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Oxidizing Biocide with function of slime prevention & removal

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Presentation on theme: "Oxidizing Biocide with function of slime prevention & removal"— Presentation transcript:

1 Oxidizing Biocide with function of slime prevention & removal
Jan 2013 Acculab

2 Bacteria ☞ Free HOBr generation mechanism of Justeq07
NaOCl + Stabilizer HOBr Bacteria NaBr Stabilized chlorine + Br- → HOBr - Steady conversion of Stabilized Chlorine and Bromide to free HOBr in process waters - Oxidation of bromide only occurs in situ (pH 5-9)

3 5~20% emission of input amount
Biocides for Cooling Water Justeq 07: stabilized chlorine/bromide ion Justeq 07 Oxidizing (NaOCl) Non-oxidizing Remark Air/water pollution No 5~20% emission of input amount (at pH 8.0~8.5) Justeq 07: Odor free (Suitable for factories in the urban areas) AOX ~2/100 less than NaOCl (B) Bio-fouling Excellent Poor Good ①Justeq 07: prevent biofilm formation at 2nd stage & remove aged bio-film within about 1 month ②increment of U value: energy saving (C) Resistance (against microbes) Yes ①Mists of non-oxidized biocide solutions have risk of skin irritation & other sensitive issues (Humidifier disinfectant) ②Non-oxidizing biocides are generally using in the paper mill General biocide usage of standard cooling tower NaOCl solution (~12%) is used as oxidizing biocide for cooling water. In order to complement NaOCl, non-oxidizing biocide may be used every two week.

4 (A-1) Chlorine emission: Hypohalous acid and haloamine flashoff
in industrial evaporative cooling systems

5 (A-1-1) Speciation of Cl2, HOCl and OCl- as a function of pH

6 (A-1-2) The speciation as a function of pH using values
for K1 = 3.9x10-4 & K2= 2.9x10-8 at 25℃

7 (A-2) Case studies : Amounts of hypochlorous acid flushoff by using
standard cooling water systems at pH 8.5 Spec of standard cooling water system Biocides Input (ppm) Amount (Kg)/month Amount of NaOCl flushoff (Kg)/month Remark RR ㎥/hr 10,000 NaOCl (ppm/RR) 1 7,200 720 Not good due to the formation of slime δT 5 Non-oxidized (ppm/HV/week) EV 86.2 Use non-oxidizing biocide to prevent & reduce the slime growth COC 7 (ppm/HV/3 month) 100 600 TBD 14.4 Justeq 07 (ppm/HV/day) 30 1,800 - No emission. Amount of biocide depends on water quality HV 2,000 Justeq 07 (ppm/HV/day) 40 2,400 ☞ Total usage of halogen can be reduced up to 1/5~1/10

8 (A-3) Relative AOX formation in cooling tower by halogen biocides
NaOCl (Un-stabilized chlorine) Stabilized bromine Justeq 07 (Stabilized chlorine) Remark 100 % 50% ~20% Based on the chorine consumption rate 100% 40% ~10% Relative AOX formation at same halogen conc (USP 5,683,654 table II) 20% ~2% Final relative AOX formation by Justeq07 AOX: Absorbable Organic Halides: For environmental protection reasons, the AOX value must be monitored at all times. A cooling cycle operating with Justeq07 shows much lower AOX values than a cycle operated with chlorine or bromine

9 (B-1) Steps in biofilm development
1) Surface conditioning - Almost immediately a organic layer deposits on the water/solid interface - Conditioning layers neutralize excessive surface charge & surface free energy The absorbed organic molecules often serve as a nutrient source for bacteria 2) Adhesion of pioneer bacteria Some of the planktonic (free-floating) bacteria will approach the wall & become entrained within the boundary layer Initial attachment is based on electrostatic attraction & physical force -Some of the reversibly adsorbed cells become irreversibly adsorbed. Stabilized chlorine/ bromide ion works in stage 2 ☞ No adhesion or removal of pioneer bacteria by killing planktonic microorganism or hindering bacteria attachment

10 4) Secondary colonizers
3) Slime formation Adsorbed bacteria excrete extracellular substance These polymeric substance, or glycocalyx, consists of charged & neutral polysaccharides groups These substance facilitate attachment & act as an ion-exchange system for trapping & concentrating trace nutrients In a mature biofilm, more of the volume is occupied by the loosely organized glycocalyx matrix (75~95%) than by bacteria cells (5~25%) 4) Secondary colonizers As well as trapping nutrient molecules, the glycocalyx net also snares other types of microbial cells through physical restraint and electrostatic interaction These secondary colonizers metabolize waste from the primary colonizer as well as produce their own waste which other cell then use in turn

11 5) Fully functioning biofilm
The mature, fully functioning biofilm is like a living tissue on the wall surface Mature biofim are imaginatively described in the article “Slime City” As stabilized chlorine & bromide ion has outstanding penetration properties it overcomes the protective barrier of the aged bio-film and then disintegrate. HOBr by reaction of stabilized chlorine & bromide ion detach the slime structures in addition to the biocidal effect.

12 (B-2) Penetration rate of chlorine-based biocides into biofilm
penetration time (min.) chloride ion 5 chlorosulfamate 6 hypochlorite 48 The mean penetration time into ~1mm thick biofilm P.S.Stewart et al. Center for Biofilm Engineering and Department of Chemical Engineering, Montana State University Journal of Applied Microbiology 2001,91,

13 ☞Additional surface area (%)
(B-3) Increment of U (overall heat transfer coefficient for condenser) by biofilm Biofilm thickness (㎛) U (Btu/ft2*hr*℉) ☞Additional surface area (%) 870 100 510 71 120 469 86 243 318 174 ☞ Additional surface area required for compensating water side biofouling

14 (B-4) Easier cleaning: reduce the cleaning effort
- Cleaning works may be hazardous to health w/o the use of protective equipment (dispersed & inhaled germ aerosols, legionella, sick building syndrome, etc)

15 No odor (B-5) Fountain Application (Everland Youngin Korea) ⇒ ⇒
with Justeq 07 after 1 week w/o biocide

16 (C-1) Mechanism of action of industrial biocide
Electrophiles Membrane active Oxidant Electrophiles Lytic Protonophores Chlorine Bromine Ozone Peroxides Isothiazolones Aldehydes Carbamates DBNPA BNPD Quats Biguanides Phenols Alchols Week acids Parabens Pyrithiones Humidifier disinfectant: PHMG, PGH, CMIT/MIT, Technical brochure of PPChem The mechanism of action of Isothiazolone Biocides Terry M. Williams DBNPA: 2,2-dibromo-2-cyanoacetamide BNPD: 2-bromo-2-nitropropane-1,3-diol

17 (C-2) Humidifier Disinfectants

18 Methylisothiazolinone, A Neurotoxic Biocide,
(C-3) Toxicities of MIT & CMIT Methylisothiazolinone, A Neurotoxic Biocide, Disrupts the Association of Src Family Tyrosine Kinases with Focal Adhesion Kinase in Developing Cortical Neurons MIT(methylisothiazolinone) and its closely related analog, chloromethylisothiazolineone or CMIT, affect the ability of young or developing neurons to grow processes (axons and dendrites) in tissue culture 2. The toxic actions of MIT on developing neurons occurs at much lower concentrations than those inducing lethal injury (1-3 micromolar). CMIT is even more potent, working at concentrations as low as 0.1 micromolar ☞ One micromolar is approximately parts per million. Journal of Pharmacology and Experimental Therapeuticsjpet.aspetjournals.org Published online before print March 17, 2006, doi: /jpet JPET June 2006 vol. 317 no Dr. Elias Aizenman, Department of Neurobiology, University of Pittsburgh School of Medicine; E1456 BST, Pittsburgh, PA 2. From Wikipedia, the free encyclopedia: Key word (methylisothiazolinone)

19 (C-4) Physico-Chemical Properties of Sodium hypochlorite solution
Melting Point: -6°C (21 deg F) (5% solution) Boiling Point: Decomposes above 40°C (104 deg F) pH value: Approx. 11 Odour chlorine (bleach) odour Odour Threshold: Not applicable. Odour is due to breakdown products such as chlorine. Stability: Sodium hypochlorite solution decomposes slowly. Decomposition is speeded up by heat (temperatures above 40 deg C) and light. Hazardous Decomposition Products: Chlorine, oxygen, sodium chlorate.

20 Corrosion: Test results of Metal corrosion (40℃)
①  ②  ③  ④ ① ② ③ ④ ① ② ③ ④ interface Nail 1day Brass 3 days Sus month ① de-ionized water ② stabilized chlorine/bromide ion:100 ppm  ③ 12% NaOCl:60ppm ④ competitor:40ppm + NaOCl:60ppm Due to corrosive gas, corrosion occur above interface of ③ & ④

21 Certification 1 : U.S.A - EPA Reg #: (Oct ) California EPA Reg (May 25, 2012) ※ Justeq 07: Brand name in U.S.A

22 Certification 2 : Japan (Dec 22 2011)
- ☞ Chromosomal aberration test ※ Ecocide 100: Brand name in Japan

23 Certification 3 : Japan (Sept 3 2010)
- 微生物を用いる變異原性試驗 (Ames 試驗) ※ Ecocide 100: Brand name in Japan

24 Registered Product Name
Sub-registration in U.S.A # Registered Product Name Distributor Name 1 Cite 8570 Cite corporation 2 Biotrol 409 U.s. water services 3 Alg-715 Aquatech 4 Qwt 2133 Quality water treatment, inc. 5 7407 Power engineering co. 6 Mitco cc-7l microbiocide Mitco inc 7 Justeq07 R2j chemical services 8 Cwt 2190 Masters chemical co inc 9 Busan 1735 Buckman laboratories inc. 10 American #818 industrial microbiocide American water treatment inc 11 United 339 cycle smart stabilized bromine treatment United laboratories, inc. 12 A-207 Chemco products inc. 13 Ml-719 Gehrke technology group 14 Jbc 22 biocide Jentek water treatment, inc. 15 Cesco act 2020 Cesco solutions, inc. 16 Aq4113 Aqualine water treatment products inc 17 Waterchem 2030 Water chemical service, inc. 18 Al-7015 Barclay water management inc 19 Oxy-brom Walling water management 20 Chemtreat inc 21 Mg-3610 Algoma products inc. 22 Pacific standard specialties U.S.EPA Reg No. : Manufactureer Name: Justeq LLC ☞: Source

25 Summery of Justeq 07 (no chemical burning & skin irritation)
Excellent biofilm penetration Not be consumed by the EPS(exo polysaccharides) contained in the slime layer NaOCl(strong oxidizer) react and are consumed by EPS Penetrate to kill the bacteria within the slime layer, leading to removal of existing slime deposits Easy installation of supply systems (Pump & tank) Protect the operating personnel - No damage by Justeq 07 (no chemical burning & skin irritation)


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