ABSTRACT
Adsorption of arsenate, phosphate, salicylic acid, and groundwater DOC onto granular ferric hydroxide (GFH) was studied in batch and column experiments. Breakthrough curves were experimentally determined and modelled using the homogeneous surface diffusion model (HSDM) and two of its derivatives, the constant pattern homogeneous surface diffusion model (CPHSDM) and the linear driving force model (LDF). Input parameters, the Freundlich isotherm constants, and mass transfer coefficients for liquid- and solid-phase diffusion were determined and analysed for their influence on the shape of the breakthrough curve. HSDM simulation results predict the breakthrough of all investigated substances satisfactorily, but LDF and CPHSDM could not describe arsenate breakthrough correctly. This is due to a very slow intraparticle diffusion and hence higher Biot numbers. Based on this observation, limits of applicability were defined for LDF and CPHSDM. When designing fixed-bed adsorbers, model selection based on known or estimated Biot and Stanton numbers is possible.
Subject(s)
Ferric Compounds/chemistry , Adsorption , Anions , Diffusion , Kinetics , Linear ModelsABSTRACT
Adsorption onto granular ferric hydroxide (GFH) with subsequent in-situ regeneration is studied as a new process for natural organic matter (NOM) removal from groundwater. Adsorbent equilibrium loadings of 10-30 mgDOC g(-1)GFH(-1) are obtained, whereas the non-adsorbable DOC fraction amounts to 1.5 mgL(-1) for all investigated groundwaters. The larger and UV-active NOM fractions (mainly fulvic acids) are well adsorbed while the smaller molecular fractions are poorly or not adsorbed. However, kinetic studies show that the smaller and medium-sized fulvic acids are removed first. The equilibrium is strongly dependent on pH but only weakly on ionic strength, pointing to ligand exchange as the dominant adsorption mechanism. With regard to NOM structure, prerequisites for adsorption onto GFH are both a minimum number of functional groups and a molecular size small enough to enter the GFH pores. NOM breakthrough curves are successfully simulated using the LDF model (homogeneous surface diffusion model (HSDM) with linear driving force approach for surface diffusion) and experimentally determined mass transfer coefficients. Regeneration of loaded GFH is possible either by use of NaOH or oxidatively by H(2)O(2). The optimal quantities and concentrations are determined.
Subject(s)
Ferric Compounds/chemistry , Humic Substances , Water Pollutants/chemistry , Water Purification/methods , Adsorption , Filtration , Germany , Hydrogen-Ion Concentration , Kinetics , Particle Size , Water SupplyABSTRACT
Breakthrough curves (BTC) for the adsorption of arsenate and salicylic acid onto granulated ferric hydroxide (GFH) in fixed-bed adsorbers were experimentally determined and modeled using the homogeneous surface diffusion model (HSDM). The input parameters for the HSDM, the Freundlich isotherm constants and mass transfer coefficients for film and surface diffusion, were experimentally determined. The BTC for salicylic acid revealed a shape typical for trace organic compound adsorption onto activated carbon, and model results agreed well with the experimental curves. Unlike salicylic acid, arsenate BTCs showed a non-ideal shape with a leveling off at c/c0 approximately 0.6. Model results based on the experimentally derived parameters over-predicted the point of arsenic breakthrough for all simulated curves, lab-scale or full-scale, and were unable to catch the shape of the curve. The use of a much lower surface diffusion coefficient D(S) for modeling led to an improved fit of the later stages of the BTC shape, pointing on a time-dependent D(S). The mechanism for this time dependence is still unknown. Surface precipitation was discussed as one possible removal mechanism for arsenate besides pure adsorption interfering the determination of Freundlich constants and D(S). Rapid small-scale column tests (RSSCT) proved to be a powerful experimental alternative to the modeling procedure for arsenic.
Subject(s)
Ferric Compounds/chemistry , Water Pollutants/isolation & purification , Water Purification/methods , Adsorption , Arsenates/isolation & purification , Arsenic/isolation & purification , Charcoal/chemistry , Chemical Precipitation , Diffusion , Filtration , Models, Chemical , Organic Chemicals/isolation & purification , Salicylic Acid/isolation & purification , Surface Properties , Temperature , Time FactorsABSTRACT
The advanced phosphorus (P) removal by adsorption was studied for its suitability as a post-treatment step for membrane bioreactor (MBR) effluents low in P concentration and particle content. Two commercial adsorbents, granulated ferric hydroxide (GFH) and activated aluminium oxide (AA), were studied in batch tests and lab-scale filter tests for P adsorption in MBR filtrates. GFH showed a higher maximum capacity for phosphate and a higher affinity at low P concentrations compared to AA. Competition by inorganic ions was negligible for both adsorbents at the original pH (8.2). When equilibrium P concentrations exceeded 2 mg L(-1) in the spiked MBR filtrates, a precipitation of calcium phosphates occurred additionally to adsorption. During column studies the effluent criteria of 50 microgL(-1) P was reached after a throughput of 8000 bed volumes for GFH and 4000 for AA. Dissolved organic carbon appears to be the strongest competitor for adsorption sites. A partial regeneration and reloading of both adsorbents could be achieved by the use of sodium hydroxide.
