17 Modern Equipment for a Pesticide Formulation Laboratory and Pilot Plant SaaEEEEEEeeseneeeeeeeeeeee 1, Introduction Allatge array of modorn equipment i available for processing, testing and anelsing of pesticide formulations. Whon establishing a formulation laboratory, the purpose and function of the laboretory should determine thy choice of equipmont. The Isboratory can have any ofthe following three "basic objectives: (a) Tosupport general production activities, including quality control; ©) To carry out formulation development, including specification and dovelopment ofthe required ingredients; (©) Toundertake basic researching pesticide fermulation and formulation ingredients, In practice, each of these may be combined with any or all of the others (1). The role of formulation laboratory can also evolve: from initially supporting production activities may eubsocuenty underteke formation research and dovelopment. Thie can be achieved by gradually adding equipments moot a roqured need and degree of sophistication. However, clear objective is known in the beginning, it wouldbe better to plan the | laboratory layout and provide the requisite support facilities and utilities, | reduction, blendig, bbe further divided into two classes: meesurement of physical characteristics ‘and chemical assays. Methods for cheiicel assay are covered in detall in 248I Modern Equipment for a Pesticide Formulation 249 Laboratory and Pilot Plant here. +2, Formulation Laboratory To Support General Production and Quelity Control Aetivities “The lunctons of such « laboratory would normally be to provide support toprocuction in the areas of physica testing including (a) essessment of the suitably of alternative filers or emulsifiers, (b) determination of the ‘quail ofincoming raw materials and(c} maintenance ofthe quality of day- {b-day production, The eboratory functions as anintegrated compenentof the production system leading to fewer losi batches and hence ¢ boltor culputrate. Itneeds tobe sultably equipped to carty out basic quality contol fests and storage stability tests on formulations such as (2) dusts and wwottable powders, (e) emulsifable concentrates and emulsion concentrates and ({] suspension concentrates. Tests to assess the performance of dusts, wettable powders and emulsifiable concentrates can all becartiadoutin simple glacsvrare using sutable balance, a stopwatch and aset of sieves. Tests such as dry sieve ‘ost, fowability, wetabily, suspensibiity andfoarring do notrieed elaborate equipment, Similarly, the performance of both wettable powders end smulsfiable concentrates can beassessedusing simple glassware. ‘Asiinple yelumetric aasesement of setting, using a graduated measuring yinderto measure the volume of compaciedsediment,cempating itwith thatota good quality sample, would give a vary good indication of whether 2 formulation will maet specications. The effect of changing Surfactants or filers ina wettable powder canbe assessed in similer vay. For emulsifiable concentrates and emulsion concentrates, a comparison of the volume of settled cream with that of a standard, using a graduated conical cylinder, willprovide emulsion stably information. would be obvious thet « new formulation or changes in adjusvanis in formulations can be usefuy assessed without eanying out aspecialcheftical determination in expensive analytical equipment Inmany cases, achemical assay can alse be carried out by a volumettiomathod. Hore, an autetitator (ex Mettler, Switzerland) Is very handy and eliminates the possiblity of tranual errors in repeat analysis, A Brockfeld viscometeris another handy device to check the stably of suspension concentrates by measuring tho non-Newtonian flow characteristics of the composition a different spindle speeds. It would be desirable to include in the processing equipmenta simall hammer mil, or equivalent, However, if thie net available, a simple coffee250 Hand Book of Agro Cr millora kitchen grinder can be equaly etlecive provided the materatio he {ground is not too hard, 2, Formulation Development Laboratory Fotalaboratory designedio develop new formulations, the equigmen requirements are basically the same except that mote sophisticated an specialized equiprient s needed, Inpertioular, more sophisticated paw, mnilis are required which can be used to yield variable particle sizes, ai mills are bestwhen itis desired'to obtain the smaliest particles. Adcitinally equipmentfor wet grinding andifor granulation would also benecessiry 3.1 Processing Equipment Atits simplest, a ie mill and, ifpossible, an air jet mill. Ph ang roduce meterials in a paricl diameter, mils bring the particle size down to 2-5 ym. These thrae mills protuca a ange of particla sizes sultable for the st lers and their physical properties. im(2). Thus, a laboratory szewet i (exW. Bachaien, Switzerland) ora 2x PE 075 vertical mil (ex Gobr. Noizech, Germany) is essential f Thisis often complemen 501 (ex Silverson Machines, England) toprovide a lumnp-free slur forfeeding into. the Dynomill. High speed homogerizersare also useful for thepreparation of emulsifiable concentrates and emulsion concentrates, | eds te andra nese siavonaryenambor Fue 6 an Figure 6.1 Laboratory Oynorni type KDL-Special (y courtesy of WA. Bachoton AG, ‘Basal, Svizetand)lodern Equipment for a Pesticide Formulation 261 Laboratory and Pilot Plant “the high sheerrate chances media action for particle size distribution {impact scion) and agglomerate separation (shea ctor) Thie is a (rs -ype mil which elinates ar enkapment and foaming during oth9 aeroratory models with 08 life and 0.6 Itre capacities are avaieo’ Livyover, or procesting smaller quantities (as smallas 79 mi). an Get tt motormil (Ex Egor Engineering England) which functions ona ses principe, can be used. One ofthe advantages of & Bynomil is that a pri rainy process can be scaled upto production batches without going through Intermediate pilot plant stusieo, bocause Dromils and SIVETES. figh sheer mixers [Figur 62) o varying processing capaci are available, Fgure 6.2 Sivoon Laraory Mor (by coutesy of SIversen Machines Li, ‘Chesern, Bucks, England)252 Hand Book of Agro Cheriesl Industias (Insecticides & Posteides ec pieces which ety chee rallnes remot Farr a rs conmined oie Gasted size end soeoneg oe ee ohaveben most common usedTor ranuesthat are totally ormainly water soluble. A multiplicity of machines is available for the ebove-deseribed operations. However for pesticide formulation process laboratory, the most decirable equipment is an Erweka multi-purpose processor (ex Etweka Apparatebau, Germary). This apparalus is similarto Pras eee stents such oe coalng pan, ron len, extruder and a palettizer, (Figure 6.2). It offers an ideal cheice in terme, of costand space requirements, ‘granules is offered by Aeromati transparent covering useful for monitoring the preeess during the) Figure 6.3. Erweka multi-purpose processor. (a) coating pan, ‘grinderio) ribbon blender (¢) tumblingand spray granulation (by courtesy Erweka Apparatebau GmbH Heusenstamm, Germany). development of a formulation (Figure. 6.4), The equipment offers tg advantago tht, in adaiton fo agglomeration and drying, operations involving impregnation, coating etc. can also be carried outin the equipment.Ee mncnstinoanen a TTT Modern Equipment for 2 Pesticide Formulation 253. Laberatory and Plot Plant invelves spraying ‘a sdlution or e concentrate: suspension of the pesticide, with or ‘without binderagent, into ¢ conical cylinder in which hot airis circulated, Solid pariicles form from the spray droplets and agglomerate during the drying process, forming Figure 6.4 Acromatisfui-bed granulate. Iboratory urit Stet (by eourtoay of | —-Reromate AG; Bubendort, Svtzerland) microgranules, These particles collect in the bottom of the cone and are emoved. Amini spray dryer for laboratory use ‘s available trom Buchi, Switzertand, early distinguishable ther devices employed for granulation include the inclined rotating cylinder, used in making fertiizars, and Lodige mixers, Which are used in food mixing, A. the developmentphase itis destable tohavea vatiely of laboratory equipment available to evaluate different techniques of granulation, However, Selection of a process willdepend upcn thetypeofproductrequred andthe == availability of the plant-size equipment { iacture. The process ‘Sams teohniques, A list of some ote more important laboratory process254 Hand Book of Agro Chemica Indusies (nsectotos & Poste {|quipment for formulation davelepment, along with the identity ofthe anufaciurers/suppliers, is given in Appendix A 4 8.2 Physical Testing Equipment Formulation chemists have to employ a number o} test methods fr the evaluation of the physical characteristics of processed formulations, These mothods can be classifiad into two categories. The frst cateyory| constitutes n d to.0 ardor to ulated The. ducts fortheiy pecilication Under the frst category, gamut of techniquesis available for teting the wide range of physical characteristics that occur in formulation evelopment, Examples range from light or electron microscopic methods through techniques for he measurement of rheological charactersics, interfacial tension, abserption isotherms ate, Equipment useful in thece {ests includes bictogical and stereo microscopes, suppor ing photographic facilities, a rotational viscometer and a tensiemeter, An exiremely important property of most solid formulations and sespersionconcentte isparldesizaCilealstasarinina sarge O-t and 10u1m. The measurement of particle sizo generally requires soptisi though some simple quaitativa tosts ero availble, +h. However, more sophisticated rnears of ‘measuring particle sizo such ac the Malvern, ate desirable, Although most of this laboratory equipment would be considered Important tor developmental purposes, procurement of tha highest love of soohisteation and sensitivity may be impeded by budgetary consirants Unfortunately the more sophisticated and mere sensitho equipmentis usually morecosty, in industrial research ono myst woigh the relationship between the data obtainable and the price of obtaining it. The formulation chemis will need to make a decision éonceming the trade-off between the cos! ol the equipmentand the quaily ofthe dats that willbe cbtainec. In thiscennacion, one ean always concentrate on the most important properties of the formulation and first try to optimize them. The second category consists of equipment that measures properties describedin the lo character: lity of P ‘as biological activites and crop tolerances are dificul te determine quantitatively in he laboratory, other parameters“cides heir 4 for ions, gory arto The their tion ting tion ods ics, 2se ‘tie nd vof es fe, of d of wasee odein’ Equipment for a Pesticide Formation 258 latoratory and Filo! Part that an be measuredreadly by physicaland chemical methods are specified ina specification. Often the method used has been testadina collaborative studyand has beer, widely approved. This includes equipment suitable for caying out an assy of the active ingrecient in a formulation and equipment able to assass both the chemical and physical stabilty of new formulations. Generally speaking, this involves, atits simplest, a UV spectrophotometer and chromatography equipment, ,e.aGC andlorHPLC. A ‘ropicalclimate tosteris desirable to study the etabilty ofa formulation undor conditions of accelerated storage and to cheok its corrpatibilty with the packaging. A suggested lst of physicaland analytical testing equipment, along with some of the identified sources, is given in Appendix B. 4. LABORATORY FOR BASIC FORMULATION RESEARCH. Tosot up « laboratory to carry outbesie research on formulations and formulaton adjuvants requires considerable expenditure of funds. In addition to the equipment cited earlier, it is essential to have available very sophisticated means of measuring particle size with a Malvern ¢ a Coulter counter. The Malvern master sizer can measure particles in the range 0.1 ° 600 jm; the Coulter counter covers the range 0,6-800 4m in diameter, One should nots, however, thatthese two machines may produce different results if thepartiole shape differs substantial irom the spherical ‘Addional desirablo equioment wouldincludo equipment to measure surface tension, zeta potential, absolute density et, nt wouldincludea drier, pan granulator, a collo blender. Such an array of equipment ivea cocd variety of approaches forthe preparation of different formulations. Je analytical side, equipment such as thermal analyses, including (OTA), dferential scanning calorimetry (OSC) and thermal cravimetric analysis (TGA), and an atomic absorption spectrophotometer are particularly useful in evaluating the suitability of a ‘mineral carrieras a pesticide diluent, These instruments yield information on the mineral characterization of clays, their crystallinity and the type of associated water (structural, bound or unbound), which mey affectthe stability, ofa formulatedpesticida nl. Here one compares the thermal curve wt race Ingredient with the curve obtained when he ‘with a potental carrier (6). ‘Atomic absorption spectroscopy can generate information on heavy metal256 HHend Book of Agro Gremital indvsrie (noctiodes & Pestictoy | the active: ee Equipment{or GLC and HPLO, wih standard dotectors, is esoenta, fora chemioal assay of active ingredients. Some eauipment is now available vith an interface with a mass spectral detector (MSD). This detector offers tan economical way fo enable one toidenity and analyse breakdown products {{poeteides inthe formulations and toanalyses pesticide reskiues Howe equipment with an MSD is quite expensive and ts acquisition hes to ba rationalized withthe evailable budget plex, tigh molecular weightor thermally fable moxures thatare dtfeultt separate jas. It supplements the capabilities of gas and liquid chromatography, combining the solublty behaviour ofliauids andthe diftusion and viscosity properties of gases. The equipment can be coupled with an SFE, which tapidly extracts the components of interest from al complor, aly and quanttativelyforsubsequentaralysis. Tho technique soll fropesticide residue analysis. 1 various spectrophotometrc techniques, UV-visible and IR ployed for assaying pesticices inthe A) system provides a high vated scansata forent piaoas of equipment by ensuring imo the equipment is ordered. This can ge andhandling. the processing of Formulations Ideally, pilot plant equipment for the provessing of fomulations vill effectively simulate, on a larger scale, the processes obsarved in he faboratory, However, it does not always succeed In this, The situation becomes particularly complex when the equipment employed for laboratory ‘soalo process developments nat available in larger capacty models or shen the larger equipments functions on a different principle, In such & “Stuation the lbboretory process needs tobe revalidated by changinaprocess paramelers such as temperatur, timo, feed rate, size, and number of recyoiings. 65, Pilot Plant EquipmentModlom Equinment for a Pesticide Formulation 257 Laboratory and Pict Plent Frequently the seme pilot plant equipmentwil he used orprocessing different pesticides, such as herbicides, fungicides, and insecticides. Contamination problerns may arise, Thus, versatile equipment should be selected which has eesy clean-up and decontamination (7). Many types of processing equipments, such as the size reduction milla, mixers and blendors and granulating systems described in Section 3.1, ate avellable in larger models and are suiteble forthe piotplant, There may be, however, scale-up problems. For examples, in the size reduction process, the choice ofthe type of size reduction millis dependent upon the physicalproperties of the feed material andthe desired size distribution of thecutpit. Insome mills, such asa high-speed hammer mil or a pin mil, tomperatura rise in the grinding chamber oczurs due to heat generated duting thoir operation, This temperature rise may cause the formation of sticky materials thet will agglomerate or t may cause heat-senstive materials to decompose. Ard of course, sticky agglomerated matarials do not grind ‘wel, Some ofthese problems may beallevatedby processing the formulation in anairjet mill.On the other hand, a relatively elficient size reduction mil known as anaitswept ultra-fine vortex mills widely used in Europe forthe production of wettatle powder formulations. The mill may provide atfinely {ground product (below 1Oum) at a much higherrate thana hammer mi and more economically than an air jet mill (7). The equipmentis available in a pilot plant sizo model from Ultrafine, France. However, sticky and heat: ‘Senslive materials cannot be processed in itunder normal conditions. Fora wet grinding process, dynomils are availablein severallarge-size models ‘Similary, larger versions of Silverson mixers are also available. Both of these machines ara commonly used in the pesticide industry for the processing of suspension concentrate formulations. ; lot h y. Fordiferent granulation processes, a varity of equipmentisavalabie {or pilot-plant scale operations, including sigma mixers, or kneaders, for dough making and screw axiruders for making extusion-type granules. Similarly fluid-bed systome are offered by Aeromatic, Switzerland, and ‘Alpine, Germany, The Aeromatic systems are available either as mult- processers oras a building block system that canbe assembled to suit the Fequired use, Spray-crying equioment is avellable from manufacturers lke ‘Anhydro, Stork Friesland and Niro Atomizer. Iicomes in a wide variety of ‘dryer shapes fo suitdiflerent products and processing conditions. To improve the control of product dryness and raise the overall energy elfciency, itis258 Hane Book of Agro Chemical Idusties (insectoides & Pag possidle to add a tluid-bed dryer io a basic spray dryer. Such g fiuid bed combinations are particularly suitable for heat-sensit 6. Conclusion pray a As rapid advances in tachnology and newer developments in high, sophisticeted processes and analytical equipment have a symbiety, ‘olationship, itis only to be expected that siats-ol-he-art equipment ig 4 soan superseded by even more versalle orsephisicated equipment. Howeves itis not nocassary to have an extremely elaborate and fully equipped Jaboratory to do usetul werk on formulations and formulation developmeny, As impertantto a goodfoimuletion laboratory as sophisticated equlpman, are innovative ideas drawn from day to-day observations, Besides, many of the techniques used in pesticide formulations are drawn, either diractly og indirectly trom food processing techniques. Itis often possible to develop new formulations with very simpleecuipmert. In this contex, an appropriate approach for equipping a pasticide formulation laboratory mightbo the gradual addition of equipmentas noaded, Let the laboratory evolve in conformity with the exposure and training of the formulation chemisis and in relation 19 the level of sophistication foreseen for various planned projects. In additoh, the financial support available would have a significant intluence oh the development ot the laboratory. (CP APPENDIXA List of processing equipment fer a pestioide formulation laboratory 4 and 8ome of tho soures for their supply. Exibrmant ‘Seurco 1. Hemmermil(Cordix ype) FG. Bode Go, GmbH 2 Laboratry atin il Schlossnthlendarn tt (Conduictype) 0. Box 900187 1D 20157 Hamburg, Gomeny 3. Pinal ‘Aline AB (Laboratory rivers! Mt) 96199 Augsbug, Germany 4. Atdetmit wierontzer ‘SurteventntentionalSaes Corp. 108 Cayton St rochester Boston, MA02122, USA ‘ Fd Enerylteratonal Sales Corp 4163 Pom Avenue Hatioid Pt 19440, USA 5. Alnswoptmicrvoetoxmi ScolatoUtaine Uso de Viflencure ‘ur Verberle 60410 Verbers, FranceModern Equipment for a Pos Laboratery ars Pile Plant © Aglatechypeheizonal Dyno 7. Agtatedbeadeand mill (Eigeeminimoter it) 8. Hiph-sheor homogenizer (Civersenleboratory mixer 9, Mulipurpose procoscor with (aypatietzer (t) eoaingpen (extruder and (d rbbon blender attachments 10, Fhictbed andlor with Wurster _acnesscry(Aeromatic Laboratory unt STREA) 11, Mtspray dryer 12, Phoughshave mixer (Lodigemier) APRENDIXB ids Formotation 259 Wily A Baokolen AG Mashinentabni, 17 Ungusse Hracos Dace, Switzerland Eger engneering Lic 40 Hacdnlek Grange, Woolstone ‘Watinglon= ChoshireWA 1 4RF, England. Siverzon Machines Lid, Walesic, ‘Chosham, Bucks HPS 1 PO, Engand Eval Apperabbu Gmibl FO. Box 1253 Otostrasse20-22 D.63160Heusenstamm, Gormany ‘Aetomate AG Hauplstmsso 145, (CH-4416 Bubenctot, Switzerland ‘Actomate Ine, Tewace, NJ 07082, USA Buch aboratriume achrile AS Faw, Swiverand (Gobruderlocige Machinerbau GmbH Postiach 2050 EisonorSrasso7-9 1.33100 Paderborn, Germany, Yet of physical testing and analytical equipment and some of the sourcts fortheirsupply Equipment Souree 4, Sevingapparatus Tipine AG, Peetach 629, (Apne Lutsrahisiot) 86199 AugsburgGermany 2 Topic Climate Tester (roaccoler- _Hereus-Vetsch Gm etedatorage studios) Bosthovenetiasso 34 72354 Batingen-Frommern, Germany 3. Blelegical and storao ‘microscopes ‘Olympus Optica Co, Lt. can-£iBulding. 22.2 Niehi Shiejuku +-Chome Shnjukuku, Tokyo, JapanHand Book of Agro Chemical Industies (Insecticides & Pes leas) Nikon Comporaton, Ful Busing, erunouch 3-Choma, hiya, Tekeye 100, Japan 4, Paitce sizeanalyser (Malvern Mas- Malvern Inskument Lt. tereizer lo moaeure 0.1-660 jm par- Springiare South, Malvern, tickesizes) Worcestershire, WRT41AQ, Engng 5 MalvernZeta Sizer Ilo ©, _Eectonic purclecountor CcoulbrBlectrenies Ine. ‘ (Couer Counter TAA) Hialeah, FLUS.A ‘ 7, Brookie VTViccometor Bjookfiec Engineering Lab 240 Cushieg Streot ‘Stoughton, MA02072, U.S.A 8. Haake Robviske MSEScertficinstuments Crate, Sussex, England, 9, Doerrheometor Intecrated Potronie Systoms: Landon, England 40, Tuedenser ‘Sheshin Enterpr'ses Co. Ltd | 527-7 Sadagaya | sShivaya Ku, Tokyo, Jepan 41. anaiical balances Sotoricus Instruments 1490 Viankogan Road MoGaw Patk,IL60085, U.S.A. 52. Aatotivatertrortizator Mettar Instrumente AG. ore cites ovted 18 caeaeconatoeen Holt Patt, i Perkin-Elmer Corporation retina nea creneoo12 USA Stim Caetn 3a chee Cito, Tye pn¥ Modein Equipment for a Pesticide Formsation 261 Laboratery and Pilot Plant 14. High pressure uid chromatograph 16. Supereiicatnuis hromatogreph 16. Infarredspectophotometer and Fourier Traneforrn IF, spectrophotometer 17. Pholodioded array U¥.visie epen- trophotoretae 18. Atomic abserpton ‘Spectophotomatar 30. Thotrtalanalyeer ‘Waters, Ovisionsot Mapore Maple Street ey, MA0N757, US A Suprex Corporation SFO Research Centre 125 Witiam Pit Wey Pltouigh, PA 18233, U.S.A. Compte: Chenical Sysioms ALATA Nowark Road, PO.Ba« 62, Avondale, PA 19311, U.S.A Peskin Eimer Lid, Nowak, CT USA. ‘Shimatdeu Corporation, Tokyo, Japan ‘Mattson Instuments ne. 4001 Fourier Dive Madson, WISS717, USA. Hanlet-Packard Co, Pedo Ate, CACA04904,U 8. ‘Backman instruments In. ‘Alex Dision, 22050 Camino Ramon, Po, Boxst01 ‘San Ramon CA9458, USA. Poskin-Emet Corporation, Nerwalk, CT 06860, U.S.A. Pye Unica Lt, York Street, Cambridge, CB1 2 PX, Encland DuPont Compny Instrument systoms ConcordPlaze Quilon Ble, Wimglon, DE 12000, U.S.A, (Metter Instumerie AG, fi Grolfensoe, Switzerland.