| Summary: | - === Calcium salts are known as compounds and minerals and they have been extensively studied due to their rich morphology and applications. They are known as biominerals, cement additives. fillers, food additives etc. In the oil and gas production calcium sulfates, carbonates and silicates form tenaciously adhering scale deposits which may stop production if the problem is not tackled timely. The motivation for this work was the well known problem of sand production during oil recovery, which occurs when the production rate exceeds a critical value. The aim has been an attempt to develop an inexpensive and environmentally friendly method to consolidate soil and sand for building purposes. The work included in this thesis, is focused in the investigation of the physico-chemical conditions at which calcium salts precipitate acting as consolidating material for soil and sand. The marked differences in the physicochernical properties of the precipitating salts enabled us to investigate the relative efficiency of three different classes of calcium salts: sulfates, carbonates and phosphates.
As a result. the present thesis is divided in three parts. In the first one, the spontaneous precipitation of calcium sulfate from supersaturated solutions and the inhibition by water soluble polymers was examined. Two kinds of polymers: three polyacrylates (PAA) with different molecular weights (2.000 (PAA1), 50,000 (PAA2) and 240.000 (PAA3)) and one co-polymer of polyacrylic with polystyrene sulfonate (PAA-PSS) were tested. Very low concentrations of all polymers tested, down to 6ppm, increased markedly the induction period preceding precipitation at supersaturations in which, in the absence of additives the precipitation was spontaneous. The “kinetic Langinuir” equation based on the assumption of Langmuir - type adsorption of the additives on the precipitating calcium sulfate dihydrate, gave satisfactory fit of the kinetic data. From the fit according to this model, the affinity constants for the polymer-gypsum surfaces were calculated. The order of the affinity was PSS>PAA3>PAA1>PAA2. The precipitation of calcium sulfate dihydrate in the presence of sand grains, resulted in crystals which formed weak bridges among the grains and the material in which precipitation took pace was rather poorly consolidated.
The second part reports on the precipitation of calcium carbonate through the enzymatic production of carbonate ions. This newly proposed method is based upon the slow evolution of the supersaturation with respect to calcium carbonate in an aqueous environment, in which one of the components of the supersaturated solution (in our case carbonate) is slowly released by a source through the action of enzymes present in the aqueous medium. The work done concerning the development of the methodology of enzyme mediated calcium carbonate formation in aqueous media involved the following steps:
(i) Investigation of the mechanism of urea (substrate) decomposition in the presence of jack bean urease (enzyme) through conductivity measurements. Urease exhibited a bell- shaped activity profile as a function of temperature with optimum value at 50CC. The reaction of urea decomposition in the presence of urease followed Michaelis-Menten type kinetics up to a concentration of about 250 mM. At concentrations exceeding 250 m.M, the reaction rate decreased as the carbonate source concentration increased, suggesting substrate inhibition.
(ii) The effect of various parameters, such as temperature, enzyme and salts concentrations, the presence of sand etc. was studied upon the rate of precipitation and the morphology of the precipitate. The rate of precipitation increased with increasing temperature up to the optimum temperature of the enzyme activity.
The experimental conditions identified through a series of batch type experiments were optimized for the consolidation of granular materials. Lab experiments done in loose sand packs have shown that consolidation may be achieved through bridges of calcium carbonate formed enzymatically. The consolidation efficiency was found to be strongly dependent on urease quality. Crude jack bean urease was more effective than refined one, due to impurities which promote calcitic rhombohedra to precipitate. Increasing the number of solution injections resulted in increased strength and reduced permeability, as expected. Resistance to uniaxial strength was found to be inversely proportional with temperature. The highest values were obtained for precipitates formed on sand grains at 25:C. The initial concentration of the supersaturated solutions were also found to affect the degree of consolidation, because of the different precipitation rates (higher at higher supersaturations) and of the amount of the material precipitated on the grains, which again was more, the higher the solution supersaturation with respect to calcium carbonate.
Next, the heterogeneous nucleation and growth of calcite was investigated both in unstable and stable solutions at supersaturations sufficiently low to allow for the measurement of induction times preceding the onset of precipitation. In the unstable regions the induction times were inversely proportional and the rates of precipitation increased with the solution supersaturation. The high order dependence of the rates of precipitation on the solution supersaturation suggested a polynucleation mechanism. Fit of the induction time-supersaturation data according to this model yielded a value of 49 mJ/m2 for the surface energy of the calcite nucleus forming. In the stable domain of the supersaturations, seeded growth experiments showed a second order dependence on the rates of crystal growth of calcite seed crystals, while quartz seed crystals failed to induce nucleation. Raising supersaturation to reach the unstable domain showed interesting features: calcite seed crystals yielded crystal growth kinetics compatible with the polynucleation model, without any induction time contrary to the quartz seed crystals that triggered secondary nucleation. The kinetics data in the latter case were consistent with the polynuclear model and the surface energy for the newly forming embryo was calculated equal to 13 mJ/m2, confirming the fact that the process is dominantly heterogeneous.
In the third part of this dissertation an attempt is presented to apply the idea of enzymatic precipitation of salts to the case of calcium phosphate formation. For this purpose, two kinds of phosphatases were tested for their PO4/3 release capacity from polyphosphates. Each type of the enzyme functioned at a different pH, so that a wide pH-range was covered (5.50-9.80). A seven-fold increase in the enzyme concentration resulted in the increase of the hydrolytic substrate decomposition percentage from 38% to 82% at pH 5.50. At pH 9.80, increasing the amount of alkaline phosphatase by a factor of five, the percentage of hydrolytic decomposition increased from 800o to 100%. The temperature dependence of the enzymes’ activity allowed for the determination of the maximum rate and the Michelis-Menten constant. At 25oC, Rmax and Kmwere calculated equal to 3.2x104 mol/h and 2.15x l0 mol/l for acid phosphatase, while the values for alkaline phosphatase were 5.9x10 mol/h and 4.26x10-3 mol/l, respectively. The activation energies were calculated to be 31 and 74 kJ/mol for acid and alkaline enzymes respectively. In terms of precipitation, the enzymic hydrolysis method is applicable for concentrations of the substrate and of the cation of the precipitating salt lower than 0.05 mol/l. For higher concentrations, insoluble complexes of Ca-substrate were formed and the precipitation of calcium phosphate was not favored. The presence of sand promoted both precipitation and hydrolysis when acid phosphatase was used, while with alkaline phosphatase the effect of the presence of sand was negligible. Consolidation experiments conducted in loose sand packs indicated that this method may be applicable only to stabilize sand with a few applications of the working solution, since the amount of the precipitate is small for the concentration levels suggested by the results of the present work. For strong consolidation, and for the composition of the solutions suggested in this work, a large number of injections is needed.
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