R.

O Biofouling Control: Case Histories Describing successful Transitioning from Oxidising to NonOxidising Microbicides
P.J. Allison, A.Maartens, E.Rava, S.Steenekamp:Buckman Laboratories M.P.Augustyn, P.G.Boshoff :- Sasol Synfuels P.J.Scurr:- Columbus Stainless

Introduction
Biofouling due to microbial growth in

R.O. Systems can be linked to 56 to 74% of typical costs of membrane operation (Kelle Zieher and Phillip,2000) Traditionally chlorine-based biocides have been used to control microbial fouling in the approach flow areas.

Susceptibility of R.O.Membranes to Chlorine attack

Cellulose acetate membranes are

resistant to chlorine whereas Thin Film Composite (TFC) Polyamide membranes are highly sensitive to oxidative degradation De-chlorination using a reductive chemical such as sodium bisulphite is required prior to PA membranes.

Advantages of Chlorination
Chlorine is relatively cheap, kills

microbes rapidly, and has a broad spectrum of control It can be applied in the form of gaseous chlorine or liquid sodium hypochlorite solutions

Disadvantages of Chlorination
Some resistant genera of bacteria such

as Brevundimonas and Pseudomonas are difficult to kill with low concentrations of chlorine Exposure of microorganisms to sublethal dosages of chlorine induces production of excessive amounts of extracellular polymeric substances (EPS) as a defense mechanism - leading to severe slime formation.

Disadvantages of Chlorine
Corrosivity of chlorine to metals. Humic acids are broken down into smaller

organic fragments ,which serve as a nutrient source in downstream chlorine - free areas of the feedwater stream. Over-dosage of bisulphite can aggravate deposition .

Refinery Case Study

A large R.O. facility at a refinery in SA was

experiencing major problems with biofouling in the T.R.O. plant that provides permeate as feedwater to a downstream polyamide spiral wound (S.R.O.) facility producing high quality boiler feedwater.
Chlorination ,followed by de-chlorination was

being practised to control TRO feedwater microbiological contaminants.

Refinery Case Study Problems experienced

Microbiological growth (including algae,

bacteria and fungi) was prevalent in the de-chlorinated feedwater to the R.O. plant R.O.membrane life was significantly lower than expected. CIP costs were elevated Operational stability was impaired due to bisulphite deposition and biofouling.

Refinery R.O. Facility Process Flow Diagram

CAE Ponds

Ash Production Ash Dams

640 m3/h

920 m3/h 524 m3/h

365 m3/h

TRO 1

TRO 2

Falling Film Evaporators

275 m3/h

SRO 345 m3/h

387 m3/h

310 m3/h

Boiler Feed Water

Raw Water Reservoir

Feedwater to T.R.O. Plants

Clear ash effluent Salty aqueous solution Not hazardous in calcium, sulphate, sodium

Tubular Reverse Osmosis (T.R.O) Plant 1

Tubular Reverse Osmosis 1

Commissioned in 1995 Capacity of plant = 14 Ml/d Design recovery = 45 %

11 modular units
960 TRO modules HP pumps, feed flow control, flow reversal system,

recovery control system and chemical cleaning change over system

T.R.O. Plant 2

Commissioned in 2002 Capacity of plant = 22 Ml/d Design recovery = 43 % 2 process lines 8 modular units 480 TRO modules HP pumps, feed flow control, flow reversal system, recovery control system and chemical cleaning change over system

Filter section:

Self cleaning filters Filter flushing Antiscalant addition Biocide shock facilities Intermediate buffering Heating of water

Tubular Reverse Osmosis Plant 2

SRO Plant

S.R.O. Plant
Commissioned in 1997 Capacity of plant = 7.4 Ml/d product

Design recovery = 90 %
3 SRO trains with polyamide membranes 3 Stages of concentration 10:5:3 configuration Single permeate stream

Final brine = concentrate from the last stage

Microbiological Monitoring Conducted

Heterotrophic Plate Counts ( HPCs) Spore Former Counts

Bacterial species identifications

Microscopic analysis of biofilm and

deposits Biocide kill studies Minimum Inhibitory Concentration Tests

log cfu/ml 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 0.00

Heterotrophic / Total Viable Plate Count

Train 1 Train 2 Date Train 3 67 Permeate

Unit 68 SRO Feed to first stage Total Viable Count

01-Dec-02 08-Dec-02 15-Dec-02 22-Dec-02 29-Dec-02 05-Jan-03 12-Jan-03 19-Jan-03 26-Jan-03 02-Feb-03 09-Feb-03 16-Feb-03 23-Feb-03 02-Mar-03 09-Mar-03 16-Mar-03 23-Mar-03 30-Mar-03 06-Apr-03 13-Apr-03 20-Apr-03 27-Apr-03 04-May-03 11-May-03 18-May-03 25-May-03 01-Jun-03 08-Jun-03 15-Jun-03 22-Jun-03 29-Jun-03 06-Jul-03 13-Jul-03 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 0.00 log cfu/ml

log cfu/ml 0.00 01-Dec-02 08-Dec-02 15-Dec-02 22-Dec-02 29-Dec-02 05-Jan-03 12-Jan-03 19-Jan-03 26-Jan-03 02-Feb-03 09-Feb-03 16-Feb-03 23-Feb-03 02-Mar-03 09-Mar-03 16-Mar-03 Date 23-Mar-03 30-Mar-03 06-Apr-03 13-Apr-03 20-Apr-03 27-Apr-03 04-May-03 11-May-03 18-May-03 25-May-03 01-Jun-03 08-Jun-03 15-Jun-03 22-Jun-03 29-Jun-03 06-Jul-03 13-Jul-03 0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 67 Permeate Train 3 Train 2 Train 1 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00

Unit 68 SRO

Pseudomonas Plate Counts

Feed to first stage
Pseudomonas

log cfu/ml

ATP Measurement
Adenosine Triphosphate = Microbial energy storing compound indicates viable organisms

Sample Point

ATP R.L.U.

HPC CFU/ml R2A Agar 3,0 x 103

U68 0.014 permeate U69 0.016 permeate

2,0 x104

Microbiological Population Study

Analysis
Aerobes Pseudomonas Aeromonas Moulds Slime-formers H2S producers Anaerobes Spore formers E. coli Coliforms Acid producers

Culture medium
R2A Pseudomonas agar Aeromonas agar Malt extract agar Sabouraud dextrose agar Kligler Iron agar Plate count agar Plate count agar + heat Petrifilm Petrifilm Dextrose Tryptone agar

Result (cfu/g)
5 x 103 2 x 102 None detected 1 x 101 5 x 102 None detected None detected 1 x 101 None detected None detected None detected

Bacterial Identifications
Pseudomonas

Widespread in the environment ,most predominant encapsulated bacterium in many industrial water systems and in medical biofilms
Spore-forming, slime-forming bacteria that produce large quantities of EPS(extracellular polymeric substances) Gram negative bacterium that produces capsular material

Bacillus

Aeromonas

Microscopy of slime deposits

Fungal hyphae

Scanning Electron Micrograph showing bacterial slime (12,000X mag)

Slime Analysis
SRO SLIME: TRAIN 2 PHASE 1 SUMMARY The dominant species were: Slime-forming bacteria : Burkholderia cepacia, Pseudomonas putida, Spore-forming ,slime former Bacillus spp Mould : Verticillium spp.

R.O. Reference for use of NonOxidising Biocides

(Motorola ,Austin Texas, USA)
Plant manufacturing semi-conductor

devices ,requiring high purity water Make up water was filtered ,treated and purified municipal water + recycled second pass R.O. reject water injected with hypochlorite ,followed by bisulphite Five double pass R.O. units each having a 7-3-1 cellulose acetate array, followed by a 4 -2 thin film composite array

High Costs associated with Biofouling

CIP Cleaning every 3 weeks High Consumables (filters) expenditure

Shock treatments of hypo

Membrane replacement before expected High labour costs for R.O. cleans

Introduction of Non Oxidising Biocide at Motorola

Added at a concentration of 15 mg/l into

R.O feed stream ,with chlorine present , followed by dechlor step . Biocide gave protection in de-chlorinated areas. TOC analyses confirmed that the biocide molecule was excluded and did not carry through in the TFC permeate

International References
Motorola, Austin Texas Temple Inland Corporation Amoco Refinery Texas Utilities

Introduction of Non Oxidising Biocides to S.A Refinery

Two alternating non oxidising biocides

(with membrane compatibility approval) were recommended to ensure broad spectrum control, and prevent bacterial resistance. Laboratory Biocide Kill studies were conducted on R.O. feedwater to assess efficacy of each biocide against indigent microflora

Results of Kill study

Minimum Inhibitory Concentration 110 100 90 80
% KILL

70 60 50 40 30 20 10 Control 5 ppm 10 ppm 15 ppm 20 ppm 25 ppm Dosages 35 ppm 50 ppm 100 ppm

BL 6057 BL 6042 BL 1421 (New)

Implementation of Biocide Treatment Programme

50 mg/l of Biocide A dosed five days per

week Supplemented with 35 mg/l of Biocide B dosed two days per week
Subsequently, dosage was optimised to

25 mg/l and 40 mg/l respectively

Results at Refinery R.O. Facility

Improved cleanliness in feedwater

stream Reduction in biofouling ,therefore reduced need for CIP Maintained R.O. Pressures No negative impact on salt passage Extended membrane life before replacement

South African Steel Plant Case History

Chlorination was used to control algal and

bacterial growth in the feedwater to a TRO facility that was used to treat effluent water from a stainless steel production facility Excessive blinding of the pre-filtration system and poor operational stability prompted a request for a plant microbiological audit and recommendation for a non oxidising biocide

Visit to Refinery
Plant personnel from the Steel plant made a

visit to the refinery to inspect the R.O. application described in the preceding Case Study . Non oxidising biocide dosage was initiated in the R.O. feedwater using an automated dosing pump. Algae contamination in the dams was treated by application of an algaecide A Coagulant was added to precipitate suspended solids and reduce the SDI.

Recommendation for Non Oxidisng Programme

Automated dosing station

Bunded areas for spill containment Bulk storage tanks with offloading facilities Timer controlled Automated flow and valve control Computerised dosing control
Frequency of dosing

2 hours every 24 hours

Biocide
Non oxidising

Process Flow Diagram

Biocide Flocculant Sandfilters Cartridge Filters (5 and 1 micron)

R.O. 1

Dam

Dam

R.O. 2

Onsite Monitoring
Microbiological Tests

Total chlorophyll a ( Algae) Heterotrophic Plate Counts ATP Adenosine Tri-phosphate (in R.L.U.- Relative Light Units)
pH Feedwater turbidity (NTU) ; SDI ; suspended solids PO4 NO3 Cr

Chemical Tests

Microbiological Monitoring Results

Sample HPC cfu/ml 4 X 104 Pseudomonas cfu/ml 6 X 103 ATP ( R.L.U.)

Pond 2

5.049

Pond 2B

5 X 103

3 x 101

1.877

Pond 3B Dam 3C RO 2 SF RO 2 CF

1 X 103 2 X 103 1 X 103 2 X 104

1 x 101 2 x 101 < 10 <10

0.155 0.659 0.115 0.025

R.O. Plant Parameters

Membrane types : Polyamide ( R.O.Plant1 :

Membratec ; R.O.Plant 2 : Trisep X 20. Low fouling type. Make up water : dam water comprising stainless steel plant effluent Permeate use: comingled with evaporator condensate and used as make-up water for the open cooling system ( high quality water for stainless steel production) Flow rates : 50 to 55 m3 per hour for each train Recovery : 60 to 65 %

Advantages of proposed programme

Low monthly cost

Shelf life longer than NaOCl COD in feed water not oxidised

No need for de-chlorination

Results at Stainless Steel Plant

Control in the pre-filtration station and

R.O. plant improved, and maintenance and consumable costs decreased. More recently ,the plant has been operating intermittently , depending on the quantity of water that needs to be desalinated. The membranes are preserved with 1000 mg/l of the non-oxidising biocide during standby periods

Conclusions
Case histories have been presented that

show how non-oxidising biocides have successfully replaced chlorine and provided improved biofouling control. Addition of a non-oxidising biocide upstream of polyamide membranes has not resulted in any carry through of biocide active ingredient in the final permeate.