Stig Wedel

The nucleation of aerosols in flue gases with a high content of alkali: A laboratory study

The formation of particles during cooling of a synthetic flue gas with vapors of sodium and potassium species is studied in a laboratory tubular reactor with laminar flow. It is shown to agree well with a theoretical model for the process. The kinetics of homogeneous nucleation of the pure chloride vapors is described by the classical nucleation theory, adapted to include the participation of stable dimer as well as monomer vapor molecules. The Tolman equation is used to describe the curvature-dependence of the surface tension of small nuclei. The values of the Tolman parameter for NaCl and KCl are determined from the measurements. The homogeneous nucleation of the pure chlorides is suppressed by even relatively small concentrations of foreign seed particles and is therefore unlikely to contribute to the creation of new particles in real flue gases. The addition of SO2 to the chloride vapor feed, in the presence of oxygen and water vapor, increases the number concentration of effluent particles significantly and affects their composition to include sulphate in addition to chloride. The sulphate content is independent of the peak temperatures of the flue gas but increases with increasing content of oxygen and SO2. The study proves that the alkali sulphates are formed by the sulphation of vapor phase rather than solid, alkali chloride. The sulphate vapors are formed in high supersaturation and show a pronounced tendency towards homogeneous nucleation, which is identified as the likely source of the submicron particles formed in alkali rich flue gases.

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al2O3) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (γ-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m2/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m2/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl2O4 intermixed with either ZnO or Al2O3 phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m2/g. The gas-to-particle conversion is initiated by the fast nucleation of Al2O3 or ZnAl2O3, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.

The kinetics of the photolytic production of aerosols from SO2 and NH3 in humid air

Abstract The reaction of SO 2 and NH 3 in humid air to produce an aerosol of ammonium sulfate is studied in a photolytic laboratory reactor. The reaction is shown to be controlled by ultraviolet irradiation in the wavelength range of 240–330 nm and is initiated by excitation of SO 2 . It is found that NH 3 has a strong catalytic effect on the photolytic oxidation of SO 2 and surprisingly high values of the quantum yield are observed with NH 3 concentration in the range of 20–400 ppm. The reaction rate increases with decreasing temperature. An overall mechanism for the formation of aerosol particles is proposed. It is concluded that aerosol formation due to sunlight photolysis by this mechanism explains the high-opacity smoke formed in industrial stack plumes with small amounts of NH 3 and SO 2 .

The Formation of Porous Membranes by Filtration of Aerosol Nanoparticles

Flame-generated aerosol particles of Al2O3 were deposited by gas filtration on two types of porous and ceramic tubes of α-Al2O3 with mean pore diameters of 450 and 2700 nm, respectively. The particles were aggregates with average mobility diameters in the range of 30–100 nm and primary particle diameters of 4–8 nm. The particles are characterized by differential mobility analysis, transmission electron microscopy, and by their specific surface area. The deposited membranes are characterized by gas permeability measurements, scanning electron microscopy, and by their pore size distribution from nitrogen capillary condensation. The particles form a distinct, homogeneous membrane layer with a porosity of ∼90% on top of the substrate surface and only penetrate slightly into the substrate structure. The mean pore sizes of the deposited membranes determined by nitrogen condensation agree approximately with those determined by gas permeation and the specific surface area. The mean pore diameter varies in the range of 30–70 nm. The gas permeability of the deposited membranes is related to the specific surface area but influenced by the high porosity. The mean pore size and the permeability of the membranes are almost independent of the substrate structure.The development of a membrane with uniform properties is preceded by a short initial period in which the deposited particles, with an equivalent membrane thickness of roughly 2 μm, have a significantly lower permeability than the ultimately developed uniform membrane layer. This effect is particularly significant for the aerosol particles with the lowest mean size, probably due to particles deposited in the pore mouths of the substrate.The particles and the deposited membranes are X-ray amorphous but retain their specific surface area on heating to even high temperatures. When the membranes are heated to 1473 K for 10 h, X-ray diffraction shows a mixture of θ- and α-alumina, accompanied by a partial disintegration of the membrane and a considerable loss of surface area.

Asymptotic stability of a catalyst particle

Abstract The catalyst asymptotic stability problem is studied by means of several new methods that allow accurate solutions to be calculated where other methods have given qualitatively erroneous results. The underlying eigenvalue problem is considered in three limiting situations Le = ∞, 1 and 0. These are solved first to give expansion functions for the full eigenproblem at an arbitrary value of Le . A modified Galerkin method based on the two sets of eigenfunctions for the Le = 1 problem even in the lowest order approximation able to solve the full problem for all Le . Perturbation methods developed from the solutions at the limiting Le -values may if properly handled be extremely useful, e.g. for calculating the stability limit. Finally approximate values of the higher eigenvalues are found by simple formulas based on the steady state solution. Thus the whole eigenvalue spectrum can be studied in detail and certain properties of the spectrum that should appear also with other rate expressions are described.