Porosity in ion-exchanged and acid activated clays evaluated using n-nonane pre-adsorption

The applicability of the n-nonane pre-adsorption method for characterising the porosity in clays is presented. Na-SD, a Na+-exchanged purified bentonite, and materials obtained by Al3+-exchange and acid treatments of Na-SD and SAz-1 were used. Nitrogen adsorption isotherms, at -196 ºC, were determined before and after n-nonane pre-adsorption on each of the samples. In all materials, n-nonane remained adsorbed in ultramicropores after outgassing at 25 ºC. Outgassing at higher temperatures (50, 75 and 200 ºC) removed nonane and ultramicropores became available for nitrogen adsorption. All treatments on Na-SD led to increase in micropore volume. Larger ultramicropore and supermicropore volumes were obtained for Na-SD acid activated with HCl at 95 ºC than for treatments at 25 ºC with HCl or following Al3+-exchange (Al-SD), and increased with increasing acid concentration to 3 M. Activation with 4 M HCl led to the largest pore volume with contribution from mesopores. However, the specific external surface area was the same as that obtained for Na-SD, Al-SD and for most of the other acid activated samples. Treatments at 95 ºC with 1 M and 6 M HCl promoted increase in specific external surface area. The micropore volumes and specific external surface area for SAz-1 treated with 1 M HCl at 95 ºC were larger than those of Al-SAz-1, but lower than those obtained for corresponding materials derived from Na-SD. The n-nonane pre-adsorption method enabled micropore volumes and specific external surface areas to be obtained for all samples.

Síntese de pigmentos cerâmicos inorgânicos nanométricos e encapsulados com estrutura core-shell pela rota dos precursores poliméricos

The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet

Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

Novel synthesis of a micro-mesoporous nitrogen-doped nanostructured carbon from polyaniline

Nanostructured carbons with relatively high nitrogen content (3–8%) and different micro and mesoporosity ratio were prepared by activation of polyaniline (PANI) with a ZnCl2–NaCl mixture in the proportion of the eutectic (melting point 270 °C). It was found that the activated carbons consisted of agglomerated nanoparticles. ZnCl2 plays a key role in the development of microporosity and promotes the binding between PANI nanoparticles during heat treatment, whereas NaCl acts as a template for the development of mesoporosity of larger size. Carbons with high micropore and mesopore volumes, above 0.6 and 0.8 cm3/g, respectively, have been obtained. Furthermore, these materials have been tested for CO2 capture and storage at pressures up to 4 MPa. The results indicate that the nitrogen groups present in the surface do not seem to affect to the amount of CO2 adsorbed, not detecting strong interactions between CO2 molecules and nitrogen functional groups of the carbon, which are mainly pyridinic and pyrrolic groups.

Post-combustion CO2 adsorption on activated carbons with different textural properties

Fixed bed CO2 adsorption tests were carried out in model flue-gas streams onto two commercial activated carbons, namely Filtrasorb 400 and Nuchar RGC30, at 303 K, 323 K and 353 K. Thermodynamic adsorption results highlighted that the presence of a narrower micropore size distribution with a prevailing contribution of very small pore diameters, observed for Filtrasorb 400, is a key factor in determining a higher CO2 capture capacity, mostly at low temperature. These experimental evidences were also corroborated by the higher value of the isosteric heat derived for Filtrasorb 400, testifying stronger interactions with CO2 molecules with respect to Nuchar RGC30. Dynamic adsorption results on the investigated sorbents highlighted the important role played by both a greater contribution of mesopores and the presence of wider micropores for Nuchar RGC30 in establishing faster capture kinetics with respect to Filtrasorb 400, in particular at 303 K. Furthermore, the modeling analysis of 15% CO2 breakthrough curves allowed identifying intraparticle diffusion as the rate-determining step of the process.

A new synthesis route for bone chars using CO2 atmosphere and their application as fluoride adsorbents

This study describes a new synthesis route for bone chars using a CO2 atmosphere and their behavior as adsorbent for fluoride removal from water. Specifically, we have performed a detailed analysis of the adsorption properties of bone char samples obtained at different carbonization conditions and a comparative study with samples of bone char obtained via pyrolysis under nitrogen. Experimental results show that the nature of the gas atmosphere (CO2 versus N2) and the carbonization temperature play a major role to achieve an effective bone char for water defluoridation. In particular, the best adsorption properties of bone char for fluoride removal are obtained with those samples synthesized at 700 °C. Carbonization temperatures above 700 °C under CO2 atmosphere cause the dehydroxylation of the hydroxyapatite in the bone char, thus reducing its fluoride adsorption capacity. The maximum fluoride adsorption capacity for the bone char obtained in this study under CO2 atmosphere (i.e., 5.92 mg/g) is higher than those reported for commercial bone chars.

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Engineered zeolitic materials: synthesis and application

Les zéolithes étant des matériaux cristallins microporeux ont démontré leurs potentiels et leur polyvalence dans un nombre très important d’applications. Les propriétés uniques des zéolithes ont poussé les chercheurs à leur trouver constamment de nouvelles utilités pour tirer le meilleur parti de ces matériaux extraordinaires. Modifier les caractéristiques des zéolithes classiques ou les combiner en synergie avec d’autres matériaux se trouvent être deux approches viables pour trouver encore de nouvelles applications. Dans ce travail de doctorat, ces deux approches ont été utilisées séparément, premièrement avec la modification morphologique de la ZSM-12 et deuxièmement lors de la formation des matériaux de type coeur/coquille (silice mésoporeuses@silicalite-1). La ZSM-12 est une zéolithe à haute teneur en silice qui a récemment attiré beaucoup l’attention par ses performances supérieures dans les domaines de l’adsorption et de la catalyse. Afin de synthétiser la ZSM-12 avec une pureté élevée et une morphologie contrôlée, la cristallisation de la zéolithe ZSM-12 a été étudiée en détail en fonction des différents réactifs chimiques disponibles (agent directeur de structure, types de silicium et source d’aluminium) et des paramètres réactionnels (l’alcalinité, ratio entre Na, Al et eau). Les résultats présentés dans cette étude ont montré que, contrairement à l’utilisation du structurant organique TEAOH, en utilisant un autre structurant, le MTEAOH, ainsi que le Al(o-i-Pr)3, cela a permis la formation de monocristaux ZSM-12 monodisperses dans un temps plus court. L’alcalinité et la teneur en Na jouent également des rôles déterminants lors de ces synthèses. Les structures de types coeur/coquille avec une zéolithe polycristalline silicalite-1 en tant que coquille, entourant un coeur formé par une microsphère de silice mésoporeuse (tailles de particules de 1,5, 3 et 20-45 μm) ont été synthétisés soit sous forme pure ou chargée avec des espèces hôtes métalliques. Des techniques de nucléations de la zéolithe sur le noyau ont été utilisées pour faire croitre la coquille de façon fiable et arriver à former ces matériaux. C’est la qualité des produits finaux en termes de connectivité des réseaux poreux et d’intégrité de la coquille, qui permet d’obtenir une stéréosélectivité. Ceci a été étudié en faisant varier les paramètres de synthèse, par exemple, lors de prétraitements qui comprennent ; la modification de surface, la nucléation, la calcination et le nombre d’étapes secondaires de cristallisation hydrothermale. En fonction de la taille du noyau mésoporeux et des espèces hôtes incorporées, l’efficacité de la nucléation se révèle être influencée par la technique de modification de surface choisie. En effet, les microsphères de silice mésoporeuses contenant des espèces métalliques nécessitent un traitement supplémentaire de fonctionnalisation chimique sur leur surface externe avec des précurseurs tels que le (3-aminopropyl) triéthoxysilane (APTES), plutôt que d’utiliser une modification de surface avec des polymères ioniques. Nous avons également montré que, selon la taille du noyau, de deux à quatre traitements hydrothermaux rapides sont nécessaires pour envelopper totalement le noyau sans aucune agrégation et sans dissoudre le noyau. De tels matériaux avec une enveloppe de tamis moléculaire cristallin peuvent être utilisés dans une grande variété d’applications, en particulier pour de l’adsorption et de la catalyse stéréo-sélective. Ce type de matériaux a été étudié lors d’une série d’expériences sur l’adsorption sélective du glycérol provenant de biodiesel brut avec des compositions différentes et à des températures différentes. Les résultats obtenus ont été comparés à ceux utilisant des adsorbants classiques comme par exemple du gel de sphères de silice mésoporeux, des zéolithes classiques, silicalite-1, Si-BEA et ZSM-5(H+), sous forment de cristaux, ainsi que le mélange physique de ces matériaux références, à savoir un mélange silicalite-1 et le gel de silice sphères. Bien que le gel de sphères de silice mésoporeux ait montré une capacité d’adsorption de glycérol un peu plus élevée, l’étude a révélé que les adsorbants mésoporeux ont tendance à piéger une quantité importante de molécules plus volumineuses, telles que les « fatty acid methyl ester » (FAME), dans leur vaste réseau de pores. Cependant, dans l’adsorbant à porosité hiérarchisée, la fine couche de zéolite silicalite-1 microporeuse joue un rôle de membrane empêchant la diffusion des molécules de FAME dans les mésopores composant le noyau/coeur de l’adsorbant composite, tandis que le volume des mésopores du noyau permet l’adsorption du glycérol sous forme de multicouches. Finalement, cette caractéristique du matériau coeur/coquille a sensiblement amélioré les performances en termes de rendement de purification et de capacité d’adsorption, par rapport à d’autres adsorbants classiques, y compris le gel de silice mésoporeuse et les zéolithes.

Activated carbons with high nitrogen content by a combination of hydrothermal carbonization with activation

This paper reports the production of carbons materials with a nitrogen content around 8%(w/w) and a well-developed porous structure, with BET surface area and pore volume up to 2130 m2 g−1 and 1.12 cm3 g−1, respectively, produced by a combination of hydrothermal carbonization, an environmental friendly method in the production of sustainable tunable carbon materials, with traditional activation methods. The porosity was developed through an activation process according to different routes, namely activation with CO2 and chemical activation using CaCO3 and K2CO3. The successful production of activated carbons using chitosan as a nitrogen source revealed to be a good alternative to post-synthesis methods.

Adsorption of pesticides onto activated carbons from wood composites

A series of activated carbon was produced from particleboard and medium-density fibreboard monoliths, which are waste originated from the industry, and then characterized and evaluated for potential application for phenoxyacetic acids removals, such 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxy acetic acid (MCPA) and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), from the liquid phase. All AC retain the shape of the precursor, and displays a microporous structure well-developed, reaching 0.58 cm 3 g -1. The adsorption isotherms for three pesticides were obtained in the optimal conditions and the AC with high superficial area and micropore volume exhibited better performance, allowing to state that, this AC could be a great substitute of those habitually used for this purpose. The pesticides adsorption data were linearized using the Langmuir and Freundlich equation, being the first a very good fit to the experimental data.

Adsorption of pesticides onto activated carbons from wood composites

A series of activated carbon was produced from particleboard and medium-density fibreboard monoliths, which are waste originated from the industry, and then characterized and evaluated for potential application for phenoxyacetic acids removals, such 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxy acetic acid (MCPA) and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), from the liquid phase. All AC retain the shape of the precursor, and displays a microporous structure well-developed, reaching 0.58 cm 3 g -1. The adsorption isotherms for three pesticides were obtained in the optimal conditions and the AC with high superficial area and micropore volume exhibited better performance, allowing to state that, this AC could be a great substitute of those habitually used for this purpose. The pesticides adsorption data were linearized using the Langmuir and Freundlich equation, being the first a very good fit to the experimental data.

Production of activated carbons from single and mixtures of synthetic polymers

The production of activated carbons (ACs) involves two main steps: the carbonization of the carbonaceous of raw materials at temperatures below 1073 K in the absence of oxygen and the activation had realized at the temperature up to 1173 but the most useful temperature at 1073 K. In our study we used the most common industrial and consumer solid waste, namely PET, alone or blended with other synthetic polymer PAN. By mixing the two polymers in different ratios, an improvement of the yield of the AC production was found and some textural properties were enhanced by comparison with the AC prepared using each polymer separately. When all the samples were exposed through the carbonization process with a pyrolysis the mixture of PAN-PET (1:1w/w) yield around 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The combine activation, with CO2 at 1073 K, allow ACs with a lower burn-off degree isothermally, when compared with those attained with PET or PAN alone, but with similarly chemicals or textural properties. The resultant ACs are microporous in their nature, as the activation time increase, the PET-PAN mixture AC are characterized by a better developed porous structure, when associated with the AC prepared from PAN. The AC prepared from PET-PAN mixture are characterized by basic surface characteristics, with a pHpzc around 10.5, which is an important characteristic for future applications on acidic pollutants removals from liquid or gaseous phase. In this study we had used the FTIR methods to determine the main functional groups in the surface of the activated carbons. The adsorbents prepared from PAN fibres presents an IR spectrum with similar characteristics to those obtained with PET wastes, but with fewer peaks and bands with less intensity, in particular for the PAN-8240 sample. This can be reflected by the stretching and deformation modes of NH bond in the range 3100 – 3300 cm-1 and 1520 – 1650 cm-1, respectively. Also, stretching mode associated to C–N, C=N, can contributed to the profile of IR spectrum around 1170 cm-1, 1585 – 1770 cm-1. And the TGA methods was used to study the loses of the precursors mass according to the excessive of the temperature. The results showed that, there were different decreasing of the mass of each precursors. PAN degradation started at almost 573 K and at 1073 K, PAN preserve more than 40% of the initial mass. PET degradation started at 650 K, but at 1073 K, it has lost 80% of the initial mass. However, the mixture of PET-PAN (1:1w/w) showed a thermogravimetric profile between the two polymers tested individually, with a final mass slightly less than 30%. From a chemical point of view, the carbonisation of PET mainly occurs in one step between 650 and 775 K.

Preparação, caracterização e modificação de adsorventes para remoção de pesticidas de águas

O objectivo principal deste trabalho de mestrado consistiu em avaliar a potencial utilização de materiais adsorventes, nomeadamente, de carvões activados (AC) preparados por activação química com KOH, a partir de PET reciclado, e de materiais com estrutura mesoporosa ordenada, do tipo MCM-41 e SBA-15, na remoção de ácido 4 - cloro - 2 - metilfenoxiacético (MCPA) e de azul de metileno (MB), presentes nas águas. Nesta tese apresentam-se estudos de preparação e caracterização de materiais micro e mesoporosos e também estudos de avaliação da capacidade adsortiva em fase líquida. Prepararam-se três materiais microporosos, nomeadamente, PET-2-700, PET-2-700ox (AC oxidado) e PET-2-700red (AC reduzido), dois materiais constituídos exclusivamente por mesoporos, Si-MCM-41 e Ti-MCM-41-50 e dois materiais contendo maioritariamente mesoporos, mas que também possuem alguma microporosidade, tais corno, Si-SBA-15 e Ti-SBA-15-50. A caracterização textural dos adsorventes foi inferida por adsorção de azoto a 77K e por de difracção de raios X. Recorreu-se a três métodos de análise das isotérmicas, nomeadamente, Dubinin-Radushkevich, Brunauer-Ernrnett-Teller e alfa-s (as). A caracterização química dos AC foi realizada recorrendo-se a técnicas de análise elementar (AE) e espectroscopia de infravermelho com transformadas de Fourier (FTIR) e à determinação do ponto de carga zero. Os três carvões activados possuem valores de área superficial externa idênticos, o PET-2-700 possui o maior volume microporoso e o PET-2-700ox exibe o maior diâmetro de poros. Por outro lado, o PET-2-700ox possui um carácter fortemente ácido, o PET-2-700 exibe carácter ligeiramente ácido e o PET-2-700red apresenta propriedades ligeiramente alcalinas. Com base na AE, todas as amostras possuem percentagens de carbono elevadas, sendo que o PET-2-700red apresenta o valor mais elevado. Os resultados obtidos para a caracterização estrutural dos revelaram a obtenção de materiais mesoporosos de alta qualidade, definida pela elevada regularidade e uniformidade da estrutura porosa. A análise dos parâmetros de caracterização textura! permitiu inferir que os quatro materiais mesoporosos possuem valores de área superficial elevados, e que os materiais SBA-15 apresentam valores de volume poroso total e de tamanho de poros superiores aos manifestados pelos MCM-41. A incorporação de titânio não conduziu a uma perda significativa de qualidade dos materiais substituídos em relação às correspondentes amostras de sílica. Efectuaram-se estudos de adsorção em fase líquida de forma a avaliar a possível aplicação dos vários adsorventes na remoção de MCPA e de MB de efluentes líquidos. concluiu-se que o tempo de equilíbrio de 72 horas seria adequado e que a capacidade de adsorção dos vários AC era superior em meio ácido. Com base nas isotérmicas de adsorção do MCPA e do MB e na aplicação da representação de Langmuir e de Freundlich, foi possível concluir que o PET-2-700 possui a maior capacidade de adsorção do MCPA, 1.42 mmol/g, enquanto que o PET-2-700ox revelou a maior capacidade de adsorção do MB, 1.43 mmol/g. Na realidade, os materiais microporosos estudados apresentaram percentagens de remoção elevadas, tanto do MCPA como do MB. Relativamente aos materiais mesoporosos ordenados preparados neste trabalho, a percentagem de remoção de para os poluentes em estudo foi relativamente baixa, constatando-se que nesta fase dos estudos não constituem uma alternativa viável à utilização dos AC. No entanto, uma funcionalização criteriosa dos mesmos pode eventualmente proporcionar um aumento da capacidade adsortiva. ABSTRACT: The work presented in this master thesis, consisted of evaluating the potential use of different adsorbents materials, like activated carbon (AC) prepared by chemical activation with KOH, from recycled poly (ethylene terephthalate) (PET) and materials with ordered mesoporous structure such as MCM-41 and SBA-15, for removing acid 4-chlorine-2-metilfenoxiacétic and methylene blue from aqueous phase. We had prepared three microporous materials, PET-200-700, PET-2-700ox (AC oxidized) and PET-2-700red (reduced AC), two materials consisting exclusively of mesopores, Si-MCM-41 and Ti-MCM-41-50 and two materials containing mainly mesopores, but also having some microporosity, such as Si-SBA-15 and Ti-SBA-15-50. The textural characterization of the adsorbents was inferred by nitrogen adsorption at 77K and X-ray diffraction. Three methods were used to analyse the isotherms, namely, Dubinin-Radushkevich, Brunauer-Emmett-Teller and alpha-s (as). The chemical characterization of AC was performed using the elementary analysis, Fourier transform infrared spectroscopy (FTIR) and determination of the point of zero charge. Concerning the AC, the three present almost the same externa! surface area, PET-2-700 has a high micropore volume and PET-2-700ox shows the largest pore size diameter. On the other hand, PET-2-700ox had a strong acid character, PET-2-700 exhibits just a slightly acid character and PET-2-700red presents alkaline properties. The AE analysis allows confirming the high carbon content of theses AC, with PET-2-700red exhibiting the highest carbon proportion. The results from the structural characterization of the mesoporous materials, had disclosed the attainment of materials with high quality, defined by the raised regularity and uniformity of the porous structure. The analysis of the textural parameters allowed inferring that the four studied mesoporous materials possess high superficial area. The SBA-15 type materials present higher values of total porous volume and pores size diameter as the MCM-41. Also, the titanium incorporation did not lead to a significant loss of quality of the materials substituted in relation to the corresponding silica samples. The adsorption studies in liquid phase allow evaluating the possibility of using the different adsorbents for the MCPA and the MB removal. The kinetic studies had allowed to state the equilibrium time as 72 hours and a higher adsorption capacity was achieved in an acid medium. The influence of the pH of the medium, on the MCPA adsorption was evaluated. The MCPA and MB isotherms were analysed based on the Langmuir and Freundlich equation, the representations presented an excellent linearity, indicating the applicability of these equations to these systems. Also, it allows concluded that PET-2-700 had a higher adsorption capacity for MCPA, 1.42 mmol/g, and PET-2-700ox had a higher adsorption capacity for MB, 1.43 mmol/g. The AC used presented high removal percentages for MCPA and MB. Concerning the mesoporous materials prepared in this work, the percentage removal for the pollutants in study was relatively low, and evidencing that at the moment these mesoporous materials do not constitute a viable alternative to the AC. However, an astute funcionalisation of the same ones can, eventually provide an increase of the adsorption capacity.