and when personal protective equipment should be worn in specific areas  In addition use educational posters as part of an on-going safety education program Product labelling is one source of information but there are others…

12 Personal Protective Equipment ( PPE ) Helmet Goggles Suit Gloves Rubber Overshoes

13 Burns caused by not wearing gloves

14 Burns caused by improper removal of gloves

15 To avoid mishandling and accidents Always ensure samples are clearly labelled Warning symbols are visible Store products in clearly labelled cabinets To prevent exposure during use Handle biocides in a fume cupboard Make sure lab technicians wear the correct protective clothing: Gloves Goggles Ensure the area where biocides are handled is kept clean Lab Safety

16 Warehouse Storage Store biocides safely To maximise the safety of people  Training  Keep pedestrians separate from product  Safety barriers around offices  Special bins for hazardous waste  Ventilate warehouse To prevent blind corners, or falling containers  Restrict pallet height  To avoid mishandling  Use painted areas  Good lighting

17 Suggestions  Be proactive  Review the MSDS and label warnings  Do a safety review of the job  Have a written procedure and follow it  Evaluate and inspect the equipment to be used  Inspect your Personal Protective Equipment  Have the spill deactivation kit equipment and chemicals in place before an incident occurs!

18 Why use biocides ? Essential To:  Maintain Efficient Heat Exchange  Prevent Corrosion  Prevent Plugging of Orifices  Prevent Potential Health Concerns  Maintain Aesthetic Appearance 18

19 Why use biocides ?  Microbes can be:  algae if light reaches the collection basin  aerobic bacteria  anaerobic bacteria (SRB’s)  Moulds and yeast 19

20 Bio-films  Microbes can attach to surfaces and produce slime  impairs the heat transfer  induces microbial corrosion (MIC)  clogs filters, screens, casings and nozzles  potentially harbours Legionella pneumophila 20

21 Biofouling Control – Biofilm Issue  A biofilm is a layer of slime that is produced by microbes after they attach to a surface  Biofilms serve to protect the microbial community that is underneath it  Corrosion and H 2 S production result from the growth of microbes within a biofilm  Removing biofilm is more difficult than preventing the formation of a biofilm Stage 1 Conditioning Layer Stage 2 Bacterial Attachment Stage 3 Slime Formation (EPS Production) Stage 4 Slime Thickening Stage 5 Slime Detachment

22 Examples of “Patchiness” in Bio-films on 316 Stainless Steel

23 23  Review of the active ingredients used in indistrial water cycles

24 Oxidisers  Cl 2, HOCl, Br 2, HoBr,  Chloramaines ; ClO 2, H 2 O 2 / Peracetic acid  Corrosive  Very fast acting  Effect is short-lived – no permanance  Generate high levels of AoX ( adsorbable organic halides ) 24

25 1, 5-pentanedial Glutaraldehyde

26  Quick kill (1-3 hours) under alkaline conditions (pH 7-9)  Broad spectrum efficacy  Highly effective against SRB, biofilm, and Legionella  Readily biodegradable at concentrations < 5-ppm  Compatible with dispersants, surfactants and most WT chemicals, including CMIT/MIT  Compatible with halogens and other WT additives  Does not contain or release formaldehyde  Kills via cross-linking proteins in cell wall Glutaraldehyde Features

27  Weak efficacy versus fungi and algae  Stability with ammonia (NH 3 ) and alkaline pH  De-activated by bisulphites  Polymerises under alkaline and high temperature conditions (haziness / yellowing)  Evaporation (volatilization) potential increases with temperature and /or aeration Glutaraldehyde Limitations

28 DBNPA 2,2-dibromo-3-nitrilopropionamide C C C N Br O N H H Registered Applications Cooling Water (Re-circulating / Once-through / Open / Closed) Retort Systems, Pasteurizers Reverse Osmosis Membranes Air Scrubbers and Washers Paper Mills Additives/Mineral Slurries Enhanced Oil Recovery Publicly Owned Treatment Works

29 DBNPA Features  Extremely fast acting ( min)  Broad spectrum efficacy  Highly effective against biofilm and Legionella  Effective at low dose levels  Easy to dose liquid  Non-corrosive at in-use concentration  Low environmental impact  Short half-life at more alkaline pH’s  Kills via reactions with sulphydryls and disruption of respiration and metabolism

30 DBNPA Limitations  Liquid product shelf life is limited (6 months)  Weak versus fungi and algae  Low solubility in water  Incompatible with strong nucleophiles and reducing agents  Not UV stable  Occasionally referred to as an oxidizer

31 THPS tetrakis(hydroxymethyl) phosphonium sulphate

32 FeatureBenefit Fast acting, broad spectrumControl of wide range of microorganisms Active against SRB; Algae and Legionella Useful for a wide range of industrial applications Dissolves FeSReduces FeS related problems such as fouling of equipment Low dosagesCost effective Favourable aquatic toxicityVery low impact on ecology and minimal effect on environment Degradation to inert components Non-foamingEasy to use in high-flow systems No organic solventsSafety in use; completely water miscible THPS

33 THPS Limitations  Known to release formaldehyde rapidly (25% of total dose)  Cationic properties react with anionic inhibitors  Not compatible with oxidizing biocides  Unstable at high pH  Issues with use of THPS in high calcium waters

34 Registered Applications  Recirculating Cooling Water (Open and Closed)  Air Washers & Industrial Scrubbing  Industrial Process Water  Brewery Pasteurizers and Can Warmers  Industrial Wastewater  RO / UF Membranes (non-medical; non-potable)  Pulp and Paper Slimicide  Additive and Slurry Preservation CMIT / MIT

35 CMIT / MIT Features Broad-spectrum activityProvides control over bacteria, algae, and fungi with no performance gaps. Effective vs Legionella, SRB, and biofilm Fast ActingProvides immediate control circa 10 minutes Stable over a wide range of pH (<9) and temperature (<40 ° C) Effective under conditions typically encountered in most processes Clear, water soluble, liquidFully water soluble at use levels and easy to dose Broad chemical compatibilityCompatible with most cooling water and papermill additives and biocides Low use ratesCost effective Biodegradable and does not generate AOX or formaldehyde Environmentally friendly Product FeatureCustomer Benefit

36  Poor stability above pH 9 and >40º C  Poor stability with nucleophiles and reducing agents (sulphides, sulphites, amines,)  Perceived weakness versus SRB  Slow killing  Safe handling concerns / sensitization / burns  New solid version will address safety issues CMIT / MIT Limitations

37 OxidizingDBNPAGlutaraldehydeTHPSCMIT/MIT Products Cl 2 /HOCl BCDMH ClO 2 AM 7287 Sump Buddy UCARCIDE 24, 50AQUCAR THPS 75 KATHON WT Rate of killVery very fast Very fastFast Slow PersistenceNo Yes Thermal resistanceExcellentMediumExcellentGoodMedium pH range Up to 8.5Up to to 9 OrganismsA,B,FA, B, F biofilm ++ A, B, (F) biofilm +++ A, BB, F, Y, M Biodegradabilityn.a.Fast (readily biodeg.) Very fast (readily biodeg.) Inherently biodegr. FA releaseNo YesNo Comparison of Biocides for WT

38 Actives Used for Industrial Water Treatment and Paper BiocideCooling Water Air Wash.RO / UFPaper Slimicide Glutaraldehydexxxx DBNPAxxxx CTACx CMIT/MITxxxx DCOITxx

39 Spasibo


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