褐煤及其干馏半焦的微孔结构分析

用CO_2吸附法于298K下研究了大雁褐煤、黄县褐煤及其干馏半焦的微孔结构特性。用由Dubinin-Astakhov方程导出的关系式计算了所研究样品的微孔孔径分布和微孔有效表面积S_(micro),讨论了干馏温度对半焦的微孔孔容及平均当量半径的影响。     

混煤热解过程中的表面形态

以管式电炉为热解室,改变热解终温,在惰性气氛下对无烟煤与烟煤的混煤进行快速加热条件下的热解。采用低温氮气吸附方法研究混煤焦表面形态的变化规律。通过对吸附等温线的分析,表明煤焦具有连续、完整的孔隙结构,无定形孔的存在使得吸附迴线存在不闭合的状态。随着热解终温的升高,混煤焦的比表面积先增加后减小;随着烟煤掺混比例的增加,混煤焦的微孔容积和表面积也先增加后减小,A1B2混煤焦具有最大微孔容积和表面积。对煤焦孔隙的分形研究发现煤焦孔隙分形维数与微孔结构关系密切。混煤焦表面形态的变化规律体现了混煤热解的独立性以及相互作用。     

Preparation and Phosphine Adsorption of Activated Carbon Prepared from Walnut Shells by KOH Chemical Activation

Walnut-shell activated carbons (WSACs) with high surface area and predominant micropore development were prepared by KOH chemical activation. The effects of carbonization temperature, activation temperature, and ratio of KOH to chars on the pore development of WSACs and PH₃ adsorption performance of the modified walnut-shell activated carbons (MWSACs) were studied. Criteria for determining the optimum preparation conditions were pore development of WSACs and PH₃ breakthrough adsorption capacity of MWSAC adsorbents. The result shows that the optimum preparation conditions are a carbonization temperature of 700°C, an activation temperature of 700°C, and a mass ratio of 3. The BET surface area and the micropore volume of the optimal WASC are 1636m²/g and 0.641cm³/g, respectively. The micropore volume percentage of WSAC plays an important role in PH₃ adsorption when there is a slight difference in BET surface areas. High-surface-area WSACs with predominant micropores are suitable for PH₃ adsorption removal. The MWSAC adsorbent owns the biggest PH₃ breakthrough adsorption capacity (284.12mg/g) due to the biggest specific surface area, total pore volume, and micropore volume percentage. The MWSAC adsorbent will be a potential adsorbent for PH₃ adsorption removal from yellow phosphorus tail gas.     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

Pore development during carbonization of coals

Changes in pore properties during carbonization at a constant heating rate and no external pressure were followed for bituminous and subbituminous coals by porosimetry, sorption and density measurements. Observations were supplemented by scanning electron microscopy and rate of volatilization measurements. All coals exhibited similar devolatilization behaviour and pore structure development, showing maximum micro and macropore volumes around 600 °C, and a partial collapse of pore structure after 800 °C. The micropore structure did not collepse in the case of non-caking coal. Pore volume maxima occur at least 100 °C above the temperature of the devolatilization rate maxima. Some interpretation is provided.     

A reactivity study of chars obtained at different temperatures in relation to their petrographic characteristics

This study reports on the reactivity of chars obtained at 1000°C and 1300°C (within the range of temperatures reached by coal particles in the near-burner zone of pulverised fuel boilers) from three different coals. The coals were selected according to petrographic criteria: two of them are high volatile bituminous coals differing in maceral composition and the third one is a vitrinite-rich low volatile bituminous coal.The morphology and optical texture of the chars were studied by optical microscopy. The kinetic parameters for the combustion of the high temperature chars under Regime I (combustion controlled by chemical kinetics) have been obtained and related to the optical texture and reflectance of the chars. The intrinsic reactivity of the high temperature chars was found to be lower than that of the low temperature chars, whereas the enhanced porosity observed in the high temperature chars had a positive effect on their combustion reactivity under Regime II (combustion controlled by oxygen pore diffusion). The intrinsic reactivities of the chars decreased following the sequence: vitrinite-rich low rank char>inertinite-rich char>vitrinite-rich high rank char. As the combustion temperature increases, the reactivity of the inertinite-rich char approaches that of the low rank vitrinite-rich char, which justifies the good performance observed for high volatile bituminous inertinite-rich coals in power plants.     

INFLUENCE OF CHAR PROPERTIES ON REACTION RATES

The reaction of coal char is affected by the char morphology, which is dependent on the temperature and pressure at which the char is prepared. Char properties, such as surface area (by CO₂ adsorption) and diffusion coefficients of CO₂ in char have been measured for chars prepared at 900-1200°C and at pressure to 16 atm at 900°C. The diffusion coefficient results strongly indicate Knudsen or activated surface diffusion. The surface areas and diffusion coefficients decrease in general at higher preparation temperatures, but have a maximum at 1000°C. There is an apparent relationship between these observations and the reactivity results which demonstrate unusual behavior above 1000°C.     

Low-temperature air oxidation of caking coals. 1. Effect on subsequent reactivity of chars produced

The effect of preoxidation of two highly caking coals in the temperature range 120–250 °C on weight loss during pyrolysis in a N₂ atmosphere up to 1000 °C and reactivity of the resultant chars in 0.1 MPa air at 470 °C has been investigated. Preoxidation markedly enhances char reactivity (by a factor of up to 40); the effect on char reactivity is more pronounced for lower levels of preoxidation. For a given level of preoxidation, the oxidation temperature and the presence of water vapour in the air used during preoxidation have essentially no effect on weight loss during pyrolysis and char reactivity. An increase in particle size of the caking coals reduces the rate of preoxidation as well as subsequent char reactivity. Preoxidation of caking coals sharply increases the surface area of the chars produced. Compared to heat treatment in a N₂ atmosphere, pyrolysis in H₂ of either the as-received or preoxidized coal results in a further increase in weight loss and a decrease in subsequent char reactivity.     

Effect of inorganic matter removal from coals and chars on their surface areas

Removal of inorganic matter from coals by acid treatment brings about random and, in some cases, significant changes in surface areas measured by adsorption of N₂ and CO₂. Changes in surface areas of chars are generally more pronounced than those found in coals. However, the surface area changes in chars are markedly dependent upon whether the acid treatment is given to the coal precursor prior to charring or to the char produced from the raw coal. Changes in surface areas of raw coals and chars produced therefrom have been attributed to: (i) ‘physical’ removal of inorganic matter from the aperture-cavity system, (ii) bonding of HCl to basic nitrogen present in pyridine-like structures, and (iii) adsorption of acid. Results suggest that the removal of inorganic matter from coals prior to charring affects the carbonization process and, hence, the surface area of the resultant char.     

Effects of coal carbonization conditions on rate of steam gasification of char

Effects of carbonization conditions on char reactivity in steam gasification were evaluated by a gravimetric method, using 12 coals varying widely in rank, type and source. The carbonization variables examined were

• 1.(1) heating rate (5–420K min⁻¹) in steam atmosphere;
• 2.(2) gaseous atmosphere (N₂,H₂,H₂O andCO₂);
• 3.(3) incomplete devolatilization in N₂ (final temperature 200–800 °C);
• 4.(4) quenching of incompletely devolatilized char; and
• 5.(5) complete carbonization (900–1400 °C).

The char reactivity to steam depended on the kind of coal but was almost independent of the carbonization conditions of heating rate, gaseous atmosphere and quenching at temperatures below ≈ 1000 °C. Carbonization above 1100 °C reduced the char reactivity, for example by a factor of 7 to 10 at 1300 °C compared with 900–1000 °C, depending on the parent coal. The char deactivation brought about by increasing carbonization temperature could be correlated with a decrease in the micropore volume of the char, unless graphitization was significant.     

Gasification studies of onakawana lignite

Onakawana lignite was gasified in air, steam and an air + steam mixture in a fixed bed reactor. The extent of devolatilization was determined by pyrolysis in nitrogen. The composition of products, expressed in terms of H₂/CO ratio, was temperature dependent. The ratio decreased with increasing temperature. During steam gasification the ratio decreased from 4.6 to 2.6 when temperature increased from 700° to 990°C. The addition of air to steam resulted in a marked decrease of this ratio. Steam gasification reactivity of chars prepared from Onakawana lignite at 500°C and 800°C were studied in the temperature range of 650°C to 1000°C. The carbon conversion results were fitted into equations describing the continuous and shrinking core models. The char prepared at 500°C was much more reactive than the one prepared at 800°C. Product distribution expressed as the H₂/CO ratio, was favourable in the temperature range. For comparison, the Kentucky #9 coal and chars derived from this coal were used as referee materials. The reactivity of these chars was markedly lower than that of chars derived from Onakawana lignite.     

Porous properties of activated carbon produced from Eucalyptus and Wattle wood by carbon dioxide activation

This work focused on the preparation of activated carbon from eucalyptus and wattle wood by physical activation with CO₂. The preparation process consisted of carbonization of the wood samples under the flow of N₂ at 400°C and 60 min followed by activating the derived chars with CO₂. The activation temperature was varied from 600 to 900°C and activation time from 60 to 300 min, giving char burn-off in the range of 20/2-83%. The effect of CO₂ concentration during activation was also studied. The porous properties of the resultant activated carbons were characterized based on the analysis of N2 adsorption isotherms at −196°C. Experimental results showed that surface area, micropore volume and total pore volume of the activated carbon increased with the increase in activation time and temperature with temperature exerting the larger effect. The activated carbons produced from eucalyptus and wattle wood had the BET surface area ranging from 460 to 1,490 m²/g and 430 to 1,030 m²/g, respectively. The optimum activation conditions that gave the maximum in surface area and total pore volume occurred at 900°C and 60 min for eucalyptus and 800°C and 300 min for wattle wood. Under the conditions tested, the obtained activated carbons were dominated with micropore structure (∼80% of total pore volume).     

Reactivity of heat-treated coals in steam

Reactivities of seventeen 40 × 100 mesh (U.S.) coals charred to 1000 °C have been measured at 910 °C in 0.1 MPa of a N₂H₂O mixture containing water vapour at a partial pressure of 2.27 kPa. Char reactivity decreases, in general, with increasing rank of the parent coal. The chars show a 250-fold difference in their reactivities. Results suggest that gasification of chars in air, CO₂ and steam involves essentially the same mechanism and that relative gasification rates are controlled by the same intermediate oxygen-transfer step. Removal of inorganic matter from raw coals prior to their charring or from chars produced from raw coals decreases the reactivities of lower-rank chars, whereas reactivities of higher-rank chars increase. Addition of H₂ to steam has a marked retarding effect on char reactivity in most cases. However, in a few cases H₂ acts as an accelerator for gasification. The effect of particle size, reaction temperature and water-vapour pressure on char reactivity is considered.     

Preparation and characterization of polymer‐based spherical activated carbons with tailored pore structure

A series of spherical activated carbons (SACs) with different pore structure were prepared from divinylbenzene‐based polymer through CO₂ activation. The effect of activation temperature and retention time on the yield and textural properties of the resulting SACs were studied. The SACs were characterized by N₂ adsorption, X‐ray diffraction, scanning electron microscopy, and aqueous adsorption assays. Either increasing activation temperature or extending retention time decreases the yield of SACs. The BET surface area and pore volume increase with activation temperature and reach a maximum at 1000°C and then decrease at higher activation temperatures. At 1000°C, BET surface area, total pore volume, and mesopore pore volume increase with retention time from 0.5 to 2 h, and meanwhile micropore volume decreases. The micropores are gradually widened into mesopores with increasing activation temperature or extending retention time. SEM and XRD analyses of SAC10 verify the presence of developed porous structure composed of disordered micrographite stacking. Aqueous adsorption assays indicate that SACs have good adsorption capacity for phenol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactivity study of combustion for coals and their chars in relation to volatile content

To determine the effect of volatile matter on combustion reactivity, the pyrolysis and combustion behavior of a set of four (R, C, M and K coals) coals and their chars has been investigated in a TGA (SDT Q600). The maximum reaction temperatures and maximum reaction rates of the coals and their chars with different heating rates (5–20 °C/min) were analyzed and compared as well as their weight loss rates. The volatile matter had influence on decreasing the maximum reactivity temperature of low and medium rank coals (R, C and M coals), which have relatively high volatiles (9.5–43.0%), but for high rank coal (K coal) the maximum reactivity temperature was affected by reaction surface area rather than by its volatiles (3.9%). When the maximum reaction rates of a set of four coals were compared with those of their chars, the slopes of the maximum reaction rates for the medium rank coals (C and M coals) changed largely rather than those for the high and low rank coals (R and K coals) with increasing heating rates. This means that the fluidity of C and M coals was larger than that of their chars during combustion reaction. Consequently, for C and M coals, the activation energies are lower (24.5–28.1 kcal/mol) than their chars (29.3–35.9 kcal/mol), while the activation energies of R and K coals are higher (25.0-29.4 kcal/mol) than those of their chars (24.1–28.9 kcal/mol).     

Coal lump devolatilization and the resulting char structure and properties

Lumps of six bituminous coals, from 20 to 40 mm in size, were devolatilized in a laboratory oven in nitrogen atmosphere at different final temperatures ranging from 300 to 800 °C. The structure and morphology of the resulting chars with different degree of devolatilization have been examined under an optical microscope in order to better understand the formation mechanism of different types of char. The swelling of the caking coals and the fissuring of the non-caking coals were characterised by image analysis and some correspondences between the distribution of lithotypes within the initial coal lumps and the char structure obtained were revealed. The relation between chars structure and properties was also investigated. The char lumps obtained from caking coal exhibit better resistance to breakage than their parent coal lumps while non-caking coals show the opposite behaviour. For both caking and non-caking coals, a significant decrease of resistance is observed in the intensive devolatilization temperature range from 400 to 600 °C.     

Importance of carbon active sites in the gasification of coal chars

A demineralized lignite has been used in a fundamental study of the role of carbon active sites in coal char gasification. The chars were prepared in N₂ under a wide variety of conditions of heating rate (10 K min^?1 to 10⁴ K s^?1), temperature (975–1475 K) and residence time (0.3 s–1 h). Both pyrolysis residence time and temperature have a significant effect on the reactivity of chars in 0.1 MPa air, determined by isothermal thermogravimetric analysis. The chars were characterized in terms of their elemental composition, micropore volume, total and active surface area, and carbon crystallite size. Total surface area, calculated from C0₂ adsorption isotherms at 298 K, was found not to be a relevant reactivity normalization parameter. Oxygen chemisorption capacity at 375 K and 0.1 MPa air was found to be a valid index of char reactivity and, therefore, gives an indication, at least from a relative standpoint, of the concentration of carbon active sites in a char. The commonly observed deactivation of coal chars with increasing severity of pyrolysis conditions was correlated with their active surface areas. The importance of the concept of active sites in gasification reactions is illustrated for carbons of increasing purity and crystallinity including a Saran char, a graphitized carbon black and a spectroscopically pure natural graphite.     

Change of pore properties during carbonization of coking coal

Porosimetry, sorption and density measurements are reported on two caking bituminous coals, West Virginia Jewel No. 2 medium volatile and a Pennsylvania Pittsburgh seam high volatile C, for final carbonization temperatures between 400 and 1000°C. Samples were not confined and heating rates of 3 and 8.2°/min were employed. The medium volatile samples exhibit pronounced maxima in pore volume, pore surface area and porosity between 600 and 800°C. These temperatures are considerably greater than the characteristic temperature and the temperature at which maximum dilation occurs. The high volatile C coal does not exhibit well defined maxima. Results are interpreted in terms of pore development mechanisms. A mathematical model for pore development is proposed and shown to correlate satisfactorily, the pore volume and surface area measurements.     

Reactivity of heat-treated coals in hydrogen

Reactivities of eighteen 40 × 100 mesh U.S. coals charred to 1000 °C have been measured in H₂ at 2.7 MPa and 980 °C. The char-hydrogen reaction usually occurs in two stages: a slow induction period followed by a constant-rate region. Reactivities of various chars in the initial stage (R_i) decrease, in general, with increasing carbon content of the parent coals, whereas reactivities in the constant-rate region (R_c) are essentially independent of the rank of the parent coals. Reactivities of chars in H₂ differ markedly from those in air and CO₂. Results of surface-area measurements of chars and activation energies for the hydrogasification reaction suggest that during the induction period the reaction is diffusion-controlled whereas in the constant-rate region it is chemically controlled. Upon removal of mineral matter, R_i values generally decrease but R_c values show a random variation. Removal of mineral matter from coals prior to their carbonization brings about profound changes in surface area and porosity of chars. The effect of char particle size on reactivity is considered.