Clinoptilolite is a precious zeolite mineral that has the most comprehensive physicochemical properties among all the zeolite group minerals. Due to these unique properties, clinoptilolite has a wide range of applications in many different industries. In Poland, the clinoptilolite occurs only as an accompanying mineral in the sedimentary rocks nearby Rzeszów. In Europe, the abundant clinoptilolite-bearing deposits are located in Slovakia and Ukraine, where clinoptilolite mineralization occurs in the volcanic tuffs. Due to clinoptilolite’s rare performance, it is extremely crucial to manage its deposits in a complementary manner. In this paper, the mineralogical and structural characterization of the clinoptilolite powders obtained by mineral processing of the clinoptilolite-rich tuffs from Slovakia and Ukraine deposits were discussed. The scope of research covered determination of the mineral composition of the tuffs, structural analysis of the clinoptilolite crystals, as well as textural and physical properties of the powders obtained by mineral processing of the tuffs. In addition, this paper includes the comparative study of the most significant zeolite deposits in the world and investigated clinoptilolite-rich tuffs. A wide spectrum of methods was used: X-ray powder diffraction (XRD), thermal analysis (DSC, TG), X-ray fluorescence (XRF), optical microscopy, Scanning Electron Microscopy (SEM-EDS), the laser diffraction technique, and low-temperature nitrogen adsorption/desorption. The test results indicated that the major component of the tuffs is clinoptilolite, which crystallized in the form of very fine-crystalline thin plates. The clinoptilolite mineralization in the Ukrainian and Slovakian tuffs exhibited a strong resemblance to the clinoptilolite crystals in Yemeni and Turkish tuffs. With respect to the mineral composition, the investigated tuffs showed excellent conformity with the Miocene white tuffs from Romania. The Ukrainian and Slovakian tuffs do not reveal the presence of the clay minerals, which is quite common for naturally occurring zeolite-rich rocks in various deposits in the world. The textural features together with mineral composition of the investigated samples incline that they are potentially suitable raw materials for the sorbent of petroleum compounds. Moreover, the obtained results can be useful indicators with respect to the crushing and compaction susceptibility of the Ukrainian and Slovakian clinoptilolite-rich tuffs.

Increasing incidents of oil spills and dynamic development of civilization are driving the demand for sorbents. The production of the overwhelming majority of mineral sorbents involves the highly energy-consuming calcination process with CO2 emissions impacting the environment. Taking into account the environmental issues related to greenhouse gas emissions, we are in urgent need of green products and green technologies. The aim of this study was to investigate the possibility of using natural zeolite dust waste to produce oil sorbents in non-calcination technology. The main advantage of the proposed solution is reduction of greenhouse gas emissions and transformation of the waste material into green, useful product. The scope of the research covered the experimental tests for compaction of the zeolite material from Ukraine and Slovakia in a roller press with different type of binding agent and the performance tests for assessing the suitability of the produced agglomerates as a petroleum sorbent. In order to evaluate the agglomerates’ properties, textural-structural analysis (optical microscopy, SEM microscopy, and low-temperature N2 sorption), petroleum sorption (Westinghouse method), and physical-mechanical tests (resistance to gravitational drop, abrasion resistance) were carried out. Properties of the manufactured agglomerates were studied in comparison to commercial sorbent DAMSORB, commonly used in Poland. The test results showed that it is doable to produce the effective surface oil-spill sorbent from zeolite waste dust in a roller press by applying the relevant binding agent. The main finding of this study was that optimum feed composition for dry granulation that provides the granular sorbent with the best properties was established: 6% of C binder and moisture content within a narrow range of 20–20.6%. The C-1 sorbent achieved the highest and closely comparable to commercial sorbent parameters of petroleum sorption and drop strength, which are key points of this study. The absorption efficiency of petroleum substances for C-1 sorbent is 8% lower than that of a commercial sorbent, and resistance to gravitational drop is lower by only 3%. However, commercial sorbent exhibited better abrasion resistance compared to produced agglomerates, which is a compelling reason to continue the research in order to enhance the abrasion performance of the manufactured granules. The effectiveness of the dust consolidation method carried out was proved by textural parameters of the obtained zeolite-based sorbents. Specific surface area (SBET) of B-2 (SBET = 28.1 m2/g) and C-2 (SBET = 28.3 m2/g) sorbents was very similar to the commercial sorbent (SBET = 28.1 m2/g). Interestingly, all granules produced from clinoptilolite dust from Slovakia (A-2, B-2, C-2) achieved an increase of 19%, 33%, and 35%, respectively, in volume of mesopores, compared to the commercial sorbent. Moreover, the presented granulation technology favorably affected the size of the specific surface area as well as volume and surface area of mesopores in the case of obtained zeolite-based sorbent A-1 and B-1, compared with the starting raw material. Zeolite-based sorbent A-1 and B-1 achieved an increase of 17% and 18%, respectively, in specific area surface and an increase of 35% and 12%, respectively, in mesopores volume, compared with the raw material. Finally, the results of this investigation proved that it is possible to produce the efficient oil sorbent in a much more eco-friendly and green way, compared with that of the commercial sorbent.

There is a large accumulation of gravel-sand aggregates of glacial origin in the north-eastern part of Poland. Crushed aggregates produced by crushing pebbles have particularly good quality parameters. So far the aggregates have not been precisely identified in terms of the alkali-aggregate reaction. The first step in evaluating the reactivity of aggregates is to carry out a detailed petrographic evaluation on the basis of which the reactive forms of silica can be identified. The paper presents selected results of tests carried out on the glacial crushed aggregates and a petrographic characterization of the latter, with special attention paid to the presence of the minerals which can react with sodium and potassium hydroxides.