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The objective of this program was to develop a commercial process for producing ethanol from refinery waste gases. this report presents results from the development phases. The major focus of this work was the preparation of the prototype design which will demonstrate this technology in a 2.5 lb/hr ethanol production facility. Additional areas of focus included efforts in obtaining an industrial partner to help finance the prototype, and advanced engineering experiments concentrating on process optimization in various areas needing future development and optimization. The advanced engineering experiments were performed in the laboratory in these areas: treatment and use of recycle water from distillation back to fermentation; alternative methods of removing cells from the fermentation broth; the fermentation of streams containing CO{sub 2}/H{sub 2} alone, with little to no CO present; dealing with methanogen contaminants that are capable of fermenting CO{sub 2} and H{sub 2} to methane; and acetate tolerance by the culture. Results from the design, industrial partner search and the laboratory R&D efforts are discussed in this report.

Refineries discharge large volumes of H2, CO, and CO 2 from cracking, coking, and hydrotreating operations. This RD III, engineering development; and IV, demonstration. Phase I, exploratory development, has been completed. The research effort has yielded two strains (Isolates O-52 and C-01) which are to be used in the pilot studies to produce ethanol from CO, CO2, and H2 in petroleum waste gas. Results from single continuous stirred tank reactor (CSTR) laboratory tests have shown that 20-25 g/L ethanol can be produced with < 5 g/L acetic acid byproduct. Laboratory studies with two CSTRs in series have yielded ethanol concentrations of 30-35 g/L with 2-4 g/L acetic acid byproduct. Water recycle from distillation back to the fermenter shows that filtration of the water before distillation eliminates the recycle of toxic materials back to the fermenter. Product recovery in the process will use direct distillation to the azeotrope, followed by adsorption to produce neat ethanol. This is less energy intensive than e.g. solvent extraction, azeotropic distillation, or pervaporation. Economic projections are quite attractive; the economics are refinery stream dependent and thus vary depending on refinery location and operation.

Oil refineries discharge large volumes of H{sub 2}, CO, and CO{sub 2} from cracking, coking, and hydrotreating operations. This program seeks to develop a biological process for converting these waste gases into ethanol, which can be blended with gasoline to reduce emissions. Production of ethanol from all 194 US refineries would save 450 billion BTU annually, would reduce crude oil imports by 110 million barrels/year and emissions by 19 million tons/year. Phase II efforts has yielded at least 3 cultures (Clostridium ljungdahlii, Isolate O-52, Isolate C-01) which are able to produce commercially viable concentrations of ethanol from CO, CO{sub 2}, and H{sub 2} in petroleum waste gas. Single continuous stirred tank reactor studies have shown that 15-20 g/L of ethanol can be produced, with less than 5 g/L acetic acid byproduct. Culture and reactor optimization in Phase III should yield even higher ethanol concentrations and minimal acetic acid. Product recovery studies showed that ethanol is best recovered in a multi-step process involving solvent extraction/distillation to azeotrope/azeotropic distillation or pervaporation, or direct distillation to the azeotrope/azeotropic distillation or pervaporation. Projections show that the ethanol facility for a typical refinery would require an investment of about $30 million, which would be returned in less than 2 years.

The purpose of the proposed research is to develop a technically and economically feasible process for biologically producing H{sub 2} from synthesis gas while, at the same time, removing harmful sulfur gas compounds. Six major tasks are being studied: culture development, where the best cultures are selected and conditions optimized for simultaneous hydrogen production and sulfur gas removal; mass transfer and kinetic studies in which equations necessary for process design are developed; bioreactor design studies, where the cultures chosen in Task 1 are utilized in continuous reaction vessels to demonstrate process feasibility and define operating conditions; evaluation of biological synthesis gas conversion under limiting conditions in preparation for industrial demonstration studies; process scale-up where laboratory data are scaled to larger-size units in preparation for process demonstration in a pilot-scale unit; and economic evaluation, where process simulations are used to project process economics and identify high cost areas during sensitivity analyses. The purpose of this report is to present results from bioreactor studies involving H{sub 2} production by water gas shift and H{sub 2}S removal to produce elemental sulfur. Many of the results for H{sub 2} production by Rhodospirillum rubrum have been presented during earlier contracts. Thus, this report concentrates mainlymore » on H{sub 2}S conversion to elemental sulfur by R. rubrum.« less

Based upon the results of this culture screening study, Rhodospirillum rubrum is recommended for biocatalysis of the water gas shift reaction and Chlorobium thiosulfatophilum is recommended for H{sub 2}S conversion to elemental sulfur. Both bacteria require tungsten light for growth and can be co-cultured together if H{sub 2}S conversion is not complete (required concentration of at least 1 ppM), thereby presenting H{sub 2} uptake by Chlorobium thiosulfatophilum. COS degradation may be accomplished by utilizing various CO-utilizing bacteria or by indirectly converting COS to elemental sulfur after the COS first undergoes reaction to H{sub 2} in water. The second alternative is probably preferred due to the low expected concentration of COS relative to H{sub 2}S. Mass transfer and kinetic studies were carried out for the Rhodospirillum rubrum and Chlorobium thiosulfatophilum bacterial systems. Rhodospirillum rubrum is a photosynthetic anaerobic bacterium which catalyzes the biological water gas shift reaction: CO + H{sub 2}O {yields} CO{sub 2} + H{sub 2}. Chlorobium thiosulfatophilum is also a photosynthetic anaerobic bacteria, and converts H{sub 2}S and COS to elemental sulfur.

Syngas is known to contain approximately 1 percent H[sub 2]S, along with CO[sub 2], C0[sub 2], H[sub 2] and CH[sub 4]. Similarly, the syngas may become contaminated with oxygen, particularly during reactor start-up and during maintenance. Previous studies with the water-gas shift bacterium Rhodospirillum rubrum have shown that the bacterium is tolerant of small quantities of oxygen, but the effects of oxygen on CO-consumption are unknown. Similarly, R. rubrum is known to be tolerant of H[sub 2]S, with high concentrations of H[sub 2]S negatively affecting CO-uptake. Batch experiments were thus carried out to determine the effects of H[sub 2]S and O[sub 2] on CO-uptake by R. rubrum. The results of these experiments were quantified by using Monod equations modified by adding terms for CO, H[sub 2]S and O[sub 2] inhibition. The techniques used in determining kinetic expressions previously shown for other gas-phase substrate bacterial systems including R. rubrum were utilized.

Research continues on the conversion of synthesis by shift reactions involving bacteria. Topics discussed here include: biological water gas shift, sulfur gas utilization, experimental screening procedures, water gas shift studies, H{sub 2}S removal studies, COS degradation by selected CO-utilizing bacteria, and indirect COS utilization by Chlorobia. (VC)