We proposed to demonstrate the effectiveness of a catalytic membrane reactor (a ceramic membrane combined with a catalyst) to selectively produce methanol by partial oxidation of methane. Methanol is used as a chemical feedstock, gasoline additive, and turbine fuel. Methane partial oxidation using a catalytic membrane reactor has been determined as one of the promising approaches for methanol synthesis from methane. In the original proposal, the membrane was used to selectively remove methanol from the reaction zone before carbon oxides form, thus increasing the methanol yield. Methanol synthesis and separation in one step would also make methane more valuable for producing chemicals and fuels. However, all the membranes tested in this laboratory lost their selectivity under the reaction conditions. A modified non-isothermal, non-permselective membrane reactor then was built and satisfactory results were obtained. The conversion and selectivity data obtained in this laboratory were better than that of the most published studies.

Silicalite-1, a pure silica zeolite, was deposited on a tubular, asymmetric, {gamma}-alumina support. Single gas permeation experiments with N{sub 2}, CH{sub 4}, and CO{sub 2} were carried out on the membrane. Separation experiments for N{sub 2}/CH{sub 4} mixtures were also conducted. Single-gas permeation of H{sub 2} and separation of H{sub 2}/SF{sub 6} mixture were also carried out with the membrane. Composite membranes of silicalite and Ni-SAPO-34 were also fabricated, but no CO{sub 2}/H{sub 2} selectivity was found. It is proposed to use these membranes for methanol synthesis and separation, and for separating H{sub 2} from gasification products for use as fuel cell fuel, etc.

Objective is to demonstrate the effectiveness of a catalytic membrane reactor (ceramic membrane combined with catalyst) to selectively produce methanol by partial oxidation of methane. None of the membranes tested in a high pressure system could selectively remove methanol, until a cooling tube was inserted inside the membrane reactor to quench the product stream; this effectively increased methanol selectivity 2[times] during methane oxidation. For both conditions, combined selectivity for methanol and CO is constant, 85%. The remaining product is CO[sub 2]. The membranes were broken when removed from the system; this was remedied when a cooling tube with a smaller diameter was used.

We proposed to demonstrate the effectiveness of a catalytic membrane reactor (a ceramic membrane combined with a catalyst) to selectively produce methanol by partial oxidation of methane. Methanol is used as a chemical feedstock, gasoline additive, and turbine fuel. Methane partial oxidation using a catalytic membrane reactor has been determined as one of the promising approaches for methanol synthesis from methane. In the original proposal, the membrane was used to be used to selectively remove methanol from the reaction zone before carbon oxides form, thus increasing the methanol yield. Methanol synthesis and separation in one step would also make methane more valuable for producing chemicals and fuels. The cooling tube inserted inside the membrane reactor has created a low temperature zone that rapidly quenches the product stream. This system has proved effective for increasing methanol selectivity during CH[sub 4] oxidation, and we are using and modifying this non-isothermal, non-permselective membrane reactor.

We proposed to demonstrate the effectiveness of a catalytic membrane reactor (a ceramic membrane combined with a catalyst) to selectively produce methanol by partial oxidation of methane. Methanol is used as a chemical feedstock, gasoline additive, and turbine fuel. Methane partial oxidation using a catalytic membrane reactor has been determined as one of the promising approaches for methanol synthesis from methane. In the original proposal, the membrane was used to selectively remove methanol from the reaction zone before carbon oxides form, thus increasing the methanol yield. Methanol synthesis and separation in one step would also make methane more valuable for producing chemicals and fuels. The cooling tube inserted inside the membrane reactor has created a low temperature zone that rapidly quenches the product stream. This system has proved effective for increasing methanol selectivity during CH{sub 4} oxidation. The membranes broke during experiments, however, apparently because of the large radial thermal gradient and axial thermal expansion difference. Our efforts concentrated on improving the membrane lifetime by modifying this non-isothermal membrane reactor.

The direct partial oxidation of CH{sub 4} to CH{sub 3}OH has been studied in a non-permselective, non-isothermal catalytic membrane reactor system. A cooling tube introduced coaxially inside a tubular membrane reactor quenches the product stream rapidly so that further oxidation of CH{sub 3}OH is inhibited. Selectivity for CH{sub 3}OH formation is significantly higher with quenching than in experiments without quenching. For CH{sub 4} conversion of 4% to 7% CH{sub 3}OH selectivity is 40% to 50% with quenching and 25% to 35% without quenching.

The objective of this work is to investigate, in the laboratory, the parameters associated with a chemically assisted in situ recovery procedure, using hydrogen chloride (HCI), carbon dioxide (CO{sub 2}), and steam (H{sub 2}O), to obtain data useful to develop a process more economic than existing processes and to report all findings. Quarter summary: all modifications previously planned where completed and a reaction experiment was run. A couple design flaws were discovered, improvements were designed, and all parts are expected in the first week of July. Experiment {number_sign}6 is expected to run the following Monday. Barring further mishap, experiments will be run one each week thereafter. The project is behind schedule, but the project is well positioned to make significant and considerable progress.

The purpose of the research project was to investigate the feasibility of the chemically assisted in situ retort method for recovering shale oil from Colorado oil shale. The chemically assisted in situ procedure uses hydrogen chloride (HCl), steam (H{sub 2}O), and carbon dioxide (CO{sub 2}) at moderate pressure to recovery shale oil from Colorado oil shale at temperatures substantially lower than those required for the thermal decomposition of kerogen. The process had been previously examined under static, reaction-equilibrium conditions, and had been shown to achieve significant shale oil recoveries from powdered oil shale. The purpose of this research project was to determine if these results were applicable to a dynamic experiment, and achieve penetration into and recovery of shale oil from solid oil shale. Much was learned about how to perform these experiments. Corrosion, chemical stability, and temperature stability problems were discovered and overcome. Engineering and design problems were discovered and overcome. High recovery (90% of estimated Fischer Assay) was observed in one experiment. Significant recovery (30% of estimated Fischer Assay) was also observed in another experiment. Minor amounts of freed organics were observed in two more experiments. Penetration and breakthrough of solid cores was observed in six experiments.

Objective is to demonstrate the effectiveness of a catalytic membrane reactor (ceramic membrane combined with catalyst) to selectively produce methanol by partial oxidation of methane. None of the membranes tested in a high pressure system could selectively remove methanol, until a cooling tube was inserted inside the membrane reactor to quench the product stream; this effectively increased methanol selectivity 2{times} during methane oxidation. For both conditions, combined selectivity for methanol and CO is constant, 85%. The remaining product is CO{sub 2}. The membranes were broken when removed from the system; this was remedied when a cooling tube with a smaller diameter was used.

The objective of this work is to investigate, in the laboratory, the parameters associated with a chemically assisted in situ recovery procedure, using hydrogen chloride (HCI), carbon dioxide (CO{sub 2}), and steam (H{sub 2}0), to obtain data useful to develop a process more economic than existing processes and to report all findings. The technical progress of the project is reported. The project status is that the progress is being made towards being able to run meaningful experiments.

The objective of this work is to investigate, in the laboratory, the parameters associated with a chemically assisted in situ recovery procedure, using hydrogen chloride (HCI), carbon dioxide (CO{sub 2}), and steam (H{sub 2}O), to obtain-data useful to develop a process more economic than existing processes and to report all findings. The technical progress of the project is reported. The progress of the project is that experiment preparations are underway. Reactor design, process design, and experiment design have been completed. The laboratory to be used has required extensive clean-up, and is nearly ready. Safety considerations are underway. Finally, an initial literature search has revealed some important aspects that need to be considered.

We proposed to demonstrate the effectiveness of a catalytic membrane reactor (a ceramic membrane combined with a catalyst) to solely produce methanol by partial oxidation of methane. Methanol is used as a chemical feedstock, gasoline additive, and turbine fuel. Methane partial oxidation using a catalytic membrane reactor has been determined as one of the promising approaches for methanol synthesis from methane. In the original proposal the membrane was used to selectively remove methanol from the reaction zone before carbon oxides form, thus increasing the methanol yield. Methanol synthesis and separation in one step would also make methane more valuable for producing chemicals and fuels. The cooling tube inserted inside the membrane reactor has created a low temperature zone that rapidly quenches the product stream. Both ceramic and metal membranes were tested in this study and similar results were obtained. This membrane reactor system has proved effective for increasing methanol selectivity during CH{sub 4} oxidation. We are currently using this non-isothermal non-permselective membrane reactor, and evaluating modifications to further improve performance. Metal membrane was used to avoid the membrane breakage problem. A series of experiments were carried out in order to optimize the operation of the process. A methanol yield of …

The objective of this work is to investigate, in the laboratory, the parameters associated with a chemically assisted in situ recovery procedure, using hydrogen chloride (HCI), carbon dioxide (CO{sub 2}), and steam (H{sub 2}O), to obtain data useful to develop a process more economic than existing processes and to report all findings. The technical progress of the project is reported. The project status is that the solutions to the problems discussed in the third quarter status, were found to function satisfactorily. Future needs have been considered, and appropriate equipment and instrumentation changes have been designed. Only one experiment was performed this quarter, with some improvement over the previous experiments. The increase in shale oil recovery followed directly from the changes discussed last quarter, but the improvement could have been larger with wider-spread implementation of the changes. Equipment was purchased to rectify the need, and will be installed shortly. Further, a minor change in the design was necessary to account for the brittleness of high temperature electrical resistance heating tapes. The focus of the work this quarter has been on the development of computer software to enable the use of on-line parameter identification, the design of the instrumentation necessary to adequately …