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Role of Heat Treatment on the Performance of Polymers As Iron Oxide Dispersants

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Role of Heat Treatment on the Performance of Polymers As Iron Oxide Dispersants APPLICATION ❙ Z. Amjad Role of Heat Treatment on the Performance of Polymers as Iron Oxide Dispersants The influence of heat treatment on the performance of various 1 Introduction polymers as iron oxide dispersants in an aqueous system has been investigated. The polymers evaluated include: homo-poly- Feed water available for domestic and industrial uses is gen- mers of acrylic acid, methacrylic acid, maleic acid; co-polymer of, erally contaminated with various forms of dissolved ions acrylic acid:2-acrylamido-2-methylpropane sulfonic acid; ter- (i. e., calcium, magnesium, carbonate, sulfate, etc.), colloi- polymers of acrylic acid:2-acrylamido-2-methyl propane sulfonic dal, and suspended matter (i. e., clay, silt, organic debris, cor- acid:sulfonated styrene, and acrylic acid:2-acrylamido-2-methyl- rosion products, etc.). The type, size, and concentration of propane sulfonic acid:t-butylacrylamide. It has been found that suspended particles affect their behavior in water systems. all polymers lose performance to a varying degree when ex- In addition, metal ions (i. e., Cu, Mn, Fe) present in feed posed to thermal treatment (150 °C, 200 °C, 20 hr). The perfor- water may get hydrolyzed and/or oxidized under conditions mance data also suggest that sulfonated styrene containing ter- typically encountered in domestic and industrial systems. polymer is a better iron oxide dispersant than the ter-polymer Maintaining this hydrolyzed and/or oxidized metal ions in containing 2-acrylamido-2-methylpropane sulfonic acid and ter- soluble and in dispersed forms can prevent the build-up of tiary butylacrylamide. In the case of co-polymer of acrylic acid:2- unwanted deposits on various substrates. acrylamido-2-methylpropane sulfonic acid, the thermal treat- Although feed waters contain a variety of suspended ment exhibits strong negative influence on the dispersancy matter, iron-based foulants (e. g., Fe2O3,Fe3O4, Fe(OH)3, power of the polymer. The results have been explained in terms FePO4) are generally considered to be one of the most chal- of loss of 2-acrylamido-2-methylpropane sulfonic acid and t-bu- lenging problems. The four major approaches to control tylacrylamide in the co- and ter-polymers, as determined by FT- iron oxide deposits are: (a) removing iron oxides (corrosion IR and NMR methods, leading to the formation of poly(acrylic products) from the systems (filtration), (b) inhibiting corro- acid). sion at its source (this is achieved by the use of corrosion in- hibitors), (c) stabilizing Fe(II) and Fe(III) ions in the feed Key words: Polymer, dispersion, thermal stability water (involves the use of iron selective chelants), and (d) treating the feed or re-circulating water with iron oxide dis- persant(s) to minimize iron oxide deposition within the sys- tem. The use of dispersant is generally considered to be the Einfluss einer Wärmebehandlung auf die Leistungsfähigkeit most economical method. von Polymeren als Eisenoxid-Dispergiermittel. Der Einfluss ei- The suspended particles typically encountered in indus- ner Wärmebehandlung wurde auf die Leistungsfähigkeit ver- trial water applications generally carry a slight negative schiedener Polymere als Eisenoxid-Dispergiermittel in wässrigen charge. Therefore, anionic polymers are normally the most Systemen untersucht. Bewertet wurden folgende Polymere: efficient dispersants because these anionic polymers in- Homopolymere von Acrylsäure, Methacrylsäure, Maleinsäure; crease the negative surface charge and keep particles in sus- Copolymere von Acrylsäure:2-Acrylamido-2-methylpropansul- pension. Cationic polymers can be used as dispersants but fonsäure; Terpolymere von Acrylsäure:2-Acrylamido-2-methyl- this requires relatively high polymer concentrations in order propansulfonsäure:sulfoniertes Styrol und Acrylsäure:2-Acryl- to first neutralize the negative surface charges and then to amido-2-methylpropansulfonsäure:t-Butylacrylamid. Es wurde transfer cationic charge to particles for efficient dispersion. gefunden, dass alle Polymere an Leistungsfähigkeit mit un- Suspension of clays, metal oxides, pigments, ceramic terschiedlichem Ausmaß einbüßen, wenn sie einer thermischen materials, and other insoluble inorganic particulate solids Behandlung (150 °C, 200 °C, 20 h) ausgesetzt werden. Die Leis- in aqueous systems through the use of small quantities of tungswerte zeigen, dass sulfoniertes Styrol mit Terpolymer ein synthetic polymers, polyphosphates and other polyelectro- besseres Eisenoxid-Dispergiermittel ist als ein Terpolymer mit lytes has become an increasingly important area of study 2-Acrylamido-2-methylpropansulfonsäure und tertiäres Butyl- with high technological relevance [1–4]. Dubin [5] in his in- acrylamid. Im Fall des Copolymers von Acrylsäure:2-Acrylamido- vestigation on the evaluation of polyphosphates, organopho- 2-methylpropansulfonsäure zeigt die thermische Behandlung ei- sphonates, poly(acrylic acid), P-AA; poly(maleic acid), P-MA; nen starken negativen Einfluss auf die Dispergierfähigkeit des and co-polymer of acrylic acid:maleic acid (P-AA:MA) as dis- Polymers. Die Ergebnisse sind erklärbar durch einen Verlust an persants for iron oxide showed that acrylic acid and maleic 2-Acrylamido-2-methylpropansulfonsäure und t-Butylacrylamid acid based polymers performed better than polyphosphates bei den Co- und Terpolymeren, was zu einer Ausbildung von and organophosphonates. The effectiveness of polymers as Polyacrylsäure führt und mittels FT-IR- und NMR-Methoden be- dispersants for clay and iron oxide has been the subject of stimmt wurde. numerous investigations. It has been reported that polymers containing different functional groups i. e., carboxyl, amino, Stichwörter: Polymer, Dispersion, thermische Stabilität sulfonic, amido, etc., are effective dispersants [5–7]. In addi- tion, it has also been shown that polymer molecular weight plays an important role in dispersing suspended matter in 242 Carl Hanser Publisher, Munich Tenside Surf. Det. 43 (2006) 5 Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants aqueous systems. Recently, the influence of polymer archi- been mostly overlooked. In the present paper, we report tecture in dispersing many ceramics has been the subject on the results of investigations conducted to gain informa- of numerous investigations. Results of these studies have tion about the impact of thermal treatment on the perfor- shown that acrylic copolymers containing acrylic acid group mance of a variety of polymers used as scale inhibitors and other monomers, such as alkyl ester group, possess and dispersants in high temperature applications. The poly- properties different from those of P-AA [8–10]. mers we have selected include: a) homo-polymers i. e., Thermal degradation of polymers is a well studied area. poly(acrylic acids), P-1, P-2; poly(methacrylic acid), P-3; However, there is little information available of real value to poly(maleic acid), P-4; b) co-polymer i. e., poly(acrylic acid: industrial technologists concerned with using low molecular 2-acrylamido-2-methylpropane sulfonic acid), P-5; and c) weight polymers. Polymers used in high temperature appli- ter-polymers i. e., poly(acrylic acid:2-acrylamido-2-methyl- cations should be able to sustain high temperature and pres- propane sulfonic acid:sulfonated styrene), P-6; poly(acrylic sure environments normally associated with boiler and ther- acid:2-acrylamido-2-methylpropane sulfonic acid: tertiary mal desalination operations. McGaugh and Kottle [11] butyl acrylamide), P-7; Poly(acrylic acid:methacrylic acid: studied the thermal degradation of poly(acrylic acid) and la- tertiary butyl acrylamide, P-8. In addition, an optical micro- ter the thermal degradation of an acrylic acid-ethylene co- scope was used to study the influence of dispersants on polymer. They used infrared and mass spectrographic analy- iron oxide particle size distribution. sis to examine the degradation processes that occurred in the temperature regions 25–150 °C, 150–275 °C, 275 to 350 °C and above 350 °C. Their results suggest that in air 2 Experimental (min heating) dry poly(acrylic acid) decomposes by forming an anhydride, probably a six-membered glutaric anhydride- 2.1 Materials type structure at temperature up to 150 °C. At 350 °C there is drastic unmeasurable change and strong unsaturation ab- Grade A glassware and reagent grade chemicals were used. sorption. Mass spectrographic analysis showed that carbon The iron oxide (Fe2O3,) used in this investigation was ob- dioxide was the major volatile product at 350 °C. tained from Fisher Scientific Co. It was characterized as he- Denman and Salutsky [12] briefly examined the thermal matite by x-ray diffraction (JCPDS phase SS664). The parti- stability of a sodium poly(methacrylate) and a sodium poly- cle size distribution (with majority of particles in the 50 to (acrylate). Under dry conditions they found no change to 150 micron range) was obtained using a Beckman Coulter 316 °C after one (1) hour but some charring at 371 °C. Mas- Counter Model LS320. The polymeric materials used as dis- ler [13] investigated the thermal stability of several homo- persants were selected from commercial and experimental polymers used in the boiler. It was demonstrated that under materials and are listed in Table 1. All dispersant solutions the experimental conditions employed (pH 10.5, 250 °C, were prepared on a dry weight basis. The desired concentra- 18 hr] that P-AA, P-MA; and poly(methacrylic acid), P-MAA tions were obtained by dilution.
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