Paper Industry Biocides - BASF
Specialty Chemicals by BASFPaper industry biocidesBASF Biocides
Innovation, preservation and disinfectionPAGE 2
BASF Biocides - protecting the worldThe biocide business for Specialty Chemicals, BASF AGBASF is one of the world’s leading suppliers ofspecialty biocides. We create products that makelife safer, simpler and more comfortable formillions of people worldwide.Our high performance biocides are used in everyaspect of life. From toiletries, to air conditionersused in both industry and home, from Iceland toEquador our technology spans the globe inpreservation and disinfection. We help to protectthe lives of millions of people across the worldevery day.Through our product range, marketing expertise,technical and regulatory knowledge, BASF’sinnovative biocides approach positions thebusiness at the very forefront of antimicrobialtechnology. The marketing, technical and researchand development headquarters for BASF’sspecialty biocide business is located inNottingham.Our products are made in ‘state of the art’manufacturing facilities at Cramlington, Englandand Ludwigshafen, Germany. In each of ourplants, the expert integration of process andenergy requirements leads to manufacturingefficiencies and quality production.To demonstrate our commitment to our customers,we have made significant investment in long termdedicated biocide resources within Europe, AsiaPacific and the USA.In 2000, we established a direct presence in theUSA with a new dedicated marketing andtechnical centre based at BASF Corporationheadquarters in Mount Olive, New Jersey. Productis supplied through an integrated BASFwarehousing facility in Charlotte, North Carolina.Our US operation is part of BASF Corporation’sChemical Division, situated in Mount Olive, NewJersey.How we work for youBASF’s biocides are sold through BASF’sestablished network of sales offices worldwide. Inthis way, we aim to offer valuable local supportand the highest standards of customer excellence.Working with BASF provides access to manyessential regulatory approvals. For example ourEPA registrations allow products and customerformulations to be sold in the USA and ourapprovals ensure supply to the paper industry inthe Nordic area. We are also well positioned tosupport our actives under the European BiocidalProducts Directive.We believe in long-term commitment to ourproducts and customers and this is reflected inour substantial registrations and the data requiredto obtain them. To this end many of our productsare supported with extensive safety andenvironmental data packages.In addition, BASF is committed to providing thehighest standard of health, safety andenvironmental protection as part of ourcommitment to Responsible Care. We continuallyresearch and innovate to produce the mostadvanced products on the market.At BASF, we are also constantly reviewing ways inwhich we can improve our products and servicesto ensure that we keep pace with the rapidlychanging developments in information technology.BASF is harnessing these changes and ensuringthat we are aligned with our customer’srequirements, making it more efficient andconvenient for you to do business with us.BASF’s specialty biocide products are marketedunder the Myacide and Protectol trade names.PAGE 3
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Introduction to the Paper Biocide IndustryMicrobiological Problems in thePaper IndustryThe paper and paperboard industry is highlydiverse. Products range from specialised papersfor currency printing through to tissue andnewsprint production and the manufacture ofpaperboard for packaging. Each of these areasdemands different approaches in terms of the rawmaterials used and the various additives neededto arrive at an acceptable finished product.paper breaks, spray nozzle blockage anddiscolouration of the finished product. Problemorganisms are the aerobic slime-forming bacteriasuch as Pseudomonas, Klebsiella, Enterobacter andBacillus spp. Anaerobic organisms such as theDesulphovibrio spp. can also accumulate underslime layers and other deposits leading to theproduction of foul odours and corrosive by-products.Water-based mill additives including mineralslurries and paper coatings are also prone tocontamination and require adequate preservationto ensure that their stability is not compromised.The major spoilage organisms are aerobicbacteria such as those mentioned above but insome instances yeasts such as Candida andSaccharomyces spp. and moulds such asAspergillus spp. can be involved. Consequentlythere may be a need for broad spectrumpreservation in many of these additive products.Preservation of bulk pulp may also be requiredduring unplanned plant shut-downs.The occurrence of these contamination andspoilage problems creates a demand forantimicrobial products, which can be ideallysatisfied by products from BASF’s specialtychemical biocide range.All of these areas, however, depend on a basicprocess where the paper fibres are suspended ina large volume of recirculating water before beingremoved by filtration and compacted and dried toform the paper sheet. Various water-basedadditives are also used to improve the efficiencyof the process and control the quality of thefinished paper. These include flocculants,retention aids, fillers and paper coatings.These conditions, together with the operatingtemperatures, which are normally above 30 C,provide the ideal environment for the growth ofmicroorganisms, mainly bacteria. Contaminationmay originate from the air, fresh water, virgin andrecycled pulp or waste water.In the manufacturing process, this can result in thebuild up of slime at key points in the process. Ifuncontrolled, the slime can accumulate andeventually break away, leading to problems such asCONTENTSPAGEMyacide AS, AS Plusand S1/S15/S30 Biocide6Protectol GA 50 / GA 24 Biocide10Protectol DZ / DZ P Biocide12Protectol HT Biocide14 PAGE 5
Myacide AS, AS Plus and S1/S15/S30BiocideMyacide AS biocide is the industrial grade of 2Bromo-2-nitropropane-1,3-diol or Bronopol. Itprovides highly effective antimicrobial activity foruse in diverse and demanding industrial biocideapplications, combining well-proven efficacy withimportant environmental safety characteristics.The main benefits of Myacide AS in the paperindustry are its proven performance as a slimicideactive ingredient in mill process water and as aneffective preservative for mill additives. The idealphysical and microbiological properties ofBronopol place it in a new generation of products,which can be seen replacing older chemistries.Concentrations (M.I.C.) of Bronopol against sixkey microorganisms.QUALITYThere have been no reported cases of resistanceto Bronopol in over twenty years of use. Recentfield trials have shown excellent activity againstPseudomonas species resistant to othercommonly used biocides such as those based onisothiazolinones.Myacide AS is an off-white to pale yellow, freeflowing, crystalline solid. The product contains aminimum of 98% 2-Bromo-2-nitropropane-1,3-diolalthough typical purity values are significantlyhigher. As supplied it is stable for a minimum of 3years when kept under good storage conditions.Test OrganismM.I.C. (ppm)Staphylococcus spp12.5 - 50Bacillus spp12.5 - 50Desulphovibrio spp12.5 - 50Pseudomonas spp12.5 - 50Candida spp400Aspergillus spp3200M.I.C. data is generated according to in-housemethodology.USAGE RECOMMENDATIONSMyacide AS Plus is marketed only in the USA asan EPA end use product. The technicalspecification and product quality are the same asMyacide AS.Liquid FormulationsA range of commercial formulations is readilyavailable.Myacide S1 is a 20% (w/v) solution indipropylene glycol monomethyl ether andwater.Myacide S15 is a 10% (w/w) solution inpropylene glycol and water.Myacide S30 is a 30% (w/w) solution inpropylene glycol and water.ANTIMICROBIAL ACTIVITYThe spoilage of paper, pulp, mineral slurries,coatings and other additives is generally due to amixed population of bacteria and to a lesserextent fungi. Bronopol is highly effective,particularly against aerobic slime-forming bacteriasuch as Pseudomonas spp., Klebsiella spp.,Bacillus spp. and the Enterobacter spp. Thefollowing table compares the Minimum InhibitoryPAGE 6Solubility, Stability and CompatibilityBronopol is readily water-soluble and solutionscontaining up to 28% w/v are possible at ambienttemperature. The compound also shows a higheraffinity for polar organic solvents (e.g. propyleneglycol 50% w/v) which makes it very easy to useeither as a liquid or a solid.Bronopol’s stability is one of the most importantfactors in the paper industry for long termpreservation. It shows optimum pH stability in theacidic range with excellent efficacy. At alkalinepH, Bronopol is less stable but still provideseffective control. In these systems, Bronopolreaches an equilibrium with its breakdownproducts, which are also microbiologically active.This self-stabilisation means that preservativeefficacy can be maintained over an extended shelflife even within aggressive, more alkalinematrices.
Bronopol is compatible with a range of materialsused in the pulp and paper industry such asretention aids, flocculants and other biocides suchas isothiazolinones. In common with other nonoxidising biocides, strong reducing agents andoxidising agents should be avoided. However,Bronopol can be used alongside oxidising biocidesin systems with alternating biocide regimes.Recommended Dose RatesPaper Mill Process WaterMyacide AS can be dosed as a solid at aconvenient point early in the recirculating systembut experience has shown that best results areobtained using formulated solutions. It should beadded to the wet end of the machine, the primarywhite water circuit, where good dispersion cantake place. The levels required will depend on thecleanliness of the system, the quality of the rawmaterial and the degree of microbial controlrequired. A typical regime may involve initiallydosing at a level of 50g Myacide AS per tonne offinished paper product, reducing to 10-20g pertonne after 2-3 weeks. When used in combinationwith other biocides, the concentrations ofMyacide AS can be further reduced.Bulk PulpTo preserve bulk pulp, control foul odours andprevent general biodeterioration of stock,Myacide AS or an associated formulation may bedosed directly into the hydropulper, machinechest or stock chest. In general, a single slugdose of between 50ppm and 250ppm activeshould provide control for up to 3 days or longer,depending on the initial level of contamination.In situations where contamination is high, repeatdosing every 1-7 days may be required.Paper Mill AdditivesMyacide AS or an associated formulation can beused as an effective preservative for a wide rangeof auxiliary products. These include mineralslurries, starch solutions, rosin sizes, polymerdispersions and paper coatings. When used aloneit can be dosed at 100-500ppm active based onfinal product volume. However, in situations whereorganisms tolerant or resistant to otherpreservatives are encountered, the performanceof Myacide AS as a combination biocide isoutstanding. In these situations the dose levels ofeach biocide can be reduced.PAGE 7
Myacide AS, AS Plus and S1/S15/S30CASE STUDYSAFETY CHARACTERISTICSThe following example (fig. 1) demonstrates theefficacy of Bronopol in preserving a typical papermill additive based on calcium carbonate.The procedure used was ASTM E 723-91 atpH 7.5 with a mixed inoculum of Pseudomonasaeruginosa, a second (1,2-Benzisothiazolin-3-one(BIT)-resistant) Pseudomonas species,Enterobacter cloacae and Klebsiella aerogenes.In order to support the safe use of Bronopol, a widerange of toxicological studies have been carriedout. The extensive nature of this database isparticularly helpful in supporting productregistrations and answering any concerns onproduct safety. Bronopol is non-carcinogenic, nonmutagenic, non-embryotoxic and non-teratogenic. Itis also non-phototoxic.Myacide AS at a level of 20ppm was able tocontrol this mixed inoculum for a period of sixweeks following a single initial challenge of106cfu/ml and a reinoculation at 21 days. BIT atlevels of up to 200ppm active was unable to controlthe Pseudomonas growth.Bronopol is biodegradable and does notaccumulate in the environment. Due to its rapidphotolysis and hydrolysis, Bronopol will not, undernormal use conditions, cause problems to effluenttreatment plants or to the environment followingdischarge into wastewaters.Bronopol is classified in the EU Council Directive 67/548 EEC as harmful, irritant and dangerous forthe environment.REGISTRATIONSNORTH AMERICAUSAEPA - BASF’s Bronopol is approved for use in paper mill pulp andprocess water, starch, pigments and extender slurries.FDA 21 CFR. - Code of Federal Regulations. Listings are:176.300 - Paper slimicides use.(fig. 1)175.105 - Indirect food contact use in adhesives.Calcium Carbonate Slurry - Bronopol Data176.170 - Components of paper and paperboard in contact withaqueous and fatty foods.87CANADAHealth Canada have approved the use of BASF’s Bronopol as aslimicide and granted a letter of ‘no objection’ for use in papercoatings intended for food contact.6543EUROPE (EU)2DENMARKPaper slimicide registrations and meets Nordic Swan ecolabelrequirements for slimicide use in printing paper.10(20ppm)PAGE 8(50ppm)(100ppm)(200ppm)FINLANDMyacide S1 is registered as a paper slimicide.
FRANCEApproved for food contact use as a paper slimicide by theMinistere de la Consommation.GERMANYBgVV - Recommendations for food-contact applications.XIV,2f - substances added to dispersions to prevent microbialattack.XXXVI, B V11 - paper and board, slimicides.NETHERLANDSWater and paper treatment registration.SWEDENMyacide S1 is registered for use as a paper slimicide.Myacide AS meets Nordic Swan labelling requirements forslimicide use in printing paper.PAGE 9
Protectol GA 50 / Protectol GA 24BiocideProtectol GA 50 biocide is a 50% solution of 1,5Pentanedial commonly known as Glutaraldehyde.It is very effective against a broad spectrum ofbacteria and fungi common to the papermakingindustry and is useful in the prevention of slimebuild-up in all areas of the manufacturing process.Protectol GA 50 has a rapid speed of kill, is costeffective and easy to use. In paper processing,the principal benefit of Protectol GA 50 is that itcan be used as a stand-alone product.M.I.C. data on Protectol GA 50 has beengenerated using in-house methodology. It shouldbe noted that due to the influence of mediaconstituents, the M.I.C. results are generallyhigher than the effective doses required in-use.Test OrganismM.I.C. (ppm)Staphylococcus spp.Bacillus spp.Desulphovibrio spp.Pseudomonas spp.QUALITYProtectol GA 50 is a clear, colourless solutioncontaining an active content of 50%Glutaraldehyde in water.Protectol GA 50 is classed as an aldehyde which iseffective against Gram positive and Gram negativebacteria and fungi.Protectol GA 24 is a clear, colourless solutioncontaining an active content of 24%Glutaraldehyde in water.Both products have a shelf life of at least six months.ANTIMICROBIAL ACTIVITYProtectol GA 50 is extremely effective againstslime forming bacteria such as Pseudomonasaeruginosa, Staphylococcus aureus, Escherichiacoli and Micrococcus spp found in fouled papermaking systems. The ability of Protectol GA 50 torapidly reduce the level of micro-organismspresent in a typical paper making process isexcellent.Candida spp.Aspergillus spp.50125060150 - 2501250475USAGE RECOMMENDATIONSSolubility, Stability and CompatibilityProtectol GA 50 is soluble in water and a range ofpolar organic solvents. This facilitates use in thevast majority of water-based systems and ensuresthat it can exert maximum effect at the site ofcontamination in the paper process. Stability isreduced above pH7 and at elevated temperatures( 40 C).Protectol GA 50 is compatible with a range ofmaterials used in the paper and pulp industry suchas retention aids, flocculants and other biocides. Incommon with other non-oxidising biocides, strongreducing and oxidising agents should be avoided.Recommended Dose RatesPaper Mill Process WaterProtectol GA 50 can be dosed at a convenientpoint early in the process, but experience hasshown that the best results are achieved byadding it to the wet end of the machine, wheregood dispersion can take place. Convenientlocations for this are the machine chest, constanthead box, machine wire pit or backwater loopsystem. The levels of Protectol GA 50 requireddepend on the cleanliness of the system, thequality of the raw materials and the degree ofmicrobial control required. A typical regime mayinvolve initially dosing at a level of 200 - 400g ofProtectol GA 50 per tonne of finished paper.PAGE 10
Bulk PulpProtectol GA 50 can be used to preserve bulkpulp and control both foul odours and generalbiodeterioration of stock. It may be dosed directlyinto the hydropulper, machine chest or stockchest. A single slug dose of between 100ppm and500ppm is sufficient to provide control in thestock. In situations where contamination is high,repeat dosing every 1 - 7 days may be required.Paper Mill AdditivesTo inhibit the growth of spoilage bacteria duringthe manufacture of water-based solutions,suspension concentrates and emulsions, ProtectolGA 50 may be dosed at 100-500ppm based onfinal formulation volume.SAFETY CHARACTERISTICSIn order to support the safe use of Glutaraldelyde,a wide range of toxicological studies has beencarried out. The extensive nature of this databaseis particularly helpful in supporting productregistrations and answering any concerns onproduct safety. Protectol GA 50 is toxic ifswallowed or inhaled and is corrosive to the skinand eyes. It may cause skin sensitation and hasbeen classed as a respiratory sensitiser in the EU.Protectol GA 50 is not teratogenic or carcinogenicand is not mutagenic in animal studies.Protectol GA 50 is readily biodegradable in theenvironment and should not cause problems insewage treatment plants and surface waters whenused as recommended.REGISTRATIONSNORTH AMERICAUSAEPA - BASF’s Glutaraldehyde is approved for use as a paperslimicide.FDA 21, CFR - Code of Federal Regulations. Listings are:173.320 - Chemicals for controlling microorganisms in cane-sugarand beet-sugar mills.176.170 - Components of paper and paperboard in contact withaqueous and fatty food.176.180 - Components of paper and paperboard in contact withdry food.176.300 - Paper slimicide use.CANADABASF’s Glutaraldehyde is registered as a technical product foruse in manufacturing registered microbiocides.EUROPE (EU)GERMANYBgVV - Recommendations for food-contact applications.XXXVI, B VII - Paper and board, slimicides.XXXVI/2, IIG - Paper and board for bakeries, slimicides.FINLANDProtectol GA 50 and GA 24 are approved for use in paperslimicides.SWEDENProtectol GA 50 is approved for use as a paper slimicide.PAGE 11
Protectol DZ / Protectol DZ PBiocideProtectol DZ biocide is the trade name forDazomet, a heterocyclic compound. Within thepulp and paper industry it is used both as apreservative for mill additives and as an activeslimicide to control growth in the process water. Itboasts excellent antimicrobial activity. ProtectolDZ is particularly active against slime-formingorganisms and sulphate reducing bacteria, whichcan be responsible for corrosion.The most important benefits of Dazomet in thepulp and paper industry are its rapid speed of killand broad spectrum activity.QUALITYProtectol DZ is a fine granular grade product andProtectol DZ P is a powder form. Both productsare off-white in colour and contain a minimum of99 % ne.BASF’s Dazomet has a shelf life of at least 2 years.It should not be stored at temperatures above 40 C.ANTIMICROBIAL ACTIVITYDazomet is extremely effective against slimeforming and spoilage organisms such asPseudomonas spp., Klebsiella spp.,Staphylococcus aureus, Aspergillus niger andCandida albicans. The Minimum InhibitoryConcentrations (M.I.C.) of D
with other biocides, the concentrations of Myacide AS can be further reduced. Bulk Pulp To preserve bulk pulp, control foul odours and prevent general biodeterioration of stock, Myacide AS or an associated formulation may be dosed directly into the hydropulper, machine chest or stock chest. In general, a single slug dose of between 50ppm and .
Some biocides are membrane-active agents and thus destroy the envelope of the cells (Table 1) [5-7]. Others react with functional groups of proteins and/or nucleic acids and as a result inhibit metabolism and cell growth. benzalkonium chloride . 3.2 Process biocides . In the context of FCMs process biocides are used to prevent microbial
patterns. BASF’s biocides has a full range of complementary products for the water and oilfield industry which help to either eradicate or control microbial growth and prevent the build-up of biofilms. CONTENTS PAGE Myacide AS and S1/S15 Biocide 6 Protectol GA 50 / GA 24 Biocide 10 Protectol DZ / DZ P Biocide 14
MDI BASF. MDI others. TDI BASF. TDI others. MDI utilization. TDI utilization Rates above 90% indicate favorable market conditions Market growth 2001-2005: 7% p.a. 2006-2015: 5% p.a. BASF volume growth 2001-2005: 13% p.a. 2006-2015: above market Additional BASF capacities 400 kto MDI in China 2010 onwards (JV with partners .
of natural gas and oil – using chemical agents (biocides). Biocides are compounds used to disinfect, decontaminate and sterilize materials (surfaces, objects) to eliminate mi-crobiological degradation processes. Chemical compounds, exhibiting biocidal properties and used as antibacterial/ antifungal preparations have a diverse structure .
appropriate biocides, we would consume far greater amounts of natural resources. The net result is that biocides support sustainable production and consumption. Keeping ships’ hulls clean of marine organisms – helps the environment 90% of the world’s goods are transported by sea. Ships are among the safest and most
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All structure profiles painted with anticorrosion Basf-Glasurit primer epoxi All body painted with Basf-Glasurit epoxi External coating by S22 and S55 from Basf-Glasurit Body underneath protect with Basf-Glasurit specia
Iowa, 348 P. Sharma, O. P. (1986) Textbook of algae. Tata Mcgrawhill Publishing company Ltd. New Delhi. 396. p. UNESCO (1978) Phytoplankton manual. Unesco, Paris. 337 p. Table 1: Relative abundance of dominant phytoplankton species in water sarnples and stomach/gut of bonga from Parrot Island. Sample Water date 15/1/04 LT (4, 360 cells) Diatom 99.2%, Skeletonema costatum-97.3% HT (12, 152 .
