Desulfurization of coal by microbial column flotation

Twenty-three strains capable of oxidizing iron were isolated from coal and ore storage sites as well as coal and ore mines, volcanic areas, and hot spring. Four strains were found to have high iron-oxidizing activity. One strain (T-4) was selected for this experiment since the strain showed the fastest leaching rate of iron and sulfate from pyrite among the four strains. The T-4 strain was assigned for Thiobacillus ferrooxidans from its cultural and morphological characteristics.Bacterial treatment was applied to column flotation. An increase of cell density in the microbial column flotation resulted in the increase of pyrite removal from a coal-pyrite mixture (high sulfur imitated coal) with corresponding decrease of coal recovery. The addition of kerosene into the microbial column flotation increased the recovery of the imitated coal from 55% (without kerosene) to 81% (with 50 muL/L kerosene) with the reduction of pyrite sulfur content from 11% (feed coal) to 3.9% (product coal). The kerosene addition could reduce the pyritic sulfur content by collecting the coal in the recovery. However, the addition could not enhance separation of pyrite from the coal-pyrite mixture, since pyrite rejection was not affected by the increase of the kerosene addition. An excellent separation was obtained by the microbial flotation using a long column which had a length-diameter (L/D) ratio of 12.7. The long column flotation reduced the pyritic sulfur content from 11% (feed coal) to 1.8% (product coal) when 80% of the feed coal was recovered without the kerosene addition. The long column flotation not only attained an excellent separation but also reduced the amount of cells for desulfurization to as little as one-tenth of the reported amount. (c) 1994 John Wiley & Sons, Inc.     

Mechanism of microbial flotation using Thiobacillus ferrooxidans for pyrite suppression

Microbial desulfurization might be developed as a new process for the removal of pyrite sulfur from coal sluries such as coal-water mixture (CWM). An application of iron-oxidizing bacterium Thiobacillus ferrooxidans to flotation would shorten the periods of the microbial removal of pyrite from some weeks by leaching methods to a few minutes. The floatability of pyrite in flotation was mainly reduced by T. ferrooxidans itself rather than by other microbial substances in bacterial culture as additive of flotation liquor. Floatability was suppressed within a few seconds by bacterial contact. The suppression was proportional to increasing the number of cells observed between bacterial adhesion and the suppression of floatability. If 25% of the total pyrite surface area covered with the bacteria, pyrite floatability would be completely depressed. Bacteria that lost their iron-oxidizing activities by sodium cyanide treatment were also able to adhere to pyrite and reduced pyrite floatability as much as normal bacteria did. Thiobacillus ferrooxidans ATCC 23270, T-1, 9, and 11, which had different iron-oxidizing abilities, suppressed floatability to similar-levels. The oxidizing ability of bacteria did not influence the suppressing effect. These results showed the mechanism of the suppression of pyrite floatability by bacteria. Quick bacterial adhesion to pyrite induced floatability suppression by changing the surface property from hydrophobic. The quick adhesion of the bacterium was the novel function which worked to change the surface property of pyrite to remove it from coal. (c) 1993 John Wiley & Sons, Inc.     

Suppression of pyritic sulphur during flotation tests using the bacterium Thiobacillus ferrooxidans

Environmental concern about sulphur dioxide emissions has led to the examination of the possibility of removing pyritic sulphur from coal prior to combustion during froth flotation, a routine method for coal cleaning at the pit-head. The bacterium Thiobacillus ferrooxidans was effective in leaching 80% and 63% -53 mum pyrite at 2% and 6% pulp density in shake flasks in 240 and 340 h, respectively.The natural floatability of pyrite was significantly reduced in the Hallimond tube following 2.5 min of conditioning in membrane-filtered bacterial liquor prior to flotation. The suppression effect was greatly enhanced in the presence of Thiobacillus ferrooxidans. A bacterial suspension in pH 2.0 distilled water showed 85% suppression, whereas in spent growth liquor this value was 95%. The optimum bacterial density was 3.25 x 10(10) cells/g pyrite in 230-ml distilled water (2% pulp density) in the Hallimond tube. The degree of suppression by the cells was related to particle size but not to pH or temperature. The sulphur content of a synthetic coal/pyrite mixture was reduced from 10.9 to 2.1% by flotation after bacterial preconditioning. It is postulated that pyrite removal in coals which are cleaned by froth flotation could be significantly reduced using a bacterial preconditioning stage with a short residence time of 2.5 min.     

Biological removal of pyritic sulfur from coal by the thermophilic organism Sulfolobus acidocaldarius

More than 90% of initial pyritic sulfur was removed from bituminous coal samples (containing 2.1% pyritic sulfur) using the thermophilic organism Sulfolobus acidocaldarius. Microbial desulfurization rate was improved nearly ten fold by adjusting the N/P and N/Mg ratios in the nutrient medium. Environmental conditions were optimized. The optimal values of temperature and pH were 70 degrees C and 1.5, respectively. The influence of certain process variables (such as coal pulp density, particle size, and initial cell number density) on the rate of pyritic sulfur removal were determined. A pulp density of 20%, particle size of D (p) < 48 mum, and an initial cell number density of 10(12) cells/g pyrite in coal were found to be optimal. The carbon dioxide enriched air did not improve the rate of pyritic sulfur removal compared to pure air at 10% pulp density of coal samples containing 2.1% pyritic sulfur. The kinetics of microbial leaching of pyritic sulfur from coal was investigated. The rate of leaching was found to be first order with respect to pyritic sulfur concentration in the reaction medium.     

Technological and economic aspects of coal biodesulfurisation

The sulfur found in coal is either part of the molecular coal structure (organically bound sulfur), is contained in minerals such as pyrite (FeS₂), or occurs in minor quantities in the form of sulfate and elemental sulfur. When pyrite crystals are finely distributed within the coal matrix, mechanical cleaning can only remove part of the pyrite. It can, however, be removed by microbial action requiring only mild conditions. The process involves simple equipment, almost no chemicals, but relatively long reaction times, and treatment of iron sulfate containing process water. Different process configurations are possibly depending on the coal particle size. Coal with particle sizes of less than 0.5 mm is preferably desulfurised in slurry reactors, while lump coal (> 0.5 mm) should be treated in heaps. Investment and operating costs are estimated for different process configurations on an industrial scale. Concerning the organically bound sulfur in coal there is up to now no promising biochemical pathway for the degradation and/or desulfurisation of such compounds.     

Continuous microbial desulfurization of coal--application of a multistage slurry reactor and analysis of the interactions of microbial and chemical kinetics

Microbial desulfurization of coal by pyrite oxidizing bacterial enrichment cultures has been studied in air-agitated slurry reactors of 4- and 20-L volumes. Batch experiments showed that inoculation with an active bacterial culture is essential to minimize the lag phase, although a considerable number of pyrite oxidizing bacteria was found on the coal prior to desulfurization. For detailed investigations of kinetics, energy requirements, and technical applicability, a bioreactor equipment consisting of a cascade of eight stages was developed and operated continuously. Microbial desulfurization of coal-monitored by measuring the axial profile of dissolved iron concentration, real and maximum oxygen consumption rates, and cell concentration-at pulp densities to 30% was performed over a period of 200 days without any disturbances concerning the aeration system, fluidization, transport of solids and microbial growth. At a pulp density of 20%, a pyrite conversion of 68% was achieved after the third reactor stage at a total residence time of five days in the first three stages. The kinetics of pyrite degradation were found to be well described by a rate equation of first order in pyrite surface area concentration if the pyrite is directly accessible for microbial attack. Rate constants were determined to 0.48 mg pyrite/(cm(2) day) in the first and to 0.24 mg pyrite/(cm(2) day) in the following reactor stages. Kinetic models taking into account adsorption/desorption as well as growth kinetics failed to describe the observed reaction rates. However, a model treating pyrite degradation and microbial growth kinetics formalistically seems to be applicable when backmixing between the reactor stages can be avoided. The advantage of a multistage reactor in comparison to single-stage equipment was shown by calculation. To obtain a pyrite conversion of 68%, a three-stage reactor would require only 58% of the volume of single-stage equipment.Measurement of oxygen consumption rates proved to provide quickly and easily measurable parameters to observe microbial coal desulfurization in technical scale: the real oxygen consumption rate is correlated to the pyrite oxidation rate and the maximum oxygen consumption rate is correlated to the concentration of viable cells. The Y(o/s) coefficient for the amount of oxygen consumed per mass unit of pyrite oxygen was determined to approximately 0.33 in comparison to 1.0 which can be calculated from stoichiornetry. This could yet not be explained. Chemical leaching experiments as well as sulfur analyses of desulfurized coal samples showed that the microorganisms play the main role in degradation of pyrite from coal and that pyrite oxidation by ferric iron can be neglected.     

Effect of rhamnolipid biosurfactants on performance of coal and mineral flotation

The effect of a concentrated rhamnolipid biosurfactant (purity > 97%) produced by Pseudomonas aeruginosa MA01 on flotation performance of coal and minerals was studied and compared with those from synthetic flotation reagents in both single and mixed systems. Results of phosphate flotation tests showed that phosphate content in the floated product decreased by rhamnolipid concentration. However, final recovery of phosphate at appropriate dosage of reagent was insignificant. This could be ascribed to the increase of iron recovery to final concentrate likely due to collecting action of rhamnolipid for iron minerals. In coal flotation, the increase of rhamnolipid concentration in mixture with pine oil reduced both ash content and coal yield of concentrates. In desulfurization of a sample iron concentrate using reverse flotation, rhamnolipid addition successfully decreased the sulfur content of the iron concentrate. The flotation responses of the studied sample ores showed that rhamnolipid can be used as a promising frother or co-frother in mineral processing practices.     

Thermoacidophilic microbial community oxidizing the gold-bearing flotation concentrate of a pyrite-arsenopyrite ore

An aboriginal community of thermophilic acidophilic chemolithotrophic microorganisms (ACM) was isolated from a sample of pyrite gold-bearing flotation concentrate at 45–47°C and pH 1.8–2.0. Compared to an experimental thermoacidophilic microbial consortium formed in the course of cultivation in parallel bioreactors, it had lower rates of iron leaching and oxidation, while its rate of sulfur oxidation was higher. A new thermophilic acidophilic microbial community was obtained by mutual enrichment with the microorganisms from the experimental and aboriginal communities during the oxidation of sulfide ore flotation concentrate at 47°C. The dominant bacteria of this new ACM community were Acidithiobacillus caldus (the most active sulfur oxidize) and Sulfobacillus thermotolerans (active oxidizer of both iron and sulfur), while iron-oxidizing archaea of the family Ferroplasmaceae and heterotrophic bacteria Alicyclobacillus tolerans were the minor components. The new ACM community showed promise for leaching/oxidation of sulfides from flotation concentrate at high pulp density (S : L = 1 : 4).     

Microbial removal of pyrite from coal using a percolation bioreactor

Summary To compare the suspension and the percolation process system for the microbial desulphurization of coal the microbial pyrite oxidation in coal during storage in dumps was investigated in laboratory experiments with Thiobacillus ferrooxidans using a percolation bioreactor and resulted in a removal of 75% of pyrite within 70 days. In the initial desulphurization phase 450 mg pyritic-S/kg coal per day were oxidized at maximum rate, while the overall rate was determined to 130 mg pyritic-S/kg coal per day. During the desulphurization the mean particle size of the coal was reduced from 0.55 mm to 0.175 mm. As shown by microscopy and elemental analyses of the coal the pyrite was completely removed from small coal particles, whereas parts of it remained in the core of the greater particles.     

A novel mineral flotation process using Thiobacillus ferrooxidans.

Oxidative leaching of metals by Thiobacillus ferrooxidans has proven useful in mineral processing. Here, we report on a new use for T. ferrooxidans, in which bacterial adhesion is used to remove pyrite from mixtures of sulfide minerals during flotation. Under control conditions, the floatabilities of five sulfide minerals tested (pyrite, chalcocite, molybdenite, millerite, and galena) ranged from 90 to 99%. Upon addition of T. ferrooxidans, the floatability of pyrite was significantly suppressed to less than 20%. In contrast, addition of the bacterium had little effect on the floatabilities of the other minerals, even when they were present in relatively large quantities: their floatabilities remained in the range of 81 to 98%. T. ferrooxidans thus appears to selectively suppress pyrite floatability. As a consequence, 77 to 95% of pyrite was removed from mineral mixtures while 72 to 100% of nonpyrite sulfide minerals was recovered. The suppression of pyrite floatability was caused by bacterial adhesion to pyrite surfaces. When normalized to the mineral surface area, the number of cells adhering to pyrite was significantly larger than the number adhering to other minerals. These results suggest that flotation with T. ferrooxidans may provide a novel approach to mineral processing in which the biological functions involved in cell adhesion play a key role in the separation of minerals.     

Intermediary sulfur compounds in pyrite oxidation: implications for bioleaching and biodepyritization of coal

Accumulation of elemental sulfur during pyrite oxidation lowers the efficiency of coal desulfurization and bioleaching. In the case of pyrite bioleaching by Leptospirillum ferrooxidans, an iron(II)-ion-oxidizing organism without sulfur-oxidizing capacity, from the pyritic sulfur moiety about 10% elemental sulfur, 2% pentathionate, and 1% tetrathionate accumulated by a recently described cyclic pyrite oxidation mechanism. In the case of pure cultures of Thiobacillus ferrooxidans and mixed cultures of L. ferrooxidans and T. thiooxidans, pyrite was nearly completely oxidized to sulfate because of the capacity of these cultures to oxidize both iron(II) ions and sulfur compounds. Pyrite oxidation in acidic solutions, mediated chemically by iron(III) ion, resulted in an accumulation of similar amounts of sulfur compounds as obtained with L. ferrooxidans. Changes of pH to values below 2 or in the iron ion concentration are not decisive for diverting the flux of sulfur compounds. The literature on pyrite bioleaching is in agreement with the findings indicating that the chemistry of direct and indirect pyrite leaching is identical. Received: 20 April 1998 / Received revision: 27 August 1998 / Accepted: 3 September 1998     

Relative contributions of biological and chemical reactions to the overall rate of pyrite oxidation at temperatures between 30 degrees C and 70 degrees C

The stoichiometry and kinetics of the spontaneous, chemical reaction between pyrite and ferric iron was studied at 30, 45, and 70 degrees C in shake flasks at pH 1.5 by monitoring the ferrous iron, total iron, elemental sulfur, and sulfate concentration profiles in time. It was found that the sulfur moiety of pyrite was oxidized completely to sulfate. Elemental sulfur was not produced in detectable amounts. The iron moiety of pyrite was released as ferrous iron. All observed initial reaction rates could be fitted into an empirical equation. This equation includes the concentrations of ferric iron and pyrite, and a constant which is dependent on the temperature and the nature of the main anion present. It was observed that ferrous iron formed during the reaction slowed down the oxidation of pyrite by ferric iron. The extent of this effect decreased with increasing temperature. With the aid of the empirical equation, the contribution of the chemical oxidation of pyrite by ferric iron to the overall oxidation in a hypothetical plug-flow reactor, in which biologically mediated oxdidation of pyrite and ferrous iron by oxygen also takes place, can be assessed. At 30, 45, and 70 degrees C, respectively, 2, 8-17, and 43% of the pyrite was oxidized chemically by ferric iron. Therefore, it is expected that only in reactors operating at high temperatures with extremely thermophilic bacteria, will chemical oxidation cause a significant deviation from the apparent first order overall kinetics of biological pyrite oxidation.     

A Novel Approach for Bioleaching of Sulfur,Iron, and Silica Impurities from Coal by Growing and Resting Cells of Rhodococcus spp

Coal is one of the most important sources of fossil energy on earth. However, direct combustion of coal with a high sulfur content can cause various environmental problems. Other constituents of coal that can cause environmental problems include iron oxide (hematite), iron hydroxide, and silica. In this study, growing and resting cells of Rhodococcus erythropolis strains PD1, R1, and FMF, and R. qingshengii were used in heterotrophic removal of sulfur and bioleaching of iron and silica from coal. All of the mentioned strains have an ability of dibenzothiophene (DBT) desulfurization via 4-S pathway. 2-hydroxybiphenyl, sulfate, and ferric ions (Fe³⁺) were assayed by Gibb’s test, barium chloride (BaCl₂), and thiocyanate ions (SCN^?), respectively. FTIR and XRF analyzer were used for detection of the coal bioleaching process by the selected strain of R. erythropolis (PD1). Results indicated that all strains have the ability to grow on coal as the sulfur source. Among them, strain PD1 produced the highest optical density and continued to grow even after 150-h incubation. In both growing- and resting-cells experiments, strain PD1 desulfurized coal most readily compared to other strains. Results of XRF showed that growing cells of strain PD1 had high desulfurizing ability of coal (46%) compared to resting cells in the absence of any carbon sources (24%). Growing cells of strain PD1 also leached 46% of the iron and 14% of the silicate after 7?days of incubation. Resting cells of PD1 leached 32% of the iron as determined by XRF analysis. Also, growing cells of PD1 removed most SiO₂ from coal as detected and confirmed by FTIR and XRF. To the best of our knowledge, this is the first report on bioleaching of iron and silica from coal by R. erythropolis strain PD1, making it a suitable candidate for coal bioremediation.     

Coal Depyritization by the Thermophilic Archaeon Metallosphaera sedula

The kinetics of pyrite oxidation by Metallosphaera sedula were investigated with mineral pyrite and two coals with moderate (Pittsburgh no. 8) and high (New Brunswick, Canada) pyritic sulfur content. M. sedula oxidized mineral pyrite at a greater rate than did another thermophile, Acidianus brierleyi, or a mesophile, Thiobacillus ferrooxidans. Maximum rates of coal depyritization were also greater with M. sedula, although the magnitude of biological stimulation above abiotic rates was notably less than with mineral pyrite. Coal depyritization appears to be limited by the oxidation of pyrite with ferric ions and not by the rate of biotic oxidation of ferrous iron, as evidenced by the maintenance of a high ratio of ferric to ferrous iron in solution by M. sedula. Significant precipitation of hydronium jarosite at elevated temperature occurred only with New Brunswick coal.     

Microbial desulfurization of coal and oxidation of pure pyrite byThiobacillus ferrooxidans andAcidianus brierleyi

Summary Thiobacillus ferrooxidans andAcidianus brierleyi were capable of oxidizing pure pyrite as well as oxidizing sulfur in coal. First order reactions were assumed in the kinetic analysis performed. For oxidation of pure pyrite the rate constant was higher forA. brierleyi than forT. ferrooxidans. For sulfur removal from coal the values of the rate constants were comparable for the two microorganisms.     

Exploring Coal Biodesulfurization Potential of a Novel Organic Sulfur Metabolizing Rhodococcus spp. (Eu-32) – A Case Study

Coal is one of the most abundant nonrenewable fossil fuels, in Pakistan. However, in general, the quality of coal is too low to offset the practical, economic, and regulatory barriers to its utilization. High sulfur content comes up as one of the bottlenecks in productive usage of indigenous coal. Biotechnology can emerge as a panacea for upgrading the huge reserves of high sulfur coal. In current study, the sulfur removal potential of Rhodococcus spp. (Eu-32) was investigated using coal from Dukki, Baluchistan, Pakistan. Biodesulfurization process was optimized for various parameters and maximum decrease of 40% and 60% in total and organic sulfur contents, respectively were achieved in 15 days. The Langmuir and Brunauer–Emmett–Teller (BET) surface areas of the biotreated coal were increased by 20 and 16 times, respectively. Scanning electron microscope showed higher tendency of attachment of bacterial cells to the coal particles. Our results revealed that Eu-32 could remove significant amounts of organic sulfur from coal and could be used in the pre-combustion operations with appropriate arrangements.     

Removal of Sulfur Compounds from Coal by the Thermophilic Organism Sulfolobus acidocaldarius

The thermophilic, reduced-sulfur, iron-oxidizing bacterium Sulfolobus acidocaldarius was used for the removal of sulfur compounds from coal. The inclusion of complex nutrients such as yeast extract and peptone, and chemical oxidizing agents, 0.01 M FeCl₃ into leaching medium, reduced the rate and the extent of sulfur removal from coal. The rate of sulfur removal by S. acidocaldarius was strongly dependent on the sulfur content of the coal and on the total external surface area of coal particles. Approximately 96% of inorganic sulfur was removed from a 5% slurry of coal which had an initial total sulfur content of 4% and an inorganic (pyritic S and sulfate) sulfur content of 2.1%. This resulted in removal of 50% of initial total sulfur present in coal.     

Leaching of Pyrites of Various Reactivities by Thiobacillus ferrooxidans

Wide variations were found in the rate of chemical and microbiological leaching of iron from pyritic materials from various sources. Thiobacillus ferrooxidans accelerated leaching of iron from all of the pyritic materials tested in shake flask suspensions at loadings of 0.4% (wt/vol) pulp density. The most chemically reactive pyrites exhibited the fastest bioleaching rates. However, at 2.0% pulp density, a delay in onset of bioleaching occurred with two of the pyrites derived from coal sources. T. ferrooxidans was unable to oxidize the most chemically reactive pyrite at 2.0% pulp density. No inhibition of pyrite oxidation by T. ferrooxidans occurred with mineral pyrite at 2.0% pulp density. Experiments with the most chemically reactive pyrite indicated that the leachates from the material were not inhibitory to iron oxidation by T. ferrooxidans.     

Continuous bacterial coal desulfurization employing Thiobacillus ferrooxidans

The leaching of pyrite sulfur from coal employing Thiobacillus Ferrooxidans was studied in a continuous stirred tank reactor at a variety of dilution rates (0.02-0.11 h(-1)) and coal surface areas (0.25-1.0 m(2)/mL). The bacterial leaching rate was found to increase with increasing coal surface area concentration and increasing dilution rate. The bacterial concentration on the coal surface was related to the bacterial concentration in solution by a irreversible second-order (of the second kind) kinetic equation. The concentration of bacteria on the coal in all experiments was the concentration at saturation. Step changes in the coal concentration were observed to result in dramatic declines in bacterial concentration in solution. A bacterial mass balance model was employed to calculate the specific growth rate on the solid which was observed to increase with increasing dilution rate.     

Sulfate reduction in lake sediments inhabited by the isoetid macrophytes Littorella uniflora and Isoetes lacustris

Sulfur cycling was examined in sediments inhabited with the isoetids Littorella uniflora and Isoetes lacustris in the oligotrophic soft-water Lake Kalgaard, Denmark. Based on short-term tracer incubations sulfate reduction was measured along a transect from the shore (0.6 m) to profundal sediments (4.6 m). The sulfate reduction rates were low (0.008–0.8 mmol m⁻² d⁻¹) in the sandy shallow sediments with low organic content (<1.3 mmol C g⁻¹ sed DW) and high redox potentials (>100 mV), whereas sulfate reduction was higher at the deeper sites (2.7–4.6 mmol m⁻² d⁻¹) with high organic content (max. 11.5 mmol C g⁻¹ sed DW) and lower redox potentials (<100 mV). High concentrations of dissolved organic carbon (DOC) were found in the low particulate organic sediments (up to 18.4 mM), and most of the DOC pool consisted of acetate (40–77%). Reoxidation of sulfides due to root oxygen release was probably important at all sites and a positive efflux of sulfate across the sediment–water interface was measured, attaining rates (up to 4.8 mmol m⁻² d⁻¹) similar to the sulfate reduction rates. Reoxidation of sulfides was also manifested by high fraction (>80%) of reduced sulfides being accumulated as elemental sulfur or pyrite (chromium reducible sulfur, CRS). The largest pools of CRS were found in high organic sediment with vertical distributions resembling those of the sulfate reduction rates. The overall effect of isoetid growth on sulfur cycling in the rhizosphere is a suppression of sulfate reduction in low organic sediments and the governing of sulfide reoxidation in sediments with higher organic content.