Catalysts for upgrading coal-derived liquids. Quarterly report, January 1-March 31, 1981

Run ZBF was conducted to determine the amount of sulfur and nitrogen removal from SRC-I/process solvent mixture in the absence of a hydrotreating catalyst. Negligible nitrogen and sulfur removal resulted from this experiment. The hydrogen content of the coal liquid increased slightly over that of the feedstock. In similar studies using other coal liquids some sulfur removal (10 to 40%) was noted under non-catalyzed conditions. Several commercial NiMo supported catalysts were analyzed for silica contents using atomic absorption. These results revealed that catalysts with large micropore size structures also contain high silica content (up to 22.5 weight percent). Several short duration runs (12 to 110 hours) were conducted in the CLTU to gather data on catalyst coking mechanisms. Using the SRC material mixed with a process solvent or creosote oil (30 weight percent SRC), solid materials were observed to form and precipitate in the latter portions of the reactor bed. The reactor system was modified to prevent the accumulation of these incompatible solids which would result in premature termination of the experimental runs. In the catalyst regeneration study (HDN-30, NiMo), a spent catalyst was regenerated and then used to hydrotreat a coal liquid consisting of 10% Synthoil II liquid mixed with raw anthracene oil. This regenerated catalyst gave equal and somewhat superior performance with respect to heteroatom removal compared to that of the fresh catalyst. A second regeneration of this same catalyst loading has been conducted and the regenerated catalyst is being prepared for a third cycle. The spent catalyst lost approximately 33% of its total surface area, yet regeneration recovered 97% of the fresh catalyst area

Catalysts for upgrading coal-derived liquids. Quarterly report, January 1-March 31, 1980

Construction of the new trickle-bed reactor was completed and one experiment was conducted. The experimental run was made using a Pamco coal-derived liquid containing 0.40% sulfur and 0.95% nitrogen. The catalyst utilized was an American Cyanamide HDN-30, Ni-Mo-Al/sub 2/O/sub 3/. Run conditions were at 399C (750F), 1500 psig and space times up to two hours. Sample analyses are not yet available from this experiment. Two runs were completed in the Catalyst Life Test Unit (CLTU) utilizing a liquid containing 50% Synthoil and 50% Raw Anthracene oil. This fluid has a 0.54% sulfur and 1.21% nitrogen. Two Ni-MoAl/sub 2/O/sub 3/ catalysts were used - Shell-324, and H-Oil. Both experiments were terminated prematurely because of equipment malfunction. Sample analyses are not yet available from these two experiments

Catalysts for upgrading coal-derived liquids. Quarterly report, October 1-December 31, 1979

The design and partial construction of a new trickle-flow, packed bed reactor system was achieved. This reactor will be used to conduct investigations of throwaway type catalysts and zoned or mixed catalyst beds. It will also be used to support studies of catalyst activity decay. Most of these decay studies will be conducted in the Catalyst Life Test Unit (CLTU). The CLTU has been improved by redesign of the H/sub 2/ flow system and several minor changes. A new H/sub 2/ supply system has been designed and items ordered for installation. One experimental run was conducted in one of the three reactors of the CLTU. Raw anthracene oil was the feedstock and a vendor catalyst was used (Nalco, NM-502, Ni-Mo-Al/sub 2/O/sub 3/). Run conditions were: 700F(371C), 1500 psig and 2.0 hour space time (volume hourly). The objective of this run was to test equipment, familiarize personnel and to obtain a data base for future experiments. The sulfur removal was better than 95% throughout the 162 hours of operation. However, nitrogen removal activity decayed from 70% to about 35% after only 30 to 50 hours

Catalysts for upgrading coal-derived liquids. Quarterly report, July 1-September 30, 1980

Data on the HDN-30 and the Ketjenfine-124 catalysts not previously reported are given. These data show pore properties and reveal that the Ketjenfine catalyst has a most frequent pore diameter at about 50 angstroms and that of the HDN-30 catalyst at about 80 angstroms. A comparative figure revealed that no difference existed in nitrogen removal for over 120 hours of catalyst-oil contact for these two catalysts and for a reactor bed consisting of a 50 volume percent mixture of each. The Catalyst Life Test Unit was modified to improve the feed control. Two high pressure feed tanks were installed which allow improved feed-pump performance while operating with preheated, heavy feedstocks. Analytical methods were developed for the scanning electron microscope and atomic absorption to assess more detailed analysis of catalysts properties and metals content of the oils. One experimental run was conducted using the HDN-30(Ni-Mo-Al/sub 2/O/sub 3/) catalyst and a feedstock consisting of 10% (vol) Synthoil II and 90% Raw Anthracene Oil. This experiment was conducted at nominal conditions of 1500 psig, 427 C and with a liquid volume hourly space time of 2.74 hours. The run duration was 103 hours of liquid-catalyst contact. Only partial results were available; all will be given in the subsequent quarterly report. Sulfur removal was noted to be 75 to 83%

Catalysts for upgrading coal-derived liquids. Quarterly report, January 1-March 31, 1980

Construction of the new trickle-bed reactor was completed and one experiment was conducted. The experimental run was made using a Pamco coal-derived liquid containing 0.40% sulfur and 0.95% nitrogen. The catalyst utilized was an American Cyanamide HDN-30, Ni-Mo-Al/sub 2/O/sub 3/. Run conditions were at 399C (750F), 1500 psig and space times up to two hours. Sample analyses are not yet available from this experiment. Two runs were completed in the Catalyst Life Test Unit (CLTU) utilizing a liquid containing 50% Synthoil and 50% Raw Anthracene oil. This fluid has a 0.54% sulfur and 1.21% nitrogen. Two Ni-MoAl/sub 2/O/sub 3/ catalysts were used - Shell-324, and H-Oil. Both experiments were terminated prematurely because of equipment malfunction. Sample analyses are not yet available from these two experiments

Catalysts for upgrading coal-derived liquids. Quarterly report, April 1-June 30, 1980

Five experimental runs were conducted in the newly constructed trickle-bed reactor. The experiments were designed to obtain data on zoned catalyst beds. This new reactor system demonstrated satisfactory performance in temperature, pressure and flow control. High desulfurization and denitrogenation were achieved on both catalysts tested at conditions of 815F, 1500 psig. These catalysts were a CoMo/Al and NiMo/Al. Zoned bed of 50-50 volume percent of the two catalysts tested revealed no advantages with respect to desulfurization, denitrogenation and activity decay. The level of nitrogen removal was initially high, but activity decay was significant over the operational interval of 100 hours. Two experimental runs were completed in the Catalyst Life Test Unit (CLTU) utilizing a liquid containing 50% Synthoil and 50% Raw Anthracene Oil. This fluid has a 0.54 weight percent sulfur and a 1.21 weight percent nitrogen. The catalyst used in this study was a Ni-Mo-Al/sub 2/O/sub 3/ (Shell 324). The objective of the experiments was to demonstrate the effect of diluting the catalyst bed with a small size inert particle to improve gas-liquid contact and reduce channeling. No difference could be distinguished between the use of particle sizes in the range of 0.25 to 1.00 mm diameter. One run was terminated prematurely because the small particles plugged the catalyst support screens. Precipitous catalyst activity decay was noted for both nitrogen and sulfur removal

Catalysts for upgrading coal-derived liquids. Quarterly report, October 1-December 31, 1979

The design and partial construction of a new trickle-flow, packed bed reactor system was achieved. This reactor will be used to conduct investigations of throwaway type catalysts and zoned or mixed catalyst beds. It will also be used to support studies of catalyst activity decay. Most of these decay studies will be conducted in the Catalyst Life Test Unit (CLTU). The CLTU has been improved by redesign of the H/sub 2/ flow system and several minor changes. A new H/sub 2/ supply system has been designed and items ordered for installation. One experimental run was conducted in one of the three reactors of the CLTU. Raw anthracene oil was the feedstock and a vendor catalyst was used (Nalco, NM-502, Ni-Mo-Al/sub 2/O/sub 3/). Run conditions were: 700F(371C), 1500 psig and 2.0 hour space time (volume hourly). The objective of this run was to test equipment, familiarize personnel and to obtain a data base for future experiments. The sulfur removal was better than 95% throughout the 162 hours of operation. However, nitrogen removal activity decayed from 70% to about 35% after only 30 to 50 hours