21 |
Kinetic and Deactivation Studies of Hydrodesulfurization CatalystsSteiner, Petr January 2002 (has links)
<p>Hydrodesulfurization is an important part of the hydrotreating process. More stringent regulations on the quality of fuels bring new requirements to the catalytic processes. The removal of sulfur has become a key issue in the oil refining and this work aims to address several aspects of the process.</p><p>Kinetic studies of the hydrodesulfurization reaction over conventional (molybdenum-based) and new (Pt/Y-zeolite) catalysts are reported. The hydrodesulfurization of both the real oil (light gas oil from Statoil Mongstad refinery) and model compounds (thiophene and dibenzothiophene) over a NiMo/γ-Al<sub>2</sub>O<sub>3</sub> catalyst were studied. In a high-pressure study of the light gas oil, substituted alkyl-DBTs were found to be the most difficult to desulfurize and the order of reactivity was found to be DBT > 4-MDBT > 4,6-DMDBT. Steric hindrance together with electronic effects were identified as possible reasons for this behavior. The difference in reactivities of the individual compounds was found to decrease with the increasing reaction temperature. A gas chromatograph equipped with the atomic emission detector (GC-AED) was used for the analysis of the individual components of the oil.</p><p>The initial deactivation and the steady-state kinetics were studied during the HDS of thiophene at atmospheric pressure. Unpromoted Mo/γ-Al<sub>2</sub>O<sub>3</sub>, CoMo/γ-Al<sub>2</sub>O<sub>3</sub>, NiMo/γ-Al<sub>2</sub>O<sub>3</sub>, and phosphorus modified NiMo/γ-Al<sub>2</sub>O<sub>3</sub> were used for the deactivation study, while NiMo/γ-Al<sub>2</sub>O<sub>3</sub>,CoMo/γ-Al<sub>2</sub>O<sub>3</sub>, and Pt/Y-zeolite (with three different pretreatments) were used for the steadystate study. Several experiments related to the deactivation of Mo/γ-Al<sub>2</sub>O<sub>3</sub> and NiMo/γ-Al<sub>2</sub>O<sub>3 </sub>catalysts prepared with the chelating agent (NTA) were also performed and NTA was found to have no significant effect on the activity of the catalysts.</p><p>In the deactivation study, a fast initial decrease in the activity was observed on all the catalysts. However, nickel promoted catalysts were found to be more resistant to deactivation than unpromoted ones. The presence of phosphorus slightly increased the activity of the catalyst towards the thiophene HDS, but had no effect on the deactivation behavior. Several methods to regenerate the catalyst were investigated. During the resulfiding experiments, a difference between Mo/γ-Al<sub>2</sub>O<sub>3</sub> and NiMo/γ-Al<sub>2</sub>O<sub>3</sub> was observed. Deactivation of the Mo catalyst was more severe with increasing temperature, while for the NiMo catalyst the opposite behavior was observed. Carbon deposition on catalysts followed the similar trend: More carbon was observed on the Mo catalyst at higher temperatures, while the opposite is true for NiMo. The restoration of the activity of NiMo was complete, while the reactivation of the Mo catalyst was only partial. The results from the reactivation experiments with pure H<sub>2</sub> and inert gas (helium) suggest that several mechanisms of the restoration of activity exist: Resulfiding of the desulfided active sites, hydrogenation and removal of the deposited carbonaceous species, and the desorption of the reactants and products from the active sites of the catalyst. Based on the observed results, the higher hydrogenation activity of nickel is assumed to be the reason for the behavior. Hydrogenation causes the faster removal of the deposited carbonaceous species and this leads to the conclusion that the desulfiding of the active sites and the adsorption of the reaction species is significantly less pronounced on the NiMo/γ-Al<sub>2</sub>O<sub>3 </sub>catalyst.</p><p>Characterization studies show differences between standard and NTA-based catalysts. The higher amount of carbon on the NTA catalysts is attributed to the presence of the carboncontaining precursor - NTA. The changes in the surface area and the pore volume were observed only during the sulfiding process. In the case of standard catalysts the surface area and the pore volume decreased, while for the NTA-based catalysts the opposite is true. No change in the surface area and the pore volume with the increasing time on stream indicates that the deactivation is not due to structural changes of the catalyst. The amount of sulfur was found to be constant during the time on stream for all the catalysts.</p><p>In the steady-state study of the HDS of thiophene, CoMo and NiMo catalysts were found to be equally active. The activity of the Pt/Y-zeolite catalyst was found to be comparable to conventional catalysts when based on the amount of active material, but a fast deactivation was observed. The product selectivities during the HDS of thiophene were found to be the same for all standard catalysts, but slightly different for the Pt/Y-zeolite catalyst. This was attributed to a higher hydrogenation activity of the Pt/Y-zeolite catalyst. </p><p>The inhibition effect of other sulfur compounds and aromatics on the high-pressure hydrodesulfurization of dibenzothiophene (DBT), the so-called “matrix effect” was studied. Thiophene and DMDS have the same inhibiting effect on the total conversion of DBT, but differences exist in the effect on the selectivities of the products at low concentrations. The results indicate that the inhibiting effect of H<sub>2</sub>S on the direct desulfurization route is stronger than the effect of thiophene on the hydrogenation pathway. In the study of aromatics, both toluene and naphthalene affect the total conversion of DBT. Naphthalene was found to be a much stronger inhibitor and inhibits mainly the direct desulfurization pathway, while the hydrogenation route is more affected by the presence of toluene.</p>
|
22 |
Kinetic and Deactivation Studies of Hydrodesulfurization CatalystsSteiner, Petr January 2002 (has links)
Hydrodesulfurization is an important part of the hydrotreating process. More stringent regulations on the quality of fuels bring new requirements to the catalytic processes. The removal of sulfur has become a key issue in the oil refining and this work aims to address several aspects of the process. Kinetic studies of the hydrodesulfurization reaction over conventional (molybdenum-based) and new (Pt/Y-zeolite) catalysts are reported. The hydrodesulfurization of both the real oil (light gas oil from Statoil Mongstad refinery) and model compounds (thiophene and dibenzothiophene) over a NiMo/γ-Al2O3 catalyst were studied. In a high-pressure study of the light gas oil, substituted alkyl-DBTs were found to be the most difficult to desulfurize and the order of reactivity was found to be DBT > 4-MDBT > 4,6-DMDBT. Steric hindrance together with electronic effects were identified as possible reasons for this behavior. The difference in reactivities of the individual compounds was found to decrease with the increasing reaction temperature. A gas chromatograph equipped with the atomic emission detector (GC-AED) was used for the analysis of the individual components of the oil. The initial deactivation and the steady-state kinetics were studied during the HDS of thiophene at atmospheric pressure. Unpromoted Mo/γ-Al2O3, CoMo/γ-Al2O3, NiMo/γ-Al2O3, and phosphorus modified NiMo/γ-Al2O3 were used for the deactivation study, while NiMo/γ-Al2O3,CoMo/γ-Al2O3, and Pt/Y-zeolite (with three different pretreatments) were used for the steadystate study. Several experiments related to the deactivation of Mo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts prepared with the chelating agent (NTA) were also performed and NTA was found to have no significant effect on the activity of the catalysts. In the deactivation study, a fast initial decrease in the activity was observed on all the catalysts. However, nickel promoted catalysts were found to be more resistant to deactivation than unpromoted ones. The presence of phosphorus slightly increased the activity of the catalyst towards the thiophene HDS, but had no effect on the deactivation behavior. Several methods to regenerate the catalyst were investigated. During the resulfiding experiments, a difference between Mo/γ-Al2O3 and NiMo/γ-Al2O3 was observed. Deactivation of the Mo catalyst was more severe with increasing temperature, while for the NiMo catalyst the opposite behavior was observed. Carbon deposition on catalysts followed the similar trend: More carbon was observed on the Mo catalyst at higher temperatures, while the opposite is true for NiMo. The restoration of the activity of NiMo was complete, while the reactivation of the Mo catalyst was only partial. The results from the reactivation experiments with pure H2 and inert gas (helium) suggest that several mechanisms of the restoration of activity exist: Resulfiding of the desulfided active sites, hydrogenation and removal of the deposited carbonaceous species, and the desorption of the reactants and products from the active sites of the catalyst. Based on the observed results, the higher hydrogenation activity of nickel is assumed to be the reason for the behavior. Hydrogenation causes the faster removal of the deposited carbonaceous species and this leads to the conclusion that the desulfiding of the active sites and the adsorption of the reaction species is significantly less pronounced on the NiMo/γ-Al2O3 catalyst. Characterization studies show differences between standard and NTA-based catalysts. The higher amount of carbon on the NTA catalysts is attributed to the presence of the carboncontaining precursor - NTA. The changes in the surface area and the pore volume were observed only during the sulfiding process. In the case of standard catalysts the surface area and the pore volume decreased, while for the NTA-based catalysts the opposite is true. No change in the surface area and the pore volume with the increasing time on stream indicates that the deactivation is not due to structural changes of the catalyst. The amount of sulfur was found to be constant during the time on stream for all the catalysts. In the steady-state study of the HDS of thiophene, CoMo and NiMo catalysts were found to be equally active. The activity of the Pt/Y-zeolite catalyst was found to be comparable to conventional catalysts when based on the amount of active material, but a fast deactivation was observed. The product selectivities during the HDS of thiophene were found to be the same for all standard catalysts, but slightly different for the Pt/Y-zeolite catalyst. This was attributed to a higher hydrogenation activity of the Pt/Y-zeolite catalyst. The inhibition effect of other sulfur compounds and aromatics on the high-pressure hydrodesulfurization of dibenzothiophene (DBT), the so-called “matrix effect” was studied. Thiophene and DMDS have the same inhibiting effect on the total conversion of DBT, but differences exist in the effect on the selectivities of the products at low concentrations. The results indicate that the inhibiting effect of H2S on the direct desulfurization route is stronger than the effect of thiophene on the hydrogenation pathway. In the study of aromatics, both toluene and naphthalene affect the total conversion of DBT. Naphthalene was found to be a much stronger inhibitor and inhibits mainly the direct desulfurization pathway, while the hydrogenation route is more affected by the presence of toluene.
|
23 |
Syntheses, characterization and kinetics of nickel-tungsten nitride catalysts for hydrotreating of gas oilBotchwey, Christian 21 July 2010
This thesis summarizes the methods and major findings of Ni-W(P)/ã-Al2O3 nitride cata-lyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts activities to their synthesis parameters and properties.<p>
The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, trans-mission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: tem-perature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydro-gen to oil ratio (600 ml/ml, STP).<p>
The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity in-creased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide.<p>
The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed active sites, catalyst particle size and BET surface area.<p>
HDS and HDN kinetic analyses, using Langmuir-Hinshelwood models, gave activation energies of 66 and 32 kJ/mol, respectively. There were no diffusion limitations in the reaction process. Two active sites were involved in HDS reaction while one site was used for HDN. HDS and HDN activities of the Ni-W(P)/ã-Al2O3 nitride catalysts were comparable to the corre-sponding sulfides.
|
24 |
Syntheses, characterization and kinetics of nickel-tungsten nitride catalysts for hydrotreating of gas oilBotchwey, Christian 21 July 2010 (has links)
This thesis summarizes the methods and major findings of Ni-W(P)/ã-Al2O3 nitride cata-lyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts activities to their synthesis parameters and properties.<p>
The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, trans-mission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: tem-perature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydro-gen to oil ratio (600 ml/ml, STP).<p>
The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity in-creased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide.<p>
The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed active sites, catalyst particle size and BET surface area.<p>
HDS and HDN kinetic analyses, using Langmuir-Hinshelwood models, gave activation energies of 66 and 32 kJ/mol, respectively. There were no diffusion limitations in the reaction process. Two active sites were involved in HDS reaction while one site was used for HDN. HDS and HDN activities of the Ni-W(P)/ã-Al2O3 nitride catalysts were comparable to the corre-sponding sulfides.
|
25 |
HdSC: modelagem de alto nível para simulação nativa de plataformas com suporte ao desenvolvimento de HdSPrado, Bruno Otávio Piedade 08 1900 (has links)
Com os grandes avanços recentes dos sistemas computacionais, houve
a possibilidade de ascensão de dispositivos inovadores, como os modernos
telefones celulares e tablets com telas sensíveis ao toque. Para gerenciar adequadamente
estas diversas interfaces é necessário utilizar o software dependente
do hardware (HdS), que é responsável pelo controle e acesso a estes
dispositivos. Além deste complexo arranjo de componentes, para atender a
crescente demanda por mais funcionalidades integradas, o paradigma de
multiprocessamento vem sendo adotado para aumentar o desempenho das
plataformas.
Devido à lacuna de produtividade de sistemas, tanto a indústria como a
academia têm pesquisado processos mais eficientes para construir e simular
sistemas cada vez mais complexos. A premissa dos trabalhos do estado da
arte está em trabalhar com modelos com alto nível de abstração e de precisão
que permitam ao projetista avaliar rapidamente o sistema, sem ter que
depender de lentos e complexos modelos baseados em ISS.
Neste trabalho é definido um conjunto de construtores para modelagem
de plataformas baseadas em processadores, com suporte para desenvolvimento
de HdS e reusabilidade dos componentes, técnicas para estimativa
estática de tempo simulado em ambiente nativo de simulação e suporte para
plataformas multiprocessadas. Foram realizados experimentos com aplica-
ções de entrada e saída intensiva, computação intensiva e multiprocessada,
com ganho médio de desempenho da ordem de 1.000 vezes e precisão de estimativas
com erro médio inferior a 3%, em comparação com uma plataforma
de referência baseada em ISS._________________________________________________________________________________________ ABSTRACT: The amazing advances of computer systems technology enabled the rise of
innovative devices, such as modern touch sensitive cell phones and tablets. To
properly manage these various interfaces, it is required the use of the Hardwaredependent
Software (HdS) that is responsible for these devices control and access.
Besides this complex arrangement of components, to meet the growing
demand for more integrated features, the multiprocessing paradigm has been
adopted to increase the platforms performance.
Due to the system design gap, both industry and academia have been researching
for more efficient processes to build and simulate systems with this
increasingly complexity. The premise of the state of art works is the development
of high level of abstraction and precise models to enable the designer
to quickly evaluate the system, without having to rely on slow and complex
models based on instruction set simulators (ISS).
This work defined a set of constructors for processor-based platforms modeling,
supporting HdS development and components reusability, techniques for
static simulation timing estimation in native environment and support for multiprocessor
platforms. Experiments were carried out with input and output intensive,
compute intensive and multiprocessed applications leading to an average
performance speed up of about 1,000 times and average timing estimation
accuracy of less than 3%, when compared with a reference platform
based on ISS.
|
26 |
Análise da eficiência de um sistema combinado de alagados construídos na melhoria da qualidade das águas / Assessment of efficiency of combined constructed wetlands system for water quality improvementCaroline de Andrade Gomes da Cunha 14 September 2006 (has links)
Este trabalho teve como objetivo avaliar a eficiência de um sistema combinado de alagados construídos, localizado no Parque Ecológico do Tietê em São Paulo, na melhoria da qualidade das águas. A estação de estudo é composta por um canal de decantação, um canal de macrófitas flutuantes (Eicchornia crassipes, Pistia stratioides, Salvinia auriculata) e emergentes (Typha angustifolia) de fluxo superficial, e duas células paralelas de solos filtrantes de fluxo vertical descendente cultivados com arroz (Oryza sativa). As coletas de água foram realizadas mensalmente, na entrada e saída de cada etapa do sistema, no período de fevereiro, março, junho e julho de 2004 e de março a setembro de 2005. As variáveis físicas, químicas e biológicas da água foram medidas e taxas de eficiência de remoção parcial e total do sistema foram calculadas. A estação construída de alagados mostrou-se eficiente principalmente na remoção de sulfato (52%), turbidez (86%), 'DBO IND.5' (41 - 64%), fósforo total (51 68%), nitrogênio albuminóide (51,7%), nitrito (77,8%) e nitrogênio amoniacal (57 84%). Os canais de macrófitas apresentaram um alto desempenho de remoção média para maioria das variáveis analisadas no trabalho, contribuindo com a maior porção na taxa de remoção total do sistema. Durante o período de estudo, provavelmente devido à falta de manejo do sistema, observou-se a volta dos nutrientes assimilados pelas macrófitas para a coluna d`água (N, P, Fe) com a decomposição das plantas e condições de anaerobiose nos solos filtrantes. Esses fatores, juntamente com a presença dos animais do parque atraídos pelo arroz, contribuíram com o baixo desempenho do canal de macrófitas e dos solos filtrantes na remoção de cor, turbidez, ferro total e coliformes em alguns meses de coleta. Para a maioria das variáveis analisadas, a água tratada pelo sistema de alagados construídos alcançou os limites e padrões estabelecidos pela Resolução CONAMA 357/2005 para águas doces de classe 2 (BRASIL, 2005). Contudo, em função dos dados obtidos, não se pode enquadrar totalmente o efluente, embora seja esperado que com a estabilização do sistema e um manejo adequado, a água tratada consiga atingir as características exigidas e possa ser enquadrada em águas doces de classe 2. / The aim of this work was evaluate the efficiency of combined constructed wetlands, located in the Tiete Ecological Park in São Paulo, in water quality improvement. The station consists of a settling channel, one free-floating (Eichhornia crassipes, Salvinia auriculata, Pistia stratiotes) and rooted emergent macrophyte-based system (Typha angustifolia) with surface flow and two cells of vertical flow filter soils in parallel, planted with rice (Oryza sativa). The water samples were collected monthly at the inlet and outlet of each step of the system, in the period of February, March, June and July of 2004 and of March to September of 2005. The physical, chemical and biological variables of the water were measured and efficiency rates of the system were made. The constructed wetlands system mainly showed efficient removal rates in sulphate (52%), turbidity (86%), BDO (41 - 64%), total phosphorus (51 - 68%), organic nitrogen (51,7%), nitrite (77,8%) and ammonia nitrogen (57 - 84%). The settling channel and macrophyte-based system presented a high removal performance for most of the variables analyzed in the work, contributing with the largest portion in the total removal rate of the system. During the study period, probably due to the lack of system management, the return of nutrients previously uptaken (N, P, Fe) by macrophytes for the water column was observed with the decay of aging plants and anaerobic conditions in the HDS system. Those factors, added with the presence of the park´s animals attracted for the rice, contributed with the low performance of macrophyte-based and HDS system in the removal of color, turbidity, total iron and coliforms in some months of collection. For most of the analyzed variables, the water treated by the constructed wetlands system reached the limits and patterns established by the Resolution CONAMA 357/2005 for fresh water of class 2 (BRAZIL, 2005). However, due to the obtained data, the treated water cannot be totally classified as class 2, although it is expected that with the stabilization of the system and appropriate handling, the treated water reach the demanded characteristics and can be classified in fresh water of class 2.
|
27 |
Child Marriage, Human Development and Welfare : Using Public Spending, Taxation and Conditional Cash Transfers as Policy InstrumentsSayeed, Yeasmin January 2016 (has links)
The theme of this thesis is to analyze the impact of policy interventions such as financing human development (HD), tax reform and conditional cash transfer programmes, under the framework of growth and sustainable development. These policy instruments are evaluated through the application of both partial and general equilibrium models, and the last paper concentrates on developing regional social accounting matrices (SAMs) as a core database for spatial general equilibrium modelling. Essay 1: Trade-offs in Achieving Human Development Goals for Bangladesh investigates the benefits and costs associated with alternative investment financing options for achieving HD goals by applying the MAMS (Maquette for Millennium Development Goals Studies) model. We find that full achievement of these goals would have led to a GDP loss that would have been significantly larger in the domestic borrowing scenario than in the tax scenario. The tax-financing alternative is thus the better option for financing large development programs. In terms of public spending composition, we find that, under some circumstances, a trade-off arises between overall Millennium Development Goal (MDG) progress and poverty reduction. Essay 2: Welfare impact of broadening VAT by exempting Small-Scale food markets: The case of Bangladesh analyses the welfare impacts of different VAT reforms. A general and uniform VAT on all commodities is preferred as it is more efficient and less administratively costly. However, due to equity concerns, food is normally exempted from VAT. On the other hand, exemptions on food mean that an implicit subsidy is provided to high-income households. Hence, we analyze a broad-based VAT regime with a high threshold that excludes small-scale operators (where the low-income households buy their products most, including food) and the simulation result shows that welfare improves for the low-income households. Essay 3: Effect of Girls’ Secondary School Stipend on Completed Schooling and Age at Marriage: Evidence from Bangladesh estimates the effect of a conditional cash transfer programme on education and age at marriage. We apply both difference in differences (DiD) and regression discontinuity methods to evaluate the impact of the policy instrument. Our estimation results show that the girls in the treatment group who were exposed to the programme had a higher average number of completed years of schooling and also delayed their first marriage compared to the girls in the control group. We also show that the DiD approach might produce a biased result as it does not consider the convergence effect. Essay 4: Estimation of Multiregional Social Accounting Matrices using Transport Data proposes a methodology for estimating multiregional SAMs from a national SAM by applying the cross-entropy method. The methodology makes possible the construction of regional SAMs that are consistent with official regional accounts and minimize deviations from transport data.
|
28 |
Treatment of Spent Pickling Acid from Stainless Steel Production : A review of regeneration technologies with focus on the neutralisation process for implementation in Chinese industryDahlgren, Lena January 2010 (has links)
Pickling is a unit operation within stainless steel production, which means treating the steel with hydrofluoric acid (HF) and nitric acid (HNO3), also called mixed acid. The whole process generates waste water streams which have to be treated before released to recipient. The aim of this degree thesis was to make an evaluation of different possibilities for reduction of emissions from the pickling process with China as a possible future market. The work consisted of two different parts; the first was to describe and evaluate different treatment methods for waste pickling acid, with emphasis on denitrification technologies. The second and main part was to make a fundamental description of the neutralisation process and outline important parameters. The work was performed by gathering information from literature but also from industry in both Sweden and China. The work has been a collaboration between the Royal Institute of Technology (KTH), the Swedish Environmental Institute (IVL) and the company Scanacon. A review of the different acid recovery methods; ionic exchange, diffusion dialysis and extraction was made. The study showed that ionic exchange is a robust method with relatively low cost and therefore it has been largely implemented both in Swedish and Chinese industry. The outflow however still requires neutralisation. Nitrate reduction can be performed as “end of pipe”, those methods investigated in this study were; biological treatment, reverse osmosis and nanofiltration. Meanwhile, internal solutions such as evaporation and electro-dialysis are two interesting technologies which reduce nitrates in combination with acid recovery. It was found that slaked lime (Ca(OH)2) is the most suitable neutralisation agent for pickling waste and, besides the choice of chemicals, many important parameters influence the process, such as the optimal pH, mixing and conditions during lime slaking. Based on information from one of the visited sites in Sweden a mass balance of the neutralisation facility was made and from that the required amount of Ca(OH)2 was calculated. The calculations were verified by an experimental part performed by IVL, using pickling acids from the same site. The amount of metals in the outgoing water was calculated using software “Medusa” but also by equilibrium equations. However, the results differed somewhat; this is probably due to the fact that Medusa takes other complexes and their interaction, besides the formed metal hydroxides, into consideration. Within the mining industry research has been made on different methods for neutralisation and some have been tested in field. An example is the High Density Sludge process (HDS), were an amount of sludge is recycled back to the neutralisation tank. It was shown that this gave improved sludge properties and decreased lime consumption. This could perhaps also be implemented for waste water in the stainless steel industry, and the method was also tested during the experimental part of this project. The dry content increased after a number of cycles but further investigation is required before any conclusion can be drawn. / Betning är en enhetsprocess inom tillverkningen av rostfritt stål då godset behandlas med fluorväte syra (HF) och salpetersyra (HNO3), också kallad blandsyra. Betningen ger upphov till vatten strömmar som måste behandlas innan de släpps ut till recipienten. Syftet med det här examensarbetet var att göra en utvärdering av olika tekniker för att reducera utsläpp till vatten från betningen med Kina som potentiell framtida marknad. Arbetet bestod av två delar; den första delen var att beskriva och utvärdera olika behandlingsmetoder av förbrukade betbad med betoning på denitrifikationstekniker. Den andra och största delen var att göra en grundläggande beskrivning av neutralisationsprocessen. Studien utfördes genom att inhämta information från litteratur samt från industrin i både Sverige och Kina. Arbetet har varit ett samarbetsprojekt mellan Kungliga Tekniska Högskolan (KTH), Svenska miljöinstitutet (IVL) och företaget Scanacon. Arbetet behandlar syraåtervinningsystemen; jonbytare, diffusions dialys samt extraktion. Nitrat reduktion kan ske internt eller externt där de externa åtgärder som behandlas i denna rapport är biologisk rening, omvänd osmos och nanofiltrering. De interna metoderna avdunstning och elektrodialys är intressanta eftersom de återvinner syran samtidigt som de reducerar nitraterna avsevärt. Studien visade att jonbyte, på grund av dess robusthet och relativt låga kostnad är den mest implementerade metoden för syraåtervinning i både svensk och kinesisk industri idag. Restprodukten från jonbytaren kräver dock fortsatt behandling, där det traditionella valet är neutralisation. Studien visade att släckt kalk (Ca(OH)2) är det mest passande kemikalien för neutralisation av betsyror. Förutom kemikalieval så finns det många parametrar som påverkar effektiviteten hos processen så som pH, omrörning och förhållanden under kalksläckningen. Baserat på information ifrån ett av de besökta stålverken i Sverige, gjordes en massbalans över dess neutralisationanläggning. Utifrån de flöden som denna gav kunde den teoretiska mängden kalk som krävdes för utfällning räknas ut. Beräkningarna verifierades med en experimentell del som utfördes av IVL på betsyror från samma verk. Resthalterna av metall i utgående vatten beräknades med programmet ”Medusa” men också med jämviktsekvationer. Resultaten mellan de två skiljde sig, detta beror förmodligen på att Medusa förutom hydroxidutfällning tar hänsyn till andra utfällningskomplex och dess interaktioner. Inom gruvvatten industrin har det forskats en del kring olika neutralisationsmetoder, en i litteraturen föreslagen sådan är ”High Density Sludge process (HDS)”. Här återförs en del av slammet tillbaka till neutralisationssteget, vilket visade sig ge förbättrade slamegenskaper och minskad kalkåtgång. Det var intressant att undersöka om denna metod också gick att implementera på förbrukade betbad och därför prövades metoden i den experimentella delen av detta projekt. Detta gav efter ett antal återföringscykler högre torrhalt på slammet, dock krävs fortsatta undersökningar innan någon slutsats kan dras.
|
Page generated in 0.0488 seconds