Modeling and process optimization for microbial desulfurization of coal by using a two-level full factorial design

The microbial sulfur removal was investigated on high sulfur content (1.9%) coal concentrate from Tabas coal preparation plant. A mixed culture of ferrooxidans microorganisms was isolated from the tailing dam of the plant. Full factorial method was used to design laboratory test and to evaluate the effects of pH, particle size, iron sulfate concentration, pulp density, and bioleaching time on sulfur reduction. Statistical analyses of experimental data were considered and showed increases of pH and particle size had negative effects on sulfur reduction, whereas increases of pulp density and bioleaching time raised microbial desulfurization rate. According to results of designing, and regarding statistical factors, the optimum values for maximum sulfur reduction were obtained; pH (1.5), particle size (-180 μm), iron sulfate concentration (2.7 mmol/L), pulp density (10%) and bioleaching time (14 d), which leaded to 51.5% reduction from the total sulfur of sample.

THE APPLICATION OF REVERSE FLOCCULATION METHOD IN HIGH SULFUR COAL DESULFURIZATION

The reverse flocculation method for removing pyritic sulfur from high sulfor coals has been conceptually beveloped and investigated. The tentative tests on China high sulfur coals have shown that this advanced physical separation techaique can be very efficient in coal desulfurization, provided the process parameters are properly optimized. Under the circumsances of acquiring high coal recovery, the total sulfur rejection with four kinds of coal samples normally falls in tbe range 57% to 71 % by one-step reverse flocculation, and within the range 40% to 59% by one-step normal flocculation process.

Progress of the technique of coal microwave desulfurization

With the advantages of its fast speed,effective and moderate controllable conditions,desulfurization of coal by microwave has become research focus in the field of clean coal technology.Coal is a homogeneous mixture which consists of various components with different dielectric properties,so their abilities to absorb microwaves are different,and the sulfur-containing components are better absorbers of microwave,which makes them can be selectively heated and reacted under microwave irradiation.There still remain controversies on the principle of microwave desulfurization at present,thermal effects or non-thermal effects.The point of thermal effects of microwave is mainly base on its characters of rapidly and selectly heating.While,in view of non-thermal effect,direct interactions between the microwave electromagnetic field and sulfur containing components are proposed.It is a fundamental problem to determine the dielectric properties of coal and the sulfur-containing components to reveal the interaction of microwave and sulfur-containing compounds.However,the test of dielectric property of coal is affected by many factors,which makes it difficult to measure dielectric properties accurately.In order to achieve better desulfurization effect,the researchers employ methods of adding chemical additives such as acid,alkali,oxidant,reductant,or changing the reaction atmosphere,or combining with other methods such as magnetic separation,ultrasonic and microorganism.Researchers in this field have also put forward several processes,and have obtained a number of patents.Obscurity of microwave desulfurization mechanism,uncertainties in qualitative and quantitative analysis of sulfur-containing functional groups in coal,and the lack of special microwave equipment have limited further development of microwave desulfurization technology.

Microorganisms desulfurization of coal

A culture of Thiobacillus ferrooxidans strain T-4, isolated from Song Zao Coal Mining, China, is able to use pyrite from coal as a source of energy. The bacterial culture solution with 108 -109 cells/ml, pH 1.55 - 1.70 was employed in the nine coal samples with -200 mesh have been studied at initial pH 1.7.30℃ , 20-30% coal pulp density. The bacterial removal sulfur from coal in samples 3, 4, 6 and 7 were reduced to 1.05 - 1.33% and 86.11% of pyritic sulfur can be removed in 4-24 hours.

Changes in sulfur form during coal desulfurization with microwave:Effect on coal properties

The changes in sulfur form in coal were analyzed by sulfur K-XANES(K-edge X-ray absorption near edge structures) spectra before and after the coal microwave desulfurization in a Na OH solution. After the desulfurization, the pyritic sulfur content of coal decreased significantly from 53.6% to 39.2%, while the sulfate sulfur content increased from 17.3% to 34.6%. Only a small amount of thiophene sulfur(20.1–16.1%) was removed. Some sulfur-containing components were oxidized to sulfate sulfur. Under the optimum conditions, the ash content decreased, while the volatile content increased. The calorific value of coal slightly decreased with a slight variation in the amplitudes. The overall structure of coal did not change significantly based on Fourier transform infrared(FTIR) spectral analyses. Thus, the desulfurization of coal with microwave irradiation in a Na OH solution did not significantly change the properties of coal.

Effect of impurities on desulfurization properties of limestone during coal gasification

In order to understand the function of calcium based sorbents on desulfurization during coal gasification and the effect of impurities on it, a series of tests using three different limestones and four kinds of different sodium salts and four kinds different chlorides were conducted by X ray diffraction and X ray photoelectron spectroscopy techniques. The structure of precursory compounds and pretreatment materials were examined by XRD. The binding energy and relative contents of sulfur, calcium and carbon, which exist in different forms in the residues after coal gasification, were measured by means of XPS. The existing forms of sulfur and calcium vary with impurities in limestone. Sodium or chloride play a promotive role on limestone desulfurization, but this promotion is affected by the chemical environment.

MOSSBAUER ANALYSIS ON THE MICROWAVE-MAGNETIC DESULFURIZATION OF RAW COAL

The selective dielectric heating of microwave energy to convert a portion of each pyrite particle to moderately magnetic pyrrhotite has been suggested to enhance the magnetic separation of inorganic sulfur from coal. The results for Mossbauer analyses show that the considerable amount of pyrrhotite produced during microwave irradiation, carrying with it some of non--magnetic pyrite (unconverted), ferrous sulfate, and troilite, is completely removed from coal after magnetic separation. The opthoum desulfurization efficiency can be attsined by appropriately controlling the irradiation time to maximize the amount of pyrrhotite formed pyrite decomposition.Excessive irradiation would be disadvantageous for improving magnetic separation due to the further decomposition of pyrrhotite to antiferromagnetic troilite.

Fractal desulfurization kinetics of high-sulfur coal

The pore structure characteristics of high-sulfur coal from Wansheng in Chongqing have been studied by a nitrogen adsorption method （BET）. The effects of grinding and pre-treating with nitric acid on the inorganic sulfur content of coal have been investigated. Organic sulfur in coal pretreated with nitric acid was desulfurized by using propylene-glycol-KOH （PG-KOH）. Fractal kinetic properties of these two desulfurization procedures were investigated by using fractal geometric theory. The results show that both the specific surface area and pore volume increased with the decrease in particle diameter. The microspore surface of coal had fractal characteristics; the fractal dimension was 2.48. The sulfur content decreased with the decrease in particle diameter by grinding. After pretreatment with nitric acid, the desulfurization ratio （DFR） of inorganic sulfur increased to over 99% and the DFR of total sulfur to over 70%. The desulfurization procedure of inorganic sulfur had fractal kinetic characteristics; its reactive frac- tal dimension was 2.94. The organic sulfur desulfurization procedure by PG-KOH was also tallied with fractal kinetic properties; the reactive fracta! dimension was 2.57. The effect of temperature on the desul- furization ratio of organic sulfur can be described with an Arrhenius empirical equation. The rate constant, pre-exponential factor and the activation energy of the reaction increased with the decrease in particle diameter.

Thermodynamic Analysis of Desulfurization of Fine Coal by Electrochemical Reduction Flotation

Problems in desulfurization of coal by electrochemical reduction is analyzed and calculated. The result shows that 1 ) the △rGm function of the reaction of pyrite into FeS and the modifying reaction decreasing the oxygenous functions on coal surface is smaller than zero in a spontaneous reaction, and greater than zero in a non-spontaneous reaction; 2) the △rGm value can be adjusted by pH and the dosage of electrolyte to make it be greaterthan zero , which is favorable for the modifying reaction and useful for desulfurization of coal. The research has provided a theoretical foundation for determining reasonable technical parameters of desulfurization。

Research on Factors Affecting Flotation and Desulfurization of Coal by Electrochemical Method

Influence of factors such as potential of electrolyte, electrolyzing time, concentration of electrolyte, and pH value on flotation and desulfurization of coal was researched. The result shows that the electrochemical reduction can enhance the desulfurization effect and increase the yield of clean coal under certain conditions. So it is an effective method.

TRACKING PYRITIC SULFUR DURING THE MICROWAVE- CHEMICAL DESULFURIZATION OF COAL USING MOSSBAUER SPECTROSCOPY

The transformations of pyrite in coal during the microwave-chemical treatment for desulfurization of coal was studied with Mossbauer spectroscopy of Fe. The results for phase analyses show that the selective dielectric heating by microwave energy can give rise to the thermal decomposition of pyrite FeS2 in coal to new phases, pyrrhotite Fe1-xS (0【x≤0.125) and troilite FeS which can be dissolved in dilute HC1 solution. Therefore the microwave irradiation combined with the acid washing treatment will be an effective method of desulfurization of coal.

AN ADVANCED COAL DESULFURIZATION PROCESS──SELECTIVE FLOCCULATION

Selective flocculation is an idea separation method to separate ultrafine pyrite from coal. A number of selective flocculation separation tests under different conditions have been done and the results are very encouraging. The results also show that desulfurization and deashing can be finished simultaneously in selective fIocculation process. It is an advanced coal desulfurization process.

EXPERIMENTAL STUDY OF DESULFURIZATION OF ZHONG LIANG SHAN HIGH SULFUR COAL BY FLOTATION

Emission of large amount of SO2 from combustion of liigh sulfur ctal causes serious envitonmcntai pollution. Pre-combustion desunrization of high sulfur coal has become a necessity.Thts paper reports test results of fine coal dcaulfurization with different flotation technology and theeffect of pyrite depressant. Test work showed that when the coal sample from Zhong Liang Shanwas processed with a Free Jet Flotation Column its pyritic sulfur content was reduced from 3.08%to 0. 84%, with 72. 22% recovery ofcomhustiblc matter in clean coal. The coneept of Desulfuriza tion Efficiency Index E for comprehensive evaluation of desumirhation process is proposed, whichis deffeed as the product of the ratio of sulfur content reduction of clean ctal and the recovery ofcomhustihle matters.

Characterization and Desulfurization Possibilities of High Sulfur Gediz-Turkey Coal

Coal is one of the important energy sources, but it causes serious environmental problems such as air pollution, acid rain and greenhouse effects. Sulfur in coal is one of the responsibilities of these negative effects. Coal includes two types of sulfur： organic and inorganic. While inorganic sulfur can be completely removed with physical desulfurization methods, organic sulfur can be removed only by chemical desulfurization methods. But chemical methods are not only expensive but also difficult processes. Firstly in desulfurization, types of the sulfur content in coal should be well characterized. High sulfur Gediz-Turkey coal has been chosen to this study. This coal basin is located in the centre of the Turkey. In this study, characterization and desulfurization possibilities of high sulfur Gediz coal were investigated. For this purpose, several physical and chemical characterization methods such as proximate and ultimate coal analysis （ash, calorific value, volatile matter, moisture and sulfur analysis）, mineralogical and petrographic analysis, fourier transform infrared spectroscopy, scanning electron microscope were used. Results of these analysis are shown that Gediz coals include 3.15% pyritic sulfur and 2.89% organic sulfur. Removing pyritic sulfur from Gediz-Turkey coal with physical methods such as gravity and sink-float separation is not possible because pyrite particle has 1-2 micron liberation size in coal.

Desulfurization kinetics of ZnO sorbent loaded on semi-coke support for hot coal gas

Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.

Desulfurization of coal by an electrochemical-reduction flotation technique

The optimum conditions for sulfur removal from coal by electrochemical reduction flotation in an aqueous NaCl solution were determined from orthogonal experiments. The effect of electrolytic conditions on the desulfurization ratio was also studied. The electrochemical-reduction processed coal was examined by X-ray diffraction, Fourier transform infrared spectroscopy and wet chemical analysis. The results show that electrochemical reduction converts hydrophobic pyrite in Nantong coal into hydrophilic FeS and S2- and leads to an increase in the concentration of hydroxyl groups and aliphatic moieties and a corresponding decrease in carboxyl and carbonyl groups, which enhances the flotation desulfurization of the coal.

EFFECT OF COAL PYRITE SURFACE OXIDA-TION ON COAL DESULFURATION BY FLOTA-TION AND METHODS OF PYRITE DEPRESSION

This paper discusses the hydrophobicity of the pyrite surface under different extents of oxidation. Experimental results demonstrate that pyrite is floatable only under initial oxidation of its surface, while the fresh unoxidized or deeply oxidized surface of pyrite is hydrophilic. In the tests an organic reductant C6H3(OH)3 was chosen as the pyrite depressant. It is highly efficient ,and the sulfur in flotation can be significantly improved.

SO_2 emission characteristics from co-firing of petroleum coke and coal in circulating fluidized bed

Combustion and sulfur retention experiments of mixed fuel of petroleum cokeand coal were conducted on a pilot-scale circulating fluidized bed (CFB) combustor with the thermalinput of 0. 6 MW. The effects of several parameters, such as the primary air percentage, excess aircoefficient, bed temperature, Ca/S molar ratio and mass ratio of petroleum coke to coal on SO_2emission were verified. Experimental results show that when the ratio of petroleum coke to coal inthe mixed fuel increases, the SO_2emission increases. The maximum SO_2 emission appears when purecoke burns. The SO_2 concentration in flue gas reduces with the increase in the primary airpercentage, excess air coefficient and Ca/S molar ratio for all kinds of fuel mixtures. Therangebetween 830 t and 850 t is the optimal temperature for sulfur retention during co-firing ofpetroleum coke and coal with the mass ratio R of 1 and 3 in CFB.

Effect of binder on the properties of iron oxide sorbent for hot gas desulfurization

The most difficult problem in hot gas desulfurization in Integrated Coal Gasification Combined Cycle （IGCC） is the pulverization of sulfur removal sorbents.Appropriate binders for hot gas sulfur removal sorbents can solve the pulverization problem.In this paper,six sorbents with binders of different argillaceous minerals were prepared by mechanical mixing method.Desulfurization behavior for hot gas desulfurization sorbents was investigated in a fixed-bed reactor.Result showed that sorbent NTKW2 with binder of clay had a better sulfidation performance.NTKW2 had a more stable performance than other sorbents in the continuous sulfidation-regeneration cycles.Sulfur capacity of sorbent remained the same in each cycle.The desulfurization efficiency and mechanical strength of NTKW2 were the best among the tested sorbents.The behavior of NTKW2 at different temperatures showed different performances,and the best reaction temperature was 550 ℃.Higher heat stability,sulfur capacity and desulfurization efficiency were found on NTKW2 in six continuous sulfidation-regeneration cycles.

Research on improvement in Zn-based sorbent for hot gas desulfurization

Two Zn-based sorbents, L-991 and L-992 used for hot gas desulfurization (HGD) were introduced. Zn/Ti ratio of the two sorbent was 1:1 and 2:3 resptively and a certain proportion of Cu and Mn metal oxide were added into L-992, which provided better performance than L-991 in aspects of suitable work temperature, sulfur capacity and agglomeration on the surface of sorbent particles. The evaluation tests were done on both sorbents include multi cycles tests. ARD and SEM analysis were done on fresh and post tests sorbent. During continuous sulfidation/regeneration, the H2S concentra- tion can be reduced from about 10 g/m3 to less than 20 mg/m3, the H2S removal effi- ciency >99 %.