The mining industry of Poland is based mostly on coal and copper ores. Strict carbon emissions and the depletion of deposits will slowly phase out coal. Therefore, metallic ores and other mineral raw materials will dominate the extractive industry of Poland. Current measured resources of the largest deposits of halloysite and diatomaceous earth in Poland are over 0.5 Mt and 10 Mt, respectively. Halloysite and diatomaceous earth samples from halloysite Dunino deposits and Jawornik diatomaceous earth deposits (composed mostly of diatomaceous skeletons (frustules)) were subjected to mineralogical analysis, scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS) nanostructural, chemical, elemental, and mineral content analysis. Both these minerals have similar properties, i.e., sorption capacity and cation exchange capacity, and are used mostly for the same purposes, e.g., adsorbents, filler material, and filtration. Samples of Dunino halloysite consist of minerals such as halloysite, kaolinite, hematite, magnetite, quartz, magnesioferrite, rutile, ilmenite, geikielite, goyazite, gorceixite, and crandallite, with little impurities in the form of iron oxides. Occasionally, halloysite nanoplates (HNP) nanotubes (HNT) were found. Diatomaceous earth is composed mainly of silica-containing phases (quartz, opal) and clay minerals (illite and kaolinite). The frustules of diatoms are mostly centric (discoid) and have radius values of approximately 50–60 μm. Large resources of these minerals could be used in the future either for manufacturing composite materials or highly advanced adsorbents.

The article presents comparative characteristics of the pore structure and sorption properties of raw halloysite (R-HAL) and after calcination (C-HAL) at the temperature of 873 K. Structural parameters were determined by optical scanning and transmission electron microscopy methods as well as by mercury porosimetry (MIP, Hg) and low-pressure nitrogen adsorption (LPNA, N₂, 77 K). The surface area parameter (LPNA) of halloysite mesopores before calcination was 54–61 m²/g. Calcining caused the pore surface to develop to 70–73 m²/g. The porosity (MIP) of halloysite after calcination increased from 29% to 46%, while the surface area within macropores increased from 43 m²/g to 54 m²/g. The total pore volume within mesopores and macropores increased almost twice after calcination. The course of CH₄ and CO₂ sorption on the halloysite was examined and sorption isotherms (0–1.5 MPa, 313 K) were determined by gravimetric method. The values of equilibrium sorption capacities increased at higher pressures. The sorption capacity of CH₄ in R-HAL was 0.18 mmol/g, while in C-HAL 0.21 mmol/g. CO₂ sorption capacities were 0.54 mmol/g and 0.63 mmol/g, respectively. Halloysite had a very high rate of sorption equilibrium. The values of the effective diffusion coefficient for methane on the tested halloysite were higher than De > 4.2 × 10⁻⁷ cm²/s while for carbon dioxide De > 3.1 × 10⁻⁷ cm²/s.

This paper presents a new, innovative technological approach, in line with Circular Economy principles, to the effective management of sludge generated during municipal wastewater treatment processes and subsequently used for biogas production. This approach allows for optimal, functional, and controlled cascade-type biotechnological thermal conversion of carbon compounds present in sewage sludge, later in solid digestate residues (after biogas production), and finally in the ash structure (after incineration, purposefully dosed nanostructural additives make the production of a useful solid product possible, especially for cyclic adsorption and slow release of nutrients (N, P, K) in the soil). The idea is generally targeted at achieving an innovative conversion cycle under a Circular Economy framework. In particular, it is based on an energy carrier (methane biogas) and direct energy production. The functionalized combustion by-products can be advantageous in agriculture. The use of ashes with nanostructural additives (halloysite, kaolinite) from combustion of sewage sludge after the anaerobic fermentation as an adsorbent of selected nutrients important in agriculture (Na⁺, K⁺, NO₃⁻, SO₄²⁻, PO₄³⁻, Cl⁻) was verified at laboratory scale. The tests were carried out both for pure ash and for the ash derived from combustion with the purposeful addition of kaolinite or halloysite. The equilibrium conditions for nitrate, potassium, sodium, phosphate(V), sulphate(VI), and chloride ions from aqueous solutions with the use of the three adsorbent structures were determined. The obtained innovative results were interpreted theoretically with adsorption isotherm models (Langmuir, Freundlich, Temkin, Jovanović). The most spectacular and clearly favorable results related to the influence of nanostructural additives in the process of sludge combustion, and formation of sorption surfaces under high temperature conditions were identified in the case of sorption-based separation of phosphate(V) ions (an increase from 1.13% to 61.24% with the addition of kaolinite, and even up to 76.19% with addition of halloysite).