Valentina Zubkova

The influence of the autohydrolysis temperature of sunflower stems (SSs) and sunflower inflorescence (SI) on the changes in the composition of the pyrolysis products of their hydrochars (HCs) was investigated. This research was carried out using a TG/FT-IR analytical device, the semi-quantitative ATR technique, the quantitative XRD technique, and the SEM (EDS) technique. It was found that a rise in autohydrolysis temperature alarmingly increases the contribution of undesirable hydrocarbons in the volatile pyrolysis products of HCs calculated with respect to the emitted CO₂ and substantially decreases the yield of pyrolyzed solid products. The rise in autohydrolysis temperature not only changes the content of inorganics in HCs but also influences the migration of inorganics in these samples during pyrolysis: intensifies the migration of Mg and Ca and reduces the migration of K. This affects the secondary reaction between the volatile pyrolysis products. The addition of 2 wt% of paracetamol to pyrolyzed HCs inhibits the migration of Mg and Ca and increases the migration of K with volatile products, which positively influences the reduction in undesirable compounds in the composition of emitted volatile products. The addition of paracetamol decreases the yield of pyrolyzed SSHCs by circa 2% and increases the yield of pyrolyzed SIHC₁₈₀ by almost 5%.

The influence of 2 wt.% additives of expired paracetamol and naproxen on the thermal behaviour of densified samples of pea husks (PH), corncobs (CC), and sunflower inflorescences (SI) was studied using an analytical TG/FTIR unit. Gaseous, liquid, and solid pyrolysis products were evaluated using XRD, SEM, and EDX techniques along with FT-IR, ATR, and UV spectroscopies. It was found that the additives changed the yield and composition of pyrolysis products differently. The addition of paracetamol increases the contribution of guaiacyl rings in the condensed material of all samples, and the addition of naproxen—that of chromophores originating from the decomposition of lignin. The additives diversely affected the contribution of hydrocarbons in the composition of volatile products of pyrolysis: they decreased this contribution in PH samples, increased it in SI samples, and did not change in CC samples. The additives used changed the morphology and composition of organic and inorganic parts of pyrolyzed biomass. These changes in inorganics caused the changes in the composition of pyrolysis products. The conducted research proves not only the possibility of the utilization of expired pharmaceuticals during their pyrolysis with densified PH and CC samples but also the ability to reduce the undesirable hydrocarbons in the obtained volatile products.

The course of pyrolysis of pea husks was studied. It was stated that the compaction of a sample during its pyrolysis causes an almost two-fold increase in the content of hydrocarbons in the composition of volatile products in the temperature range of 350–470 °C. Low density polyethylene (LDPE), novolac, and coal tar pitch (CTP) wastes were added to feedstocks in the amount of 2 wt% in order to decrease the contribution of saturated and unsaturated hydrocarbons along with oxygen-containing compounds in volatile products. The analysis of the obtained products of pyrolysis was conducted using the techniques of thermogravimetry/Fourier transform infrared spectroscopy (TG/FT-IR), attenuated total reflectance (ATR) and ultraviolet (UV)-spectroscopies, gas chromatography-mass spectrometry (GCMS), X-ray diffractions (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray analysis (EDX). It was determined that pitch took the first place in a series of effectiveness in decreasing the content of harmful compounds in pyrolysis products; novolac was the second. A temperature of 370 °C (CTP) lowers the contribution of compounds with carbonyl groups (by approx. 2.7 times) and the contribution of alcohols, phenols, and esters (by approx. 4.4 times). At a temperature of 465 °C, this additive reduces the contribution of saturated and unsaturated hydrocarbons in the composition of volatiles (by approx. 5.8 times) and at a temperature of 520 °C, a more substantial decrease is observed (by approx. 14.3 times). During the pyrolysis in the temperature range of 420–520 °C, LDPE actively emits its own products of decomposition in the form of aliphatic hydrocarbons that negatively affect the environment. The composition of condensed pyrolysis products changes under the influence of additives. In water condensates, the concentration of determined phenols and anhydrosugars increases slightly under the influence of additives. The SEM and XRD investigations proved that inorganics interact with volatile pyrolysis products from the blends of pea husks with additives and change their composition. After the transformation of chemical composition, inorganics catalyse secondary reactions that take place in the pyrolysis products of blends.

This paper presents a review of the recent advances in research on the interactions between the components of lignocellulosic biomass. The literature reports on the effects of interaction between lignocellulosic biomass components, such as cellulose–lignin, lignin–hemicellulose, and hemicellulose–cellulose, were discussed. The results obtained by other researchers were analyzed from the viewpoint of the interactions between the pyrolysis products formed along with the impact effects of the organic and inorganic components present or added to the biomass with regard to the yield and composition of the pyrolysis products. Disagreements about some statements were noted along with the lack of an unequivocal opinion about the directivity of interactions occurring during biomass pyrolysis. Based on the data in the scientific literature, it was suggested that the course of the pyrolysis process of biomass blends can be appropriately directed by changes in the ratio of basic biomass components or by additions of inorganic or organic substances.

TG/FT-IR techniques, UV-spectroscopy, microwave extraction, XRD and SEM were used to study how densification of the three types of agricultural biomass wastes (wheat straw, soft wood, and sunflower husk) changes the composition and structure of their pyrolysis products. It was determined that densification changes the composition of volatile products of pyrolysis at the temperature of 420 °C: sunflower husk emits 4.9 times less saturated and unsaturated hydrocarbons and 1.9 times less compounds with carbonyl group; soft wood emits 1.8 times more saturated and unsaturated hydrocarbons and compounds with carbonyl groups and 1.3 times more alcohols and phenols; and wheat straw emits 2 times more compounds with carbonyl groups. These changes are probably caused by the differences in interaction of formed volatiles with the surface of chars. These differences can be caused by distinct places of cumulation of inorganic components in the densified samples. In the densified char, the inorganics cumulate on the surface of sunflower husk whereas for wheat straw they cumulate inside the sample. In the case of soft wood, the inorganics cumulate both inside and on the surface. The decreased contribution of hydrocarbons in volatiles can be connected with the morphology of nano-particles formed in inorganics.

A research study was conducted on the thermal behaviour of leaves of urban greenery (birch, maple, and rowan) and the products of their pyrolysis and extraction as assisted by microwaves. The obtained products of pyrolysis and extraction were investigated with the use of FT-IR and UV spectroscopies and XRD techniques. A contractive analysis of samples of chars, condensates, after-extraction residue, and extracts showed that the changes in structural-chemical parameters of leaves of different types of trees during pyrolysis and extraction take place in distinct ways. About 22% of material was removed from birch leaves during extraction, and more than 17% of material was extracted from maple and rowan leaves. It was determined that, during pyrolysis of after-extraction residue of leaves, many fewer PAH compounds with carbonyl groups along with alcohols and phenols are emitted than during pyrolysis of non-extracted leaves. Taking into account that pyrolysis is the first stage of combustion, a decrease in the amount of dangerous compounds in the volatile products of pyrolysis leads to a lower contribution of such compounds in combustion products. This indicates that leaves of urban greenery can be subjected to combustion after extraction, and the obtained extracts can be used as a source of phytochemicals and chemical reagents.

The course of thermal behavior of a fresh bituminous high-volatile coal during carbonization and pyrolysis was compared to that of this coal thawed after storage. The research was carried out using the following techniques: X-raying, thermogravimetry/Fourier transform-infrared spectroscopy (TG/FT-IR), extraction, Diffuse Reflectance Infrared Fourier Transform Spectroscopes (DRIFT), Attenuated Total Reflectance (ATR), and SEM. The increase in range of the viscous-liquid state and a decrease in temperature of its appearance were stated along with the formation of a more compact residue at the re-solidification stagtablee for the thawed coal during its carbonization. There is a fourfold reduction in the charge volume. The leakage of bitumen that contains 87 At % of C atoms from swollen grains and a fourfold increase in the yield of the material extracted from these grains are the proof of a greater plasticization of thawed coal. During the pyrolysis of thawed coal, the yield in volatile products of pyrolysis increases, and the composition of these products changes. The contribution ratio of saturated and unsaturated hydrocarbons, CO₂, alcohols, and phenols decreases in the composition of volatile products of thawed coal. It is suggested that the use of freezing during the storage of a freshly mined coal that has a poorer caking ability can improve its plasticization during carbonization.