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1.
The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N2 physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (Stotal) and micropore surface area (Smicro) reached maximum values of 30.94 and 21.81 m2/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on Stotal and Smicro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.  相似文献   

2.
A study of the possibilities of pyrolysis for recovering wastes of the rope's industry has been carried out. The pyrolysis of this lignocellulosic residue started at 250 °C, with the main region of decomposition occurring at temperatures between 300 and 350 °C. As the reaction temperature increased, the yields of pyrolyzed gas and oil increased, yielding 22 wt.% of a carbonaceous residue, 50 wt.% tars and a gas fraction at 800 °C. The chemical composition and textural characterization of the chars obtained at various temperatures confirmed that even if most decomposition occurs at 400 °C, there are some pyrolytic reactions still going on above 550 °C. The different pyrolysis fractions were analyzed by GC–MS; the produced oil was rich in hydrocarbons and alcohols. On the other hand, the gas fraction is mainly composed of CO2, CO and CH4. Finally, the carbonaceous solid residue (char) displayed porous features, with a more developed porous structure as the pyrolysis temperature increased.  相似文献   

3.
Organosolv lignin has been selected to investigate the thermal behavior of lignin over zeolites by using a thermogravimetric analyzer coupled with a Fourier-transform infrared spectrometer (TG-FTIR). The chemical structure of this lignin has been determined by 1H NMR to obtain the distribution of main functional groups such as methoxyl groups and free aliphatic and phenolic hydroxyl groups. All three zeolite catalysts tested, HZSM-5, H-β, and USY, exerted significant influences on the dehydration reaction in the initial stage, the deoxygenation reaction of oxygenated compounds such as methanol and phenols, and the char-forming process during lignin pyrolysis in the range 30–800 °C. The dehydration reaction was enhanced in the order USY > HZSM-5 > H-β, while char formation was suppressed in the reverse order. The presence of HZSM-5 and H-β catalyzed the conversion of both oxygenated compounds and chars into the low-molecular-weight gases CO, CO2, and methane. The addition of USY clearly aided decomposition of the oxygenated compounds, but had little effect on the char degradation.  相似文献   

4.
Poly(p-phenylene benzobisoxazole) (PBO) was impregnated with small amounts of H3PO4, and the effects of this additive on the porosity and other characteristics of chars and activated carbon fibers (ACFs) derived from this polymer were investigated. To this end, PBO-AS impregnated with 5, 10 or 15 wt.% H3PO4 was pyrolyzed at 850 °C, and the resulting chars were physically activated with carbon dioxide at 800 °C to different burn-off (BO) degrees. Thermal analysis techniques only detected minor effects of H3PO4 on PBO pyrolysis. The char yield and char reactivity towards CO2 increased following PBO-AS impregnation with H3PO4. Structural (X-ray diffraction), porous textural (CO2 adsorption) and surface chemical (temperature-programmed desorption, X-ray photoelectron spectroscopy) characterizations of the pyrolysis chars indicated that the increase in char reactivity is probably associated with a higher content of oxygenated functionalities. Following CO2 activation, the surface area and pore volume of the obtained ACFs chiefly depended on the BO degree, but impregnation with H3PO4 restricted the pore size to the micropore and narrow mesopore range, thus producing adsorbents with a slightly narrower pore size distribution than in the absence of H3PO4. The results are compared with those previously obtained under equivalent conditions with other high-crystallinity polymers as precursors for ACFs.  相似文献   

5.
Gasification uses steam increases H2 content in the syngas. Kinetics of gasification process can be improved by using K2CO3 catalyst. Controlled heating rate in pyrolysis step determines the pore size of charcoal that affects yield gas and H2 and CO content in the syngas. In previous research, pyrolisis step was performed without considering heating rate in pyrolysis step. This experiment was performed by catalytic steam gasification using lignite char from pyrolysis with controlled heating rate intended to produce maximum yield of syngas with mole ratio of H2/CO ≈ 2. Slow heating rate (3 °C/min) until 850 °C in the pyrolysis step has resulted in largest surface area of char. This study was performed by feeding Indonesian lignite char particles and K2CO3 catalyst into a fixed bed reactor with variation of steam/char mole ratio (2.2; 2.9; 4.0) and gasification temperature (750 °C, 825 °C, and 900 °C). Highest ratio of H2/CO (1.682) was obtained at 750 °C and steam/char ratio 2.2. Largest gas yield obtained from this study was 0.504 mol/g of char at 900 °C and steam/char ratio 2.9. Optimum condition for syngas production was at 750 °C and steam/char mole ratio 2.2 with gas yield 0.353 mol/g of char and H2/CO ratio 1.682.  相似文献   

6.
In the present work four different biomass samples (pine cone, soybean cake, corn stalk and peanut shell) were pyrolyzed to 550 °C in an inert gas atmosphere and a comparison between the properties of chars produced has been performed. Characterization of biomass samples was carried out with FT-IR, 13C NMR, SEM and EDX. The influence of the parent material on char quality was investigated. The chars were characterized by their proximate and ultimate analysis and surface areas by N2 adsorption at 77 K using BET equation. The morphological changes in carbonaceous solids were observed by scanning electron microscopy (SEM), and FT-IR spectra were obtained to evaluate the functional groups. The results obtained from the different techniques were combined to give an overview of the chemical and physical properties of the biomass char samples.  相似文献   

7.
The determination of chromium (VI) compounds in plants by electrothermal atomic absorption spectrometry (ET AAS) is proposed based on their leaching with 0.1 M Na2CO3. Due to the presence of relatively high amounts of Na2CO3 in the resulting samples, the temperature and time of pyrolysis and atomization stages must be optimized to minimize the influence of the matrix. A limit of detection (LOD) for determination of Cr(VI) in plants by ET AAS was found to be 0.024 μg g−1.The concentration of Cr(VI) and total chromium in plants collected in different geographical areas (South Africa and Russia), grown on soils high in chromium was determined. The concentration of Cr(VI) and total Cr in stems and leaves of plants was in the range of 0.04–0.7 μg g−1 and 0.5–10 μg g−1, respectively. The limited uptake of Cr(III) by plants, in comparison to its concentration in soil, can be explained by the very low solubility of natural Cr(III) compounds.Results for the determination of Cr(VI) were confirmed by the analysis of BCR CRM 545 (Cr(VI) in welding dust) with good agreement between certified (39.5 ± 1.3 μg mg−1) and found (38.8 ± 1.2 μg mg−1) values. The total concentration of Cr in plants has also been determined by ET AAS after dry ashing of samples at 650 °C. Results were confirmed by the analysis of BCR CRM 281 (Trace elements in Rye Grass) with good agreement between the found (2.12 ± 0.16 μg g−1) and certified value (2.14 ± 0.12 μg g−1).  相似文献   

8.
The gas release properties and char structural evolution during the pyrolysis of cotton stalk were investigated. The evolution characteristics of volatile products were examined by pyrolysis–Fourier transform infrared spectroscopy (FTIR)/thermal conductivity detection (TCD) analysis (Py–FTIR/TCD). The char chemical structure and physical characteristics were investigated by means of FTIR and N2 physisorption techniques. Evolution characteristics of the main volatile products were given. The evolution of CO2 was approximately 26 °C earlier than that of CO. CH4 evolution covered over a wider temperature range of 300–600 °C, with a maximum at 394 °C. The amount of hydroxyl, aliphatic CH and olefinic CC bonds in the char decreased significantly above 250 °C. The aromatization process started at ≈350 °C and continued to higher temperatures, leaving the char enriched with condensed aromatic ring systems. The BET surface area increased continually with increasing temperature to reach a maximum value of 4.68 m2/g at 500 °C and decreased at higher temperatures. The micropore volume showed a similar behavior to the surface area, while the mesopore volume and total pore volume always increased.  相似文献   

9.
The thermal treatment of coal causes a development of internal porosity of the resultant char due to the changes in the coal char pores, i.e. the opening of original closed pores, the formation of new pores, and an increase in pore size of existing and newly formed pores. Furthermore, the porosity formed during de-volatilisation causes changes in pore structural characteristics such as: density, pore size distribution, total open pore volume, porosities and average pore diameter. Much research has been conducted in this area, but was mainly focused on fine particle sizes (<1 mm) and vitrinite-rich coals, particularly from the Northern hemisphere. The objective of this study was to obtain an understanding of both the macro- and micro-porosity development within the de-volatilisation zone of a packed bed consisting of lump inertinite-rich coal (75 mm × 6 mm) from the Highveld coalfield in South Africa. This was achieved by generating samples in an air-blown packed bed reactor and conducting proximate, CO2 reactivity, mercury intrusion porosimetry, and BET CO2 surface area analyses on the dissected coal/char/ash samples.From mercury-intrusion porosimetry results obtained for the de-volatilisation reaction zone of the reactor, it was found that although the percentage macro-porosity and average pore diameter increased by 11% and 77% respectively (which confirms pore development), that these developments do not enlarge the surface area, and thus has no significant contribution on the reactivity of the coal/char. On the other hand, the micro-pore surface area, pore volume and pore diameter were all found to increase during de-volatilisation, resulting in an increase in the coal char reactivity. The micro-porosity is thus generally responsible for the largest internal surface area during de-volatilisation, which enables increased reactivity. The CO2 gasification reactivity (at 1000 °C) increased from 3.8 to 4.5 h−1 in the first stage of de-volatilisation, and then decreased to 3.8 h−1 in a slower de-volatilisation regime. This is due to the maximum pore expansion and volatile matter evolution reached at 4.5 h−1, before coalescence and pore shrinkage occur with a further increase in temperature within the slower de-volatilisation region of the reactor. During de-volatilisation there is thus both an increase and decrease in reactivity which might suggest two distinct intermediate zones within the de-volatilisation zone.  相似文献   

10.
The evolution of gases and volatiles during Sulcis coal pyrolysis under different atmospheres (N2 and H2) was investigated to obtaining a clean feedstock of combustion/gasification for electric power generation. Raw coal samples were slowly heated in temperature programmed mode up to 800 °C at ambient pressure using a laboratory-scale quartz furnace coupled to a Fourier transform infrared spectrometer (FTIR) for evolved gas analysis. Under both pyrolysis and hydropyrolysis conditions the evolution of gases started at temperature as low as 100 °C and was mainly composed by CO and CO2 as gaseous products. With increasing temperature SO2, COS, and light aliphatic gases (CH4 and C2H4) were also released. The release of SO2 took place up to 300 °C regardless of the pyrolysis atmosphere, whilst the COS emissions were affected by the surrounding environment. Carbon oxide, CO2, and CH4 continuously evolved up to 800 °C, showing similar release pathways in both N2 and H2 atmospheres. Trace of HCNO was detected at low pyrolysis temperature solely in pure H2 stream. Finally, the solid residues of pyrolysis (chars) were subjected to reaction with H2 to produce CH4 at 800 °C under 5.0 MPa pressure. The chars reactivity was found to be dependent on pyrolysis atmosphere, being the carbon conversions of 36% and 16% for charN2 and charH2, respectively.  相似文献   

11.
《Solid State Sciences》2007,9(3-4):240-246
In this paper, we present the synthesis and characterizations of NaSICON-type ionic conducting ceramics of the general formula Na1+xM1.775Six−0.9P3.9−xO12 with 1.8  x  2.2 and M = Zr or Hf. The effect of the total substitution of zirconium by hafnium on electric properties has been studied. The various compositions were prepared by using the sol–gel method and the synthesized precursors were characterized by coupled DTA–TG. The oxides obtained after pyrolysis of the precursors were identified by X-ray diffraction. A sintering study by thermodilatometry permits to select the best thermal cycle adapted to our ceramics. Furthermore, the electric conductivity of the sintered ceramic samples was characterized by complex impedance spectroscopy. These results show that ceramics containing Zr synthesized by soft method, present a higher total conductivity than those obtained in literature (to be around 10−4 S cm−1). The total substitution of Zr by Hf still improves this conductivity for some compositions.  相似文献   

12.
The kinetics of the diazotization reaction of procaine in the presence of anionic micelles of sodium dodecyl sulfate (SDS) and cationic micelles of cetyltrimethyl ammonium bromide (CTAB), dodecyltrimethyl ammonium bromide (DDTAB) and tetradecyltrimethyl ammonium bromide (TDTAB) were carried out spectrophotometrically at λmax = 289 nm. The values of the pseudo first order rate constant were found to be linearly dependent upon the [NaNO2] in the concentration range of 1.0 × 10−3 mol dm−3 to 12.0 × 10−3 mol dm−3 in the presence of 2.0 × 10−2 mol dm−3 acetic acid. The concentration of procaine was kept constant at 6.50 × 10−5 mol dm−3. The addition of the cationic surfactants increased the reaction rate and gave plateau like curve. The addition of SDS micelles to the reactants initially increased the rate of reaction and gave maximum like curve. The maximum value of the rate constant was found to be 9.44 × 10−3 s−1 at 2.00 × 10−3 mol dm−3 SDS concentration. The azo coupling of diazonium ion with β-naphthol (at λmax = 488) nm was found to linearly dependent upon [ProcN2+] in the presence of both the cationic micelles (CTAB, DDTAB and TDTAB) and anionic micelles (SDS). Both the cationic and anionic micelles inhibited the rate of reactions. The kinetic results in the presence of micelles are explained using the Berezin pseudophase model. This model was also used to determine the kinetic parameters e.g. km, Ks from the observed results of the variation of rate constant at different [surfactants].  相似文献   

13.
Hydropyrolysis of rice husk was performed using nickel-loaded Loy Yang brown coal char (Ni/LY) catalyst in a fluidized bed reactor at 500, 550, 600 and 650 °C with an aim to study the influence of catalyst and catalytic hydropyrolysis temperature on product yields and the composition of bio-oil. An inexpensive Ni/LY char was prepared by the ion-exchange method with nickel loading rate of 9 ± 1 wt.%. Nickel particles which dispersed well in Loy Yang brown coal char showed a large specific surface area of Ni/LY char of 350 m2/g. The effects of catalytic activity and hydropyrolysis temperature of rice husk using Ni/LY char were examined at the optimal condition for bio-oil yield (i.e., pyrolysis temperature 500 °C, static bed height 5 cm, and gas flow rate 2 L/min without catalyst). In the presence of catalyst, the oxygen content of bio-oil decreased by about 16% compared with that of non-catalyst. Raising the temperature from 500 to 650 °C reduced the oxygen content of bio-oil from 27.50% to 21.50%. Bio-oil yields decreased while gas yields and water content increased with increasing temperature due to more oxygen being converted into H2O, CO2, and CO. The decreasing of the oxygen content contributed to a remarkable increase in the heating value of bio-oil. The characteristics of bio-oil were analyzed by Karl Fischer, GC/MS, GPC, FT-IR, and CHN elemental analysis. The result indicated that the hydropyrolysis of rice husk using Ni/LY char at high temperature can be used to improved the quality of bio-oil to level suitable for a potential liquid fuel and chemical feedstock.  相似文献   

14.
This paper describes the conventional and microwave-assisted pyrolysis of coffee hulls at 500, 800 and 1000 °C. The influence of the pyrolysis method and temperature on the product yields and on the characteristics of the pyrolysis products is discussed. It was found that the pyrolysis of this particular residue gives rise to a larger yield of the gas fraction compared to the other fractions, even at relatively low temperatures. A comparison of microwave-assisted pyrolysis and conventional pyrolysis showed that microwave treatment produces more gas and less oil than conventional pyrolysis. In addition, the gas from the microwave has much higher H2 and syngas (H2 + CO) contents (up to 40 and 72 vol.%, respectively) than those obtained by conventional pyrolysis (up to 30 and 53 vol.%, respectively), in an electric furnace, at similar temperatures. From the pyrolysis fraction yields and their higher heating values it was found that the energy distribution in the pyrolysis products decreases as follows: gas > solid > oil. Moreover, the energy accumulated in the gas increases with the pyrolysis temperature. By contrast, the energy accumulated in the char decreases with the temperature. This effect is enhanced when microwave pyrolysis is used.  相似文献   

15.
This work reports on a novel chitosan–hematite nanotubes composite film on a gold foil by a simple one-step electrodeposition method. The hybrid chitosan–hematite nanotubes (Chi–HeNTs) film exhibits strong electrocatalytic reduction activity for H2O2. Interestingly, two electrocatalytic reduction peaks are observed at −0.24 and −0.56 V (vs SCE), respectively, one controlled by surface wave and the other controlled by diffusion process. The Chi–HeNTs/Au electrode shows a linear response to H2O2 concentration ranging from 1 × 10−6 to 1.6 × 10−5 mol L−1 with a detection limit of 5 × 10−8 mol L−1 and a sensitivity as high as 1859 μA μM−1 cm−2.  相似文献   

16.
A simple and fast method based on graphite furnace atomic absorption spectrometry (GF AAS) and slurry sampling technique (SlS) was developed to determine trace Cd, Co and Pb in high-sulphur coal (Sulcis, Italy) and coal chars derived at 600, 750 and 950 °C under N2 atmosphere for developing a clean coal for electricity production. The proposed method was then coupled to a four-step sequential chemical extraction method for assessment of metals distribution in coaled samples. The slurries were prepared by varying sample mass (1–50 mg), volume (1–3 mL) and kind of dispersing medium (1% v/v Triton X-100 and 2 N HNO3), and sonication time (5–30 min). Pyrolysis/atomization temperatures as well carrier gas flow rate were optimised. Pd(NO3)2 and NH4H2PO4 were employed to stabilize Cd and Pb, respectively, in the pyrolysis stage of furnace program. The use of HNO3 as dispersing agent was found to be effective in lowering the high level of background absorption on the Cd analytical signal produced by raw coal matrix. Conversely, coal charred samples did not show significantly level of background interferences, so that Triton X-100 dispersing agent could be used for all analytes. Calibration curve against acid-matched standards was allowed for Cd, whereas the standard addition calibration was used for Co and Pb owing to chemical matrix interferences. The precision, expressed as relative standard deviation (% RSD, n = 5), was better than 5% for Cd, Co, and Pb at 1, 10, and 15 μg L? 1 levels, respectively. The accuracy of the analytical method was checked by analyzing a BCR No. 182 steam coal certificated reference material and the results were in good agreement with certificated and informed values. The solid detection limits (3σblank) were as low as 0.001 Cd, 0.01 Co, and 0.01 Pb mg kg? 1, using 30 mg sample mass and slurry concentration of 30 m v? 1 for Cd, and 50 mg sample mass and 50 m v? 1 slurry concentration for Co and Pb. The content of elements in Sulcis coal was found to be 0.33 Cd, 4.0 Co, and 3.8 Pb mg kg? 1 and mostly associated to sulphates and di-sulphides as indicated by the leaching test. Under pyrolysis conditions Cd significantly volatilised (about 64%) at temperature higher than 600 °C, whereas residue chars at 950 °C are enriched in Co and Pb up to 20%. The proposed method is suitable for routine metals monitoring in coaled samples.  相似文献   

17.
This work shows that highly ordered and mechanically stable micrometer-long Ta2O5 nanotube arrays can be fabricated by galvanostatic anodization in a few seconds. Typically, ~ 7.7 μm long nanotubes can be grown at 1.2 A cm 2 in only 2 s. Such nanotubes can be converted to Ta3N5 nanotube arrays by nitridation. Photoelectrochemical (PEC) water splitting using AM 1.5G illumination yields for the Ta3N5 nanotube photoanode modified with cobalt phosphate (Co–Pi) remarkable photocurrents of 5.9 mA cm −2 at 1.23 VRHE and 12.9 mA cm −2 at 1.59 VRHE and after Ba-doping a value of 7.5 mA cm −2 at 1.23 VRHE is obtained.  相似文献   

18.
Heat capacities of 2,2-dimethyl-1,3-propanediol(CH3)2C(CH2OH)2 were measured in the temperature range between T =  13 K and T =  350 K using an adiabatic calorimeter. The compound underwent a first-order phase transition at T =  (314.5  ±  0.1) K. The enthalpy and the entropy of transition were (12.52  ±  0.02)kJ · mol  1and (39.81  ±  0.08)J · K  1· mol  1, respectively. Measurement of the fusion peak by d.s.c. showed that the purity of the sample was 0.9999 mass fraction and the entropy of fusion was 9.9 J · K  1· mol  1. Another first-order phase transition was observed at T =  (60.4  ±  0.1) K with the associated entropy change of (2.93  ±  0.05)J · K  1· mol  1. Heat capacities of two deuterated samples,(CH3)2C(CH2OD)2 and(CD3)2C(CD2OD)2 , were also measured and the results were compared with those on the natural compound. Possible mechanisms of the transition have been discussed from the isotope effects on the thermodynamic quantities associated with the transition. Standard thermodynamic functions of the compounds are tabulated.  相似文献   

19.
Oxidative pyrolysis of pine wood was studied by thermogravimetric analysis (TGA) coupled with mass spectrometer (MS) and differential scanning calorimetry (DSC) methods. The effects of oxygen concentration on pyrolysis behavior, carbon oxide production and heat properties were investigated. Several parameters were defined to evaluate the oxygen influence. It was found that oxygen dramatically promotes the oxidative degradation and char oxidation rate. The reactivity index was found to be proportional to the oxygen concentration, which suggested that oxidative degradation reactions were under increasingly kinetic control in elevated oxygen concentration environments. Carbon oxides evolution properties were investigated. There are two releasing peaks in MS curves for oxidative condition comparing with one peak under inert condition. They are related with oxidative degradation and char oxidation, respectively. Both total amounts and rates of carbon oxides emission were found to increase with oxygen concentration. The cumulative emission ratio of CO to CO2 first decreases then increases with oxygen concentration with 10% as turning point. It may be caused by different oxygen diffusion behaviors with variable oxygen concentrations. The absolute reaction heat value of oxidative pyrolysis (−7.23 MJ kg−1, 5% O2) is much larger than that of inert condition (+0.28 MJ kg−1). Increasing of oxygen concentration results in an increase of heat emission. Comparing with pine wood low heat value, the net heat emission efficiencies under different oxygen concentrations (5%, 10%, 15%, 21%) are 39.73%, 44.84%, 68.90% and 78.41%, respectively.  相似文献   

20.
Nano-sized nickel ferrite (NiFe2O4) was prepared by hydrothermal method at low temperature. The crystalline phase, morphology and specific surface area (BET) of the resultant samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and nitrogen physical adsorption, respectively. The particle sizes of the resulting NiFe2O4 samples were in the range of 5–15 nm. The electrochemical performance of NiFe2O4 nanoparticles as the anodic material in lithium ion batteries was tested. It was found that the first discharge capacity of the anode made from NiFe2O4 nanoparticles could reach a very high value of 1314 mAh g−1, while the discharge capacity decreased to 790.8 mAh g−1 and 709.0 mAh g−1 at a current density of 0.2 mA cm−2 after 2 and 3 cycles, respectively. The BET surface area is up to 111.4 m2 g−1. The reaction mechanism between lithium and nickel ferrite was also discussed based on the results of cycle voltammetry (CV) experiments.  相似文献   

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