Seawater polymerization reactions

A study of the bulk properties of seawater humic substances was carried out by Kerr and Quinn (1975), while a detailed structural analysis was undertaken by Stuermer (1975) and Stuermer jmd Harvey (1978). Stuermer discussed the structural features in terms of origin, chemical and physical properties, interaction in the sea and eventual fate. As an example of the formation of a humic substance in seawater, we will discuss Stuermer s proposed structure of seawater fulvic material (Gagosian and Stuermer, 1977), the precursor compounds to its formation, and the condensation and polymerization reactions responsible for its synthesis. Although the material isolated by Stuermer represents only a small portion of the total hiunic material, it serves as an example of a possible condensation product. 

Orthosilicic acid, Si(OH)4, could be an appropriate precursor, but it cannot be stored in monomeric form at reasonable concentrations in aqueous solutions. It enters easily into polycondensation reactions (1) that result in its polymerization. As a monomer, the orthosilicic add exists in aqueous solutions at a concentration of less than 100 ppm [18]. This is too small to fabricate sol-gel derived materials, although diatoms and sponges have the property of concentrating silica from seawater containing only a few mg per liter [60]. Sol-gel processing in the laboratory can be performed with a rather concentrated solution of orthosilicic add. This requires freshly prepared add the procedure is time consuming which restrids its widespread use. 

The basic structure of humic substances involves a backbone composed of alkyl or aromatic units crosslinked mainly by oxygen and nitrogen groups. Major functional groups attached to the backbone are carboxylic acids, phenolic hydroxyls, alcoholic hydroxyls, ketones, and quinones. The molecular structure is variable as it is dependent on the collection of DOM available in seawater to undergo the various polymerization, condensation, and oxidation reactions and reaction conditions involved in humification, as well as the ambient physicochemical reaction conditions, such as temperature and light availability. 

The initial studies by Cadotte on interfacially formed composite polyamide membranes indicated that monomeric amines behaved poorly in this membrane fabrication approach. This is illustrated in the data listed in Table 5.2, taken from the first public report on the NS-100 membrane.22 Only the polymeric amine polyethylenimine showed development of high rejection membranes at that time. For several years, it was thought that polymeric amine was required to achieve formation of a film that would span the pores in the surface of the microporous polysulfone sheet and resist blowout under pressure However, in 1976, Cadotte and coworkers reported that a monomeric amiri piperazine, could be interfacially reacted with isophthaloyl chloride to give a polyamide barrier layer with salt rejections of 90 to 98% in simulated seawater tests at 1,500 psi.4s This improved membrane formation was achieved through optimization of the interfacial reaction conditions (reactant concentrations, acid acceptors, surfactants). Improved technique after several years of experience in interfacial membrane formation was probably also a factor. 

RO is the most relevant membrane-based technique for seawater desalination [98]. Similar to NF, RO is carried out using asymmetric membranes with a nonporous skin layer. Membranes can be integrally skinned or TFC. The most important technique for the preparation of such membranes is IP, which has been already described in Section 1.6.3 devoted to NF membranes. As reported by Lee et al. [99], the studies about the preparation of polymeric membranes for RO application, from 1950 to 1980, focused on the search for optimum membrane materials. Subsequently, the performance of RO membranes was improved by controlling membrane formation reactions and using catalysts and additives. 

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