High efficiency synthesis of HKUST-1 under mild conditions with high BET surface area and CO2 uptake capacity

This study focuses on the development of a hydrothermal method for the rapid synthesis of good quality copper benzene-1,3,5-tricarboxylate (referred to as HKUST-1) with high yield under mild preparation conditions to address the issues associated with reported methods. Different synthesis conditions and activation methods were studied to understand their influence on the properties of HKUST-1. It was found that mixing the precursors at 50 °C for 3 h followed by activation via methanol refluxing led to the formation of a product with the highest BET specific surface area of 1615 m2/g and a high yield of 84.1%. The XRD and SEM data illustrated that the product was highly crystalline. The sample was also tested on its capacity in CO2 adsorption. The results showed strong correlation between surface area of the sample and its CO2 uptake at 1 bar and 27 °C. The HKUST-1 prepared in this study demonstrated a high CO2 uptake capacity of 4.2 mmol/g. It is therefore concluded that this novel and efficient method can be used in the rapid preparation of HKUST-1 with high surface area and CO2 uptake capacity

Synthesis of metal-organic framework structures as effective carbon dioxide sorbents

W niniejszym artykule przedstawiono wstępne doświadczenia z badań innowacyjnej grupy stałych materiałów porowatych - struktur metaloorganicznych (MOF), mogących znaleźć zastosowanie w adsorpcyjnym wychwycie i separacji ditlenku węgla. Przedstawiono syntezę kilku struktur: MOF-5, MOF-199, Zn-MOF-74, Mg-MOF-74, Ni2(BDC)2(Dabco), Zn2(BDC)2(Dabco) oraz Mg2(BDC)2(Dabco). Pierwsze dwa z nich zbudowane są z trójwymiarowego szkieletu sześciennych cząsteczek metaloorganicznych, kolejne dwa charakteryzują się dwuwymiarową strukturą, natomiast ostatnie trzy przypominają modyfikowane glinokrzemiany warstwowe. Zaprezentowano wyniki analiz stabilności termicznych otrzymanych próbek oraz wyznaczono metodą termograwimetryczną ich pojemności sorpcyjne względem CO2 w temperaturze 25°C w ciśnieniu atmosferycznym.In the presented article were shown preliminary experiences in building a research base in the subject of innovative porous materials - metal-organic framework structures (MOFs). These materials can be applicable in adsorptive capture and separation of carbon dioxide. These structures are hybrids of metals or metal building units and organic ligands as linkers. Within the article there were presented and conducted reconstructive procedures of synthesis of several MOFs. MOF-5 is composed of zinc acetate molecules connected with terephtalate ligands in cubic macroparticles which create a 3D porous structure. MOF-199 shows quite similar construction with exception of replacement of terephtalate linker by benzenetricarboxylate ligand. Zn-MOF-74 and Mg-MOF-74 present a 2D structure appearing as tunnels built by connecting metals with dihyroxytereftalate ligand. Last synthesized group of MOFs is Me2(BDC)2Dabco, where Me is Ni, Zn or Mg. Structure of these materials is similar to pillared clays (such as bentonites), with layers constructed by metals and terephtalic acid ligands which are pillared by molecules of diazabicyclooctane. Within the article were presented results of thermal stability of synthesized samples, in order to determine its suitability to the technological processes. The most important part of this paper is determination of adsorption capacities of synthesized samples relative to the carbon dioxide as an adsorbate in temperature of 25°C and at atmospheric pressure

Technologie CCU w zielonej gospodarce

The paper presents the development of CCU (Carbon Capture and Utilization) technology and its significance in the green economy. The focus was on CO2 utilization technologies with high potential for commercial application. Carbon dioxide captured from coal-fired power plants, cement plants or in other industry sectors offers an alternative source of coal for obtaining fuels, chemicals and materials. The focus of the paper is on the technological, environmental and financial barriers to the implementation of CCU technologies on an industrial scale.W artykule przedstawiono rozwój technologii CCU (Carbon Capture and Utilization), a zarazem jej znaczenie w zielonej gospodarce. Skupiono się na technologiach utylizacji CO2 o dużym potencjale i możliwościach ich komercyjnego wykorzystania. Ditlenek węgla wychwycony z elektrowni węglowych, cementowni czy innych gałęzi przemysłu może stanowić alternatywne źródło węgla do pozyskiwania paliw, chemikaliów i materiałów. W artykule zwrócono ponadto szczególną uwagę na techniczne, środowiskowe i finansowe bariery wdrażania technologii CCU na skalę przemysłową

Evaluation of adsorbents usability for carbon dioxide separation in vacuum systems - thermogravimetric tests

Badania z zastosowaniem metod termo grawimetrycznych (układ TG-Vacuum) prowadzono pod kątem sprawdzenia przydatności wytypowanych adsorbentów do procesu wychwytu dwutlenku węgla z gazów spalinowych metodą VSA. Testy przeprowadzono na zeolicie 5A, na zeolicie 13X oraz na węglu aktywnym z łupin orzecha kokosowego w atmosferze dwutlenku węgla oraz w atmosferze spalin pochodzących z konwencjonalnego procesu spalania, tzn. 16% CO2, 3,5% O2,80,5% N2. Zakres badań obejmował: test stabilności termicznej adsorbentów, izotermiczny test adsorpcji, test programowanej temperaturowo adsorpcji oraz test wieloetapowej cyklicznej adsorpcji/desorpcji w układzie TG-Vacuum. Wybór odpowiedniego adsorbentu do stosowania w adsorpcyjnej instalacji separacji CO2 dokonywany jest na podstawie oceny jego pojemności sorpcyjnej, zdolności regeneracji, profili i kinetyki adsorpcji/desorpcji oraz stabilności termicznej. Wstępna ocena tych parametrów może zostać dokonana z wykorzystaniem metod termograwimetrycznych, będących szybkim i użytecznym narzędziem do określenia szczególnie pojemności sorpcyjnej oraz profili adsorpcji/desorpcji. Dla 100% CO2 największą pojemność sorpcyjną wynoszącą 130 mgCO2/g sorbentu stwierdzono dla zeolitu komercyjnego 13X, zaś najmniejszą dla węgla aktywnego AC - ok. 58 mgCO2/g sorbentu. W przypadku zastosowania mieszaniny gazowej o zawartości 16% CO2 stwierdzono niższe pojemności sorpcyjne w każdym z testowanych sorbentów. Pojemność sorpcyjna węgla aktywnego, podobnie jak zeolitów, obniża się gwałtownie wraz ze wzrostem temperatury.The paper presents the results of tests carried outusing a thermogravimetric analyzer (TG-Vacuum system) to verify the suitability of selected adsorbents for carbon dioxide capture from flue gases in VSA process. Sorption capacity of solid sorbents of carbon dioxide was characterized in relation to the CO2 concentration. Zeolite 5A, zeolite 13X and coconut shell steam activated carbon were used in the study underconditions typical of flue gas content in the combustion process, i.e. 16% CO2, 3.5% O2,80.5% N2. The scope of the research included a thermal stability test of adsorbents, isothermal test of adsoption and multi-stage cyclic adsorption/desorption (TG-Vacuum system) test. Selection of a suitable adsorbent to be used in adsorption installation is made based on evaluation of its sorption capacity, ability to regenerate, adsorption/desorption profiles and stability in the number of cycles and the kinetics of adsorption/desorption process. Zeolite 13X exhibited the highest sorption capacity of 130 mg CO2/g sorbent (among the adsorbents tested) when the adsorption step was carried out in pure CO2. In the case of gas mixture containing 16% of CO2 a significant decrease in sorption capacity was observed for each sorbent. Similar by to zeolites, sorption capacity of the activated carbon decreases rapidly as the temperature rises

Bio-Waste as a Substitute for the Production of Carbon Dioxide Adsorbents: A Review

Bioadsorbent, obtained as a result of the processing of bio-waste, has recently gained popularity as a material that adsorbs greenhouse gases, mainly carbon dioxide. Bio-waste, mainly residues from food industry operations, is a waste to be landfilled or composted and can be a potential substrate for bioadsorbent production. Bioadsorbents used for carbon capture must, above all, have low production costs and high adsorption efficiency. This review covers popular bioadsorbents that have been tested for their ability to adsorb carbon dioxide. The paper compares bioadsorbent production methods, physicochemical properties, adsorption isotherms, surfaces, and their porosity. There is a lack of data in the literature on the topic of carbon dioxide adsorption on large-scale plants in the target environment. Therefore, further research needs to fill in the gaps to identify the promised potential of these bioadsorbents

Co2 separation research on selected sorbents by pressure swing adsorption method

Przedstawiono rezultaty badań nad zastosowaniem wybranych sorbentów komercyjnych i syntezowanych z popiołów lotnych w adsorpcyjnej metodzie separacji dwutlenku węgla z gazów pochodzących ze spalania węgla w atmosferze wzbogaconej tlenem, jako jednej z metod wychwytywania CO2 po procesie spalania. Jako gaz surowy zastosowano symulowaną mieszaninę gazów spalinowych zawierających CO2, N2, O2, która podlegała rozdziałowi w dwukolumnowej instalacji adsorpcji zmiennociśnieniowej PSA. Proces prowadzono przy różnym ciśnieniu i przepływach gazu zasilającego oraz różnych udziałach strumienia gazu płuczącego. Dla wybranej konfiguracji procesu przedstawiono wyniki w postaci średniego stężenia dwutlenku węgla w produkcie niskociśnieniowym i odzysku CO2 z gazu surowego.The paper presents the research results of applying selected commercial sorbents and synthesized from fly ash ones in adsorption method applying for carbon dioxide separation from flue gases emitted during coal burning, in oxygen-enriched atmosphere, as the one of the post-combustion CO2 capture methods. The feed gas is a simulated flue gas mixture containing: CO2, N2, O2 separated in two-bed pressure swing adsorption (PSA) installation. The process was carried out under different pressures and velocity of feed gas as well as different purge ratios. The results of average concentration of CO2 in low- pressure product and average recovery of CO2 from feed gas were presented for specific configuration of conducted process

Parametric Study towards Optimization of a Short Duration Carbonation Process of Recycled Cement Paste

The recycling process of concrete originates a byproduct, cement paste powder (CPP), which is a material composed mainly of hydrated cement. This cementitious material has demonstrated promising results when applied as a binder in new concrete batches, provided it has been subjected to a previous carbonation process. One of the obstacles to the industrial application of this strategy is the long duration of the typical carbonation process, which requires from 3 to 28 days. Recently, the authors have developed a short two-hour carbonation process and thoroughly analysed it over its entire extension. In this paper, a parametric analysis of the carbonation process is performed towards CO2 uptake maximization, aiming to increase the feasibility of its short duration. CO2 uptake is evaluated using the ignition by furnace method and thermogravimetric analysis. Among the parameters considered, the initial water content and the CPP thickness present the highest impact on CO2 uptake. The investigation of different CO2 concentrations inside the carbonation chamber showed that the maximum CO2 uptake does not occur for the highest concentration value. Moreover, a minimum resident time for the forced carbonation of CPP in industrial contexts is presented, and is found to be highly dependent on the CO2 concentration. The particle size and purity degree of CPP revealed a limited influence on the CO2 uptake achieved. Additionally, this paper provides further insight into the mechanisms involved in the carbonation of mature cement paste while increasing the feasibility of our recently proposed short duration carbonation process