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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Untersuchung zur Chemie des Deacon-Prozesses in Salzschmelzen

Tokmakov, Pavel 13 June 2018 (has links) (PDF)
HCl ist ein Nebenprodukt bei vielen organischen Chlorierungsprozessen. Die Aufarbeitung von HCl wäre wirtschaftlich sinnvoll. Eine der möglichen Optionen ist die Rückgewinnung des Chlors durch die katalytische HCl-Oxidation mit O2 (Deacon-Prozess). Das Hauptziel dieser Arbeit war es, die katalytische Aktivität von kupferchlorid-haltigen Schmelzen in Abhängigkeit von der Temperatur und dem Verhältnis der Reaktionsgase zu untersuchen. Dazu wurden Versuche unter stationären und instationären Reaktionsbedingungen im Temperaturintervall zwischen 400 und 500 °C durchgeführt. Für das bessere Verständnis des Katalysator-Systems wurde ein thermodynamisches Modell für das Stoffsystem MeCl-CuCl-CuCl2-CuO-HCl-H2O-Cl2-O2 (Me = Li, Na, K) erstellt. Weiterhin wurden mithilfe von kinetischen Untersuchungen Hinweise auf die Rolle der gelösten oxidischen Zwischenverbindungen im stufenweisen Reaktionsmechanismus gefunden. Mit den Versuchsergebnissen wurde gezeigt, dass die MeCl-CuCl-CuCl2-Schmelzen eine genügende katalytische Aktivität besitzen und damit eine Alternative zu den mit Feststoffträgern arbeitenden Katalysatoren darstellen. Zur Minderung von Korrosionsproblemen wurden mehrstufige Prozessführungen kritisch diskutiert.
2

Untersuchung zur Chemie des Deacon-Prozesses in Salzschmelzen

Tokmakov, Pavel 05 September 2018 (has links)
HCl ist ein Nebenprodukt bei vielen organischen Chlorierungsprozessen. Die Aufarbeitung von HCl wäre wirtschaftlich sinnvoll. Eine der möglichen Optionen ist die Rückgewinnung des Chlors durch die katalytische HCl-Oxidation mit O2 (Deacon-Prozess). Das Hauptziel dieser Arbeit war es, die katalytische Aktivität von kupferchlorid-haltigen Schmelzen in Abhängigkeit von der Temperatur und dem Verhältnis der Reaktionsgase zu untersuchen. Dazu wurden Versuche unter stationären und instationären Reaktionsbedingungen im Temperaturintervall zwischen 400 und 500 °C durchgeführt. Für das bessere Verständnis des Katalysator-Systems wurde ein thermodynamisches Modell für das Stoffsystem MeCl-CuCl-CuCl2-CuO-HCl-H2O-Cl2-O2 (Me = Li, Na, K) erstellt. Weiterhin wurden mithilfe von kinetischen Untersuchungen Hinweise auf die Rolle der gelösten oxidischen Zwischenverbindungen im stufenweisen Reaktionsmechanismus gefunden. Mit den Versuchsergebnissen wurde gezeigt, dass die MeCl-CuCl-CuCl2-Schmelzen eine genügende katalytische Aktivität besitzen und damit eine Alternative zu den mit Feststoffträgern arbeitenden Katalysatoren darstellen. Zur Minderung von Korrosionsproblemen wurden mehrstufige Prozessführungen kritisch diskutiert.:1 Einleitung. . . . . . . . . . .7 2 Theoretische Grundlagen zum Deacon-Prozess in Salzschmelzen. . . . . . . . . . .9 2.1 Thermochemie des Deacon-Prozesses. . . . . . . . . . .9 2.1.1 Oxidation von HCl mit O2 ohne Katalysator. . . . . . . . . . .9 2.1.2 Oxidation von HCl mit O2 in Gegenwart von CuCl2-haltigen Katalysatoren. . . . . . . . . . .10 2.2 Kinetik der Teilreaktionen in kupferchlorid-haltigen Salzschmelzen. . . . . . . . . . .13 2.2.1 Zersetzung des CuCl2. . . . . . . . . . .14 2.2.2 Oxidation von CuCl. . . . . . . . . . .15 2.2.3 Reaktion zwischen CuO-haltiger Schmelze und Chlorwasserstoff. . . . . . . . . . .17 3 Thermodynamische Modellierung der Mischungen aus LiCl, NaCl, KCl, CuCl und CuCl2. . . . . . . . . . .19 3.1 Thermodynamische Daten der reinen Stoffe. . . . . . . . . . .20 3.2 Mischungsmodelle. . . . . . . . . . .22 3.3 Vorgehensweise bei der Optimierung. . . . . . . . . . .25 3.4 System LiCl-NaCl-KCl. . . . . . . . . . . 25 3.5 System LiCl-CuCl. . . . . . . . . . .26 3.6 System NaCl-CuCl. . . . . . . . . . .28 3.7 System KCl-CuCl. . . . . . . . . . .29 3.8 System LiCl-CuCl2. . . . . . . . . . .30 3.9 System NaCl-CuCl2. . . . . . . . . . .33 3.10 System KCl-CuCl2 . . . . . . . . . . .34 3.11 System CuCl-CuCl2. . . . . . . . . . . 35 3.12 Ternäre Systeme. . . . . . . . . . .39 4 Untersuchungen zur CuO-Löslichkeit und der Stabilität von Oxidchloriden des Kupfers. . . . . . . . . . .46 4.1 Präparation von Cu2OCl2 und K4Cu4OCl10. . . . . . . . . . .46 4.2 Untersuchungen zur CuO-Löslichkeit. . . . . . . . . . .47 4.2.1 Thermodynamische Reaktionsdaten. . . . . . . . . . .47 4.2.2 Auswertung der Literatur. . . . . . . . . . .48 4.2.3 O2-Titration kupferchlorid-haltiger Schmelze. . . . . . . . . . .49 4.2.4 Hochtemperatur-Filtration und CuO-Analyse. . . . . . . . . . .53 4.2.5 Thermischer Zerfall von Cu2OCl2. . . . . . . . . . .55 4.2.6 Thermischer Zerfall von K4Cu4OCl10. . . . . . . . . . .57 4.3 Thermodynamische Modellierung CuO-haltiger Systeme. . . . . . . . . . .59 4.3.1 Cu2OCl2. . . . . . . . . . .59 4.3.2 K4Cu4OCl10. . . . . . . . . . .60 4.3.3 CuO-Löslichkeit. . . . . . . . . . .62 4.3.4 Salzschmelzenmodell mit oxidhaltigen Systemen. . . . . . . . . . .63 4.4 Thermochemie des Deacon-Prozesses mit Modell-Daten. . . . . . . . . . .69 5 Experimentelle Untersuchungen zur katalytischen Oxidation von HCl in Salzschmelzen. . . . . . . . . . .72 5.1 Versuchsprogramm. . . . . . . . . . .72 5.2 Allgemeine Vorgehensweise. . . . . . . . . . .72 5.2.1 Versuchsapparatur. . . . . . . . . . .72 5.2.2 Vorbereitung der Salzmischungen. . . . . . . . . . .74 5.2.3 Bestimmung der Gaszusammensetzung und Umsatzberechnungen. . . . . . . . . . .75 5.2.4 Bestimmung der Schmelzenzusammensetzung. . . . . . . . . . .77 5.2.5 Charakteristik der Reaktoreinsätze Spirale und Fritte. . . . . . . . . . .77 5.3 Versuche mit Salzmischungen auf der Basis von Kupferchlorid. . . . . . . . . . .81 5.3.1 Stationäre Strömungsverhältnisse. . . . . . . . . . .81 5.3.2 Instationäre Bedingungen. . . . . . . . . . .95 6 Vorschläge zur Technologie. . . . . . . . . . .106 7 Zusammenfassung. . . . . . . . . . .112 Literaturverzeichnis. . . . . . . . . . .115 Anhang. . . . . . . . . . .124 A.1 Thermodynamische Standard-Daten. . . . . . . . . . .124 A.2 Thermodynamische Daten für das Modell LiCl-NaCl-KCl-CuCl-CuCl2-CuO-H2O-HCl-O2-Cl2. . . . . . . . . . .126 A.3 Charakteristika der kupferoxidhaltigen Verbindungen. . . . . . . . . . .133 A.3.1 P-XRD- und Raman-Aufnahmen der synthetischen Oxidchloriden. . . . . . . . . . .133 A.3.2 O2 -Titration kupferchlorid-haltiger Schmelze. . . . . . . . . . .134 A.3.3 Thermischer Zerfall von Cu2OCl2 und K4Cu4OCl10. . . . . . . . . . .137 A.3.4 Phasendiagramm KCl-CuCl2-CuO. . . . . . . . . . .138 A.4 Katalytische Oxidation von HCl in Salzschmelzen. . . . . . . . . . .138 A.5 Physikalische Eigenschaften von (Alk-Cl)-CuCl-CuCl Salzschmelzen. . . . . . . . . . .156 A.6 Chemikalien. . . . . . . . . . .161 A.7 Geräte, Anlagen. . . . . . . . . . .162 A.8 Methode zur titrimetrischen Bestimmung von Cu+, Cu+2 und CuO. . . . . . . . . . .164 A.9 Berechnete Chlor- und Sauerstoffpartialdrücke für (Alk-Cl)-CuCl-CuCl2-Schmelzen. . . . . . . . . . .164 A.10 Berechnete Aktivitäten der geschmolzenen Kupferchloride in (Alk-Cl)-CuCl-CuCl2-Schmelzen. . . . . . . . . . .171
3

Caracterização e gênese de Espodossolos da planície costeira do Estado de São Paulo / Characterization and genesis of Spodosols on the São Paulo State sandy coastal plain

Coelho, Maurício Rizzato 12 February 2009 (has links)
A gênese, a química, a macro e micromorfologia dos solos desenvolvidos nos ambientes arenosos da planície costeira do Estado de São Paulo foram investigadas. Nesses ambientes, genericamente denominados de restinga, a podzolização é o processo pedogenético predominante, sendo os Espodossolos e Neossolos Quartzarênicos os solos mais comumente encontrados. Os municípios paulistas de Cananéia, Ilha Comprida e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares, de vegetação remanescente e de solos, representativos da planície costeira do Estado de São Paulo. Nesses locais foram descritos e amostrados 31 perfis, muitos deles em cronosseqüência. A idade dos sedimentos e da matéria orgânica de horizontes cimentados selecionados (ortstein) também foram investigadas e, juntamente às análises químicas, incluindo procedimentos de dissolução seletiva do Fe e Al (DC, oxalato e pirofosfato para Fe e Al; NaOH, KCl, LaCl3 e CuCl2 para Al) e às micromorfológicas, permitiram concluir que: (a) os Espodossolos mais evoluídos e antigos, dotados de horizontes ortstein, podem ser considerados indicadores dos sedimentos pleistocênicos da Formação Cananéia das planícies costeiras quaternárias estudadas e, possivelmente, são paleossolos; (b) o tempo e o relevo foram os principais fatores de formação, condicionantes da diferenciação dos Espodossolos na paisagem; (c) os solos mais antigos, bem drenados devido às condições de relevo e dinâmica sedimentar (Ilha de Cananéia e Bertioga), apresentam grande variabilidade e diversidade de seus horizontes e atributos morfológicos, diferindo daqueles mais jovens e mal drenados, mais homogêneos, geralmente destituídos de horizonte Bs (Bertioga); (d) a química da maioria dos solos estudados são típicas daqueles já descritos para as áreas sob vegetação de restinga: baixas soma e saturação por bases, extremamente a fortemente ácidos, capacidade de troca de cátions dependente da matéria orgânica e saturada com Al trocável, aumento do carbono orgânico em profundidade; (e) o Al é o principal cátion envolvido na podzolização, sendo que suas formas ativas são: complexos de Alhúmus e compostos inorgânicos pouco cristalinos. Os primeiros predominam nos horizontes superficiais e horizontes espódicos hidromórficos; as formas inorgânicas se relacionam a alguns horizontes espódicos (Bs, Bh, Bhs e Bsm) situados na base de perfis bem drenados; (f) Al inorgânico pouco cristalino também foi extraído pelos reagentes pirofosfato e CuCl2, geralmente utilizados para avaliar Al unido à matéria orgânica; ao contrário, LaCl3 extraiu apenas as formas ativas da interação Al-húmus, sendo que KCl não incluiu todas essas formas reativas; (g) a decomposição de raízes in situ e, sobretudo, os processos de formação e transporte de complexos Al-húmus foram observados em alguns (decomposição de raízes) ou em todos os perfis estudados (complexos Al-húmus), originando os horizontes espódicos às expensas dos eluviais; (h) a imobilização desses complexos se dá por diferentes mecanismos: filtragem físicomecânica dos poros do solo, aumento do pH em profundidade, incorporação adicional de Al durante seu transporte e o efeito da absorção seletiva das raízes. Neste último processo, as raízes absorvem seletivamente água e nutrientes, segregando e precipitando ao seu redor os complexos Al-húmus da solução do solo, mobilizados dos horizontes superiores ou presentes nas águas de drenagem. / The genesis, chemistry and macro and micromorphology of soils developed on the sandy coastal plain of the São Paulo State were investigated. In these environments, often designated restinga, podzolization is the main pedogenetic process, being Spodosols and Quartzipsamments the soils most commonly found. Cananéia, Ilha Comprida and Bertioga cities were selected for the development of this research due to the representativeness of this environmental condition in the São Paulo State. In these environments 31 soil profiles were described and sampled, mainly in chronosequences. Age of sediments and of organic matter of cemented horizons (ortstein) were investigated as well. These data associated to the chemical analysis, including Fe and Al selective dissolution procedures (dithionite-citrate, oxalate and pyrophosphate for Fe and Al; NaOH, KCl, LaCl3 and CuCl2 for Al) and micromorphological analysis allowed the following conclusions: (a) the most developed Spodosols have ortstein horizons and can be considered indicators of sediments of Pleistocene age from the Cananéia Formation of the studied quaternary coastal plain and possibly are paleosols; (b) time and relief were the main soil formation factors responsible for differentiation of Spodosols on the landscape; (c) the oldest and well drained soils due to relief conditions and sedimentary dynamics (Cananéia and Bertioga) showed great variability and diversity of their horizons and morphological properties, differing from the youngest, poorly drained and more homogeneous Spodosols usually without Bs horizon (Bertioga). The youngest and well drained Spodosols (Ilha Comprida) showed an advanced degree of degradation; (d) the chemical properties of the studied soils are similar to other soils already described in the restinga: low in exchangeable bases, low in base saturation, strongly acidic, organic-matter dependent and Al-saturated CEC, increase in organic carbon with depth; (e) Al is main metal related to the podzolization process. The reactive forms of this element are Al-humus complexes and inorganic poorly crystalline compounds. Alhumus complexes predominate in the superficial and spodic, poorly drained horizons; the Alinorganic forms occur in some well drained spodic horizons (Bs, Bh, Bhs and Bsm) situated at the bottom of the well-drained soil profiles; (f) Al inorganic, poorly crystalline forms were extracted by pyrophosphate and CuCl2 reagents, usually used to determinate Al bound to organic matter; unlike, LaCl3 only extracted the reactive forms of Al-humus interaction, whereas KCl did not include these reactive forms; (g) Al-humus formation and mobilization were the main pedogenetic processes, but roots decomposition were observed in some horizons; (h) different mechanisms are related to Al-humus complexes immobilization: physical-mechanical filtering effect on soil pores, precipitation as pH increases with depth, precipitation with the decrease of C-to-metal ratio during organic matter complexation and roots selective absorption effect. In the latter, there is selective absorption of water and nutrients with segregation and precipitation of Al-humus complexes around roots. These Al-humus complexes are either mobilized from the superficial horizons or already dissolved in the draining water.
4

Caracterização e gênese de Espodossolos da planície costeira do Estado de São Paulo / Characterization and genesis of Spodosols on the São Paulo State sandy coastal plain

Maurício Rizzato Coelho 12 February 2009 (has links)
A gênese, a química, a macro e micromorfologia dos solos desenvolvidos nos ambientes arenosos da planície costeira do Estado de São Paulo foram investigadas. Nesses ambientes, genericamente denominados de restinga, a podzolização é o processo pedogenético predominante, sendo os Espodossolos e Neossolos Quartzarênicos os solos mais comumente encontrados. Os municípios paulistas de Cananéia, Ilha Comprida e Bertioga foram selecionados para o desenvolvimento desta pesquisa devido à presença de diferentes unidades sedimentares, de vegetação remanescente e de solos, representativos da planície costeira do Estado de São Paulo. Nesses locais foram descritos e amostrados 31 perfis, muitos deles em cronosseqüência. A idade dos sedimentos e da matéria orgânica de horizontes cimentados selecionados (ortstein) também foram investigadas e, juntamente às análises químicas, incluindo procedimentos de dissolução seletiva do Fe e Al (DC, oxalato e pirofosfato para Fe e Al; NaOH, KCl, LaCl3 e CuCl2 para Al) e às micromorfológicas, permitiram concluir que: (a) os Espodossolos mais evoluídos e antigos, dotados de horizontes ortstein, podem ser considerados indicadores dos sedimentos pleistocênicos da Formação Cananéia das planícies costeiras quaternárias estudadas e, possivelmente, são paleossolos; (b) o tempo e o relevo foram os principais fatores de formação, condicionantes da diferenciação dos Espodossolos na paisagem; (c) os solos mais antigos, bem drenados devido às condições de relevo e dinâmica sedimentar (Ilha de Cananéia e Bertioga), apresentam grande variabilidade e diversidade de seus horizontes e atributos morfológicos, diferindo daqueles mais jovens e mal drenados, mais homogêneos, geralmente destituídos de horizonte Bs (Bertioga); (d) a química da maioria dos solos estudados são típicas daqueles já descritos para as áreas sob vegetação de restinga: baixas soma e saturação por bases, extremamente a fortemente ácidos, capacidade de troca de cátions dependente da matéria orgânica e saturada com Al trocável, aumento do carbono orgânico em profundidade; (e) o Al é o principal cátion envolvido na podzolização, sendo que suas formas ativas são: complexos de Alhúmus e compostos inorgânicos pouco cristalinos. Os primeiros predominam nos horizontes superficiais e horizontes espódicos hidromórficos; as formas inorgânicas se relacionam a alguns horizontes espódicos (Bs, Bh, Bhs e Bsm) situados na base de perfis bem drenados; (f) Al inorgânico pouco cristalino também foi extraído pelos reagentes pirofosfato e CuCl2, geralmente utilizados para avaliar Al unido à matéria orgânica; ao contrário, LaCl3 extraiu apenas as formas ativas da interação Al-húmus, sendo que KCl não incluiu todas essas formas reativas; (g) a decomposição de raízes in situ e, sobretudo, os processos de formação e transporte de complexos Al-húmus foram observados em alguns (decomposição de raízes) ou em todos os perfis estudados (complexos Al-húmus), originando os horizontes espódicos às expensas dos eluviais; (h) a imobilização desses complexos se dá por diferentes mecanismos: filtragem físicomecânica dos poros do solo, aumento do pH em profundidade, incorporação adicional de Al durante seu transporte e o efeito da absorção seletiva das raízes. Neste último processo, as raízes absorvem seletivamente água e nutrientes, segregando e precipitando ao seu redor os complexos Al-húmus da solução do solo, mobilizados dos horizontes superiores ou presentes nas águas de drenagem. / The genesis, chemistry and macro and micromorphology of soils developed on the sandy coastal plain of the São Paulo State were investigated. In these environments, often designated restinga, podzolization is the main pedogenetic process, being Spodosols and Quartzipsamments the soils most commonly found. Cananéia, Ilha Comprida and Bertioga cities were selected for the development of this research due to the representativeness of this environmental condition in the São Paulo State. In these environments 31 soil profiles were described and sampled, mainly in chronosequences. Age of sediments and of organic matter of cemented horizons (ortstein) were investigated as well. These data associated to the chemical analysis, including Fe and Al selective dissolution procedures (dithionite-citrate, oxalate and pyrophosphate for Fe and Al; NaOH, KCl, LaCl3 and CuCl2 for Al) and micromorphological analysis allowed the following conclusions: (a) the most developed Spodosols have ortstein horizons and can be considered indicators of sediments of Pleistocene age from the Cananéia Formation of the studied quaternary coastal plain and possibly are paleosols; (b) time and relief were the main soil formation factors responsible for differentiation of Spodosols on the landscape; (c) the oldest and well drained soils due to relief conditions and sedimentary dynamics (Cananéia and Bertioga) showed great variability and diversity of their horizons and morphological properties, differing from the youngest, poorly drained and more homogeneous Spodosols usually without Bs horizon (Bertioga). The youngest and well drained Spodosols (Ilha Comprida) showed an advanced degree of degradation; (d) the chemical properties of the studied soils are similar to other soils already described in the restinga: low in exchangeable bases, low in base saturation, strongly acidic, organic-matter dependent and Al-saturated CEC, increase in organic carbon with depth; (e) Al is main metal related to the podzolization process. The reactive forms of this element are Al-humus complexes and inorganic poorly crystalline compounds. Alhumus complexes predominate in the superficial and spodic, poorly drained horizons; the Alinorganic forms occur in some well drained spodic horizons (Bs, Bh, Bhs and Bsm) situated at the bottom of the well-drained soil profiles; (f) Al inorganic, poorly crystalline forms were extracted by pyrophosphate and CuCl2 reagents, usually used to determinate Al bound to organic matter; unlike, LaCl3 only extracted the reactive forms of Al-humus interaction, whereas KCl did not include these reactive forms; (g) Al-humus formation and mobilization were the main pedogenetic processes, but roots decomposition were observed in some horizons; (h) different mechanisms are related to Al-humus complexes immobilization: physical-mechanical filtering effect on soil pores, precipitation as pH increases with depth, precipitation with the decrease of C-to-metal ratio during organic matter complexation and roots selective absorption effect. In the latter, there is selective absorption of water and nutrients with segregation and precipitation of Al-humus complexes around roots. These Al-humus complexes are either mobilized from the superficial horizons or already dissolved in the draining water.

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