Thesis (Ph. D.)--University of Notre Dame, 1941. / Cover title. Bibliography: p. 11.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1955. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 82-86).

Thesis (M. Sc.)--University of Canterbury, 2006. / Typescript (photocopy). Includes bibliographical references (leaves 73-90). Also available via the World Wide Web.

Thesis (M. Sc.)--University of Canterbury, 2008. / Typescript (photocopy). Includes bibliographical references (leaves 63-74). Also available via the World Wide Web.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.

Piperazine (PZ) is a cyclic diamine, which means it can absorb two moles of CO2 per mole of amine and potentially has a higher capacity for CO2 capture than monoethanolamine, the current solvent of choice for flue gas treatment. Nitrosamines are formed from the reaction between secondary or tertiary amines and nitrites or nitrogen oxides. Over 80% of nitrosamines are carcinogenic. The reaction of PZ and nitrite can form 1-nitrosopiperazine (also mononitrosopiperazine, MNPZ) and N-N,dinitrosopiperazine (DNPZ). Carcinogenicity of DNPZ is almost 20 times as that of MNPZ. There is also a possibility of nitrosamine formation of PZ in the CO2 capture process because of NOx in input flue gas, with the oxidative and thermal degradation products of PZ. Analytical methods were developed in order to perform kinetic studies of the reaction between a nitrite solution and PZ over a range of temperature from 20 to 150 °C at two different PZ concentrations, 8 and 2 mol/kg of solution, and three levels of CO2 loading, 0.3, 0.2, and 0.1 mole CO2/mole of alkalinity. At less than 75 °C, nitrite reacts with PZ and disappears during the reaction to an equilibrium concentration while at the higher temperature; the concentration of nitrite quickly decreases to a very low value. There is no evidence of DNPZ as a reaction product in all reaction conditions, but MNPZ is formed at the temperature greater than 75 °C. The MNPZ concentration approaches a maximum value consistent with the material balance and nitrite disappearance. By developing the time of reaction at the higher temperature a decomposition of MNPZ has been observed, by either the reverse of the formation reaction or decomposition to other compounds. By increasing the temperature, the maximum value of MNPZ concentration is achieved more quickly and the rate of MNPZ decomposition increases. Reactions follow the same trend at both PZ concentration and at the three different degrees of CO2 loading. A model has been established considering temperature, PZ concentration, and CO2 loading. The calculated activation energies of MNPZ production and decomposition were determined. MNPZ decomposition is more rapid than PZ degradation. / text

Aqueous piperazine (PZ) blended with N-(2-aminoethyl) piperazine (AEP) is an attractive solvent for CO₂ capture from coal-fired power plants. Blending PZ with AEP can remediate the precipitation issue of concentrated PZ while maintaining its high CO₂ absorption rate, and high resistance to degradation. 5 m PZ/2 m AEP also shows a milder nitrosamine issue than concentrated piperazine. A rigorous thermodynamic model was developed in Aspen Plus® to predict properties of PZ/AEP/H₂O/CO₂, using the electrolyte-Nonrandom Two-Liquid (eNRTL) activity coefficient model. A sequential regression was performed to represent CO₂ solubility, speciation, and amine volatility data over operationally significant loading and temperature ranges. The model predicts a CO₂ cyclic capacity of 0.78 mol/kg (PZ + AEP + water) for 5 m PZ/2 m AEP, compared to 0.50 mol/kg for 7 m MEA and 0.86 mol/kg for 8 m PZ. The predicted heat of absorption is 75 to 80 kJ/mol CO₂ at the operating loading range (0.290-0.371 mol CO₂/mol alkalinity). Although 5 m PZ/2 m AEP has a slightly lower CO₂ capacity than 8 m piperazine, its higher heat of absorption may offset the negative effect on energy consumption. Speciation for PZ/AEP/H₂O at various CO₂ loading and temperature was also predicted, from which behavior of CO₂ in the amine system was proposed. / text

by Kwok Chun-kiu. / Thesis (M.Ph.)--Chinese University of Hong Kong, 1987. / Bibliography: leaves 69-74.

Sulfate accumulates in the post-combustion CO₂ capture system and must be removed to re-use amine efficiently. Removal of sulfate from the amine-based postcombustion CO₂ capture system through a solvent reclaiming process may reduce CO₂ capture costs. This work determines the solubility of K₂SO₄ and Na₂SO₄ in 2 to 8 m PZ loaded with CO₂ and develops a thermodynamic and process model for the reclaiming process. At 40°C the solubility of Na2SO₄ in 8 m PZ with a CO₂ loading of 0.3 is 0.3 m Na2SO₄ and that of K₂SO₄ is 0.1 m K₂SO₄. Sulfate solubility in PZ solutions is represented by the empirical models: K₂SO₄: ln(Ksp) = 10.53I[superscript 0.3] - 0.98[PZ][subscript T] -3440/T - 2.42 ; Na₂SO₄: ln(Ksp) = 2.137I[superscript0.3] - .6505[PZ][subscript T] -826/T + 265 where [PZ][subscript T] = 2*(molality of PZ). A K₂SO₄ and Na₂SO₄ solubility thermodynamic model was developed in the eNRTL framework in the Fawkes model for PZ/CO₂/H₂O in Aspen Plus[trademark]. The energy cost of the Na process when removing the equivalent of 100 ppm SO₂ from the flue gas, ranging from $0.1-0.5/ton CO₂, was practically the same as the K process(ranging from $0.1-0.8/ton CO₂). The K₂SO₄ recovered in the process can be used as fertilizer. However, the KOH will still cost $0.6/tonne CO₂. If it is not possible to sell the K₂SO₄ as fertilizer because of the impurities that may be present on the K₂SO₄crystals, the chemical cost of the process would increase to $2/tonne CO₂. The chemical cost for the Na case is $0.7/tonne of CO₂. / text

The equilibrium partial pressures of monoethanolamine (MEA), piperazine (PZ), and water were measured in a stirred reactor with a recirculating vapor phase by FTIR analysis at 35 - 70 Celsius degrees. MEA and PZ volatility were measured in two separate pilot plant campaigns to capture CO₂ from flue gas under a range of absorber conditions. The laboratory data were regressed to determine NRTL binary interaction parameters that predicted the experimental points within 10 - 20%. It was proven that MEA volatility (0.45<MEA<0.55) is a viable concern in CO₂ capture processes from an economic, environmental, and overall health perspective. PZ, on the other hand, was not observed to be as volatile (0.06<PZ<0.08) as predicted by previous models and therefore volatility loss would not be a significant drawback for using it as a CO₂ capture solvent. Pilot plant results show an average MEA gas phase concentration at the absorber outlet to be approximately 45 ppm while the PZ concentrations averaged 6 ppm and 8 ppm at the absorber inlet and outlet, respectively.