催化裂化抗氮中毒技术的研究进展

从调节催化剂酸性或向反应体系外加抗氮剂的角度,介绍了加强催化裂化抗氮中毒能力,以增产汽油、柴油、丙烯或抑焦为目的的研究进展。针对于调变催化剂本身的酸性存在灵活性差、成本高的缺点,认为开发性优价廉的抗氮助剂改善原料质量,减缓催化剂中毒是有前景的抗氮中毒技术。     

Structural and catalytic properties of Ti–MCM-41 synthesised at room temperature up to high Ti content

A study of the pore structural properties and catalytic activity of MCM-41 containing titanium, prepared by direct synthesis at ambient temperature and pressure, using tetraethoxysilane, titanium alcoxides, cationic surfactants and ammonia is presented. The influence of different metal sources (titanium ethoxide, isopropoxide or n-butoxide), alcohols (ethanol or propan-2-ol), metal content (2  Si/Ti  100) and surfactants (tetra-, hexa- or octadecyltrimethylammonium bromide) is considered. The materials were characterised by X-ray diffraction, nitrogen adsorption at 77 K and diffuse reflectance UV–Vis spectroscopy. The catalytic activity was evaluated in the model reaction of oxidation of cyclohexene with anhydrous tert-butylhydroperoxide, for representative samples. It is concluded that this method allows the preparation in a short period of time of well structured and catalytically active Ti–MCM-41. Down to Si/Ti = 10 the materials have high pore volumes and very uniform pore size, with highest conversion and excellent selectivity demonstrated in the compositional range 30  Si/Ti  100, corresponding to materials containing predominantly isolated and tetracoordinated Ti. The increase in Ti content to Si/Ti ratios of 10 and 5 implied a reduction both in conversion and selectivity, although the MCM-41 structure was still observed for Si/Ti = 2.     

Nitrogen input, <Superscript>15</Superscript>N balance and mineral N dynamics in a rice–wheat rotation in southwest China

A field experiment and farm survey were conducted to test nitrogen (N) inputs, ¹⁵N-labelled fertilizer balance and mineral N dynamics of a rice–wheat rotation in southwest China. Total N input in one rice–wheat cycle averaged about 448 kg N ha⁻¹, of which inorganic fertilizer accounted for 63% of the total. The effects of good N management strategies on N cycling were clear: an optimized N treatment with a 27% reduction in total N fertilizer input over the rotation decreased apparent N loss by 52% and increased production (sum of grain yield of rice and wheat) compared with farmers’ traditional practice. In the ¹⁵N-labelled fertilizer experiment, an optimized N treatment led to significantly lower ¹⁵N losses than farmers’ traditional practice; N loss mainly occurred in the rice growing season, which accounted for 82% and 67% of the total loss from the rotation in farmers’ fields and the optimized N treatment, respectively. After the wheat harvest, accumulated soil mineral N ranged from 42 to 115 kg ha⁻¹ in farmers’ fields, of which the extractable soil NO₃ ⁻–N accounted for 63%. However, flooding soil for rice production significantly reduced accumulated mineral N after the wheat harvest: in the ¹⁵N experiment, farmers’ practice led to considerable accumulation of mineral N after the wheat harvest (125 kg ha⁻¹), of which 69% was subsequently lost after 13 days of flooding. Results from this study indicate the importance of N management in the wheat-growing season, which affects N dynamics and N losses significantly in the following rice season. Integrated N management should be adopted for rice–wheat rotations in order to achieve a better N recovery efficiency and lower N loss.     

Agroecological analysis and economic benefit of organic resources and fertiliser in till and no-till sorghum production after a 6-year fallow in semi-arid West Africa

A field experiment was conducted in Gampela (Burkina Faso) in 2000 and 2001 to assess the impact of organic and mineral sources of nutrients and combinations thereof in optimising crop production in till and no-till systems and to assess the economic benefit of these options. The study showed that under conditions of rainfall deficiency, the use of a single organic resource at an equivalent dose of 40 kg N ha⁻¹ better secured crop yield than the application of an equivalent amount as urea-N, while a combination of organic resources and fertiliser was better in increasing crop yield than the application of the same N amount in the form of urea. In a year of rainfall deficiency, a mix of organic resources and fertiliser in both till and no-till systems increased crop water use efficiency, with the result that the farmer was able to purchase only half of the normal quantity of N fertiliser to obtain a higher yield that he would have done when all of the N was supplied in the form of urea. Under conditions where soil N is deficient, an economic benefit was achieved when urea was combined with easily decomposable organic material (e.g. sheep dung); mixing the urea at a dose of 40 kg N ha⁻¹ with maize straw was not sufficient in alleviating the negative interaction due to the enhanced N immobilisation. The results demonstrate that the use of N fertiliser alone was risky and that a higher yield, with the accompanying economic benefit, was scarcely achieved under the prevailing rainfall conditions. The application of soil and water conservation measures can contribute greatly to increasing the economic benefit of mineral, organic or combined organic and mineral-derived nutrient application under semi-arid conditions.     

Crop residue,manure and fertilizer in dryland maize under reduced tillage in northern China: I grain yields and nutrient use efficiencies

The rapidly increasing population and associated quest for food and feed in China has led to increased soil cultivation and nitrogen (N) fertilizer use, and as a consequence to increased wind erosion and unbalanced crop nutrition. In the study presented here, we explored the long-term effects of various combinations of maize stover, cattle manure and nitrogen (N) and phosphorus (P) fertilizer applications on maize (Zea mays L.) yield and nutrient and water use efficiencies under reduced tillage practices. In a companion paper, we present the effects on nutrient balances and soil fertility characteristics. The ongoing factorial field trial was conducted at Shouyang Dryland Farming Experimental Station in northern China from 1993 onwards. The incomplete, determinant-optimal design comprised 12 treatments, including a control treatment, in duplicate. Grain yields and N, P, and potassium (K) uptakes and N, P and K use efficiencies were greatly influenced by the amount of rain during the growing season (GSR), and by soil water at sowing (SWS). There were highly significant interactions between GSR and added stover and manure, expressed in complex annual variations in grain yield and N, P and K use efficiencies. Annual mean grain yields ranged from 3,000 kg ha⁻¹ to 10,000 kg ha⁻¹ and treatment mean yields from 4,500 kg ha⁻¹ to 7,000 kg ha⁻¹. Balanced combination of stover (3,000–6,000 kg), manure (1,500–6,000 kg) and N fertilizer (105 kg) gave the highest yield. Stover and manure were important for supplying K, but the effects differed greatly between years. Overall mean N recovery efficiency (NRE) ranged from 28% to 54%, depending on N source. NRE in wet years ranged from 50% to 90%. In conclusion, balanced combinations of stover, manure and NP fertilizer gave the highest yield and NRE. Reduced tillage with adding stover and manure in autumn prior to ploughing is effective in minimizing labor requirement and wind erosion. The potentials of split applications of N fertilizer, targeted to the need of the growing crop (response farming), should be explored to further increase the N use efficiency.     

旋转吹氮铝液精炼方式的改进及效果研究

为了改善铝合金重力铸造中针孔及夹杂缺陷，通过对吹氮净化铝液工艺中的旋转喷头的改进，来细化氮气气泡的体积，增加氮气与铝液的接触面积，从而提高除气除渣的效果，达到铝液净化的目的，最终提高产品的质量。     

Effect of nitrogen on corrosion behavior of 28Cr-7Ni duplex and microduplex stainless steels in air-saturated 3.5 wt% NaCl solution

The corrosion behavior of 28Cr-7Ni-O-0.34N duplex stainless steels in air-saturated 3.5-wt% NaCl solution at pH 2, 7, 10 and 27 °C was studied by the potentiodynamic method. Two types of microstructures were investigated: the as-forged duplex and microduplex (average austenite grain size 5-16 μm) structures. The austenite volume fractions of the tested steels were between 0.35 and 0.64. The nitrogen effect on corrosion behaviors of both duplex and microduplex stainless steels were the same. At pH 2, the corrosion potential increased when the nitrogen content increased, however, corrosion current density as well as corrosion rate decreased. At pH 7 and 10, the effect of nitrogen on corrosion potential and corrosion rate could not be observed. Corrosion potential at pH 10 was lower than at pH 7. Pitting potential increased when the nitrogen content in the tested steels increased at all tested pH. For the nitrogen effect on the passive current density, it seemed that only at pH 2, the average passive current densities reduced when the nitrogen content increased. Nitrogen may have participated in the passive film or has been involved in the reaction to build up passive film. The ammonium formation and nitrogen enrichment at the interface metal/passive film with adsorption mechanism were discussed. The dissolute nitrogen might have combined with the hydrogen ions in solution to form ammonium ions, resulting in increasing solution pH. The steel could then easily repassivate, hence the corrosion potential and pitting potential would increase. However, the ammonium formation mechanism could not explain the decrease of corrosion potential in basic solution. Nitrogen enrichment at the metal/passive film interface with adsorption mechanism seemed to be an applicable consideration in increasing pitting potential. However, this mechanism did not involve the ammonium ion formation. In general, for the duplex and microduplex stainless steels tested, nitrogen increased the general corrosion resistances in acid solution and pitting corrosion resistance at all solution pH. Metallographic observation in both tested duplex and microduplex steels after pitting corrosion at all tested pH revealed that, the corroded structure in the tested steels without nitrogen alloying was austenite, but those with nitrogen alloying was ferrite. Even though ferrite had a higher chromium content than austenite but higher dissolved nitrogen in austenite than in ferrite may have increased the pitting resistance equivalent number (PRE) of austenite to be higher than that of ferrite.     

Hydrogen effects on the passive film formation and pitting susceptibility of nitrogen containing type 316L stainless steels

The effects of hydrogen on the passivity and pitting susceptibility of type 316L stainless steels have been investigated with alloys containing different nitrogen contents (0.015, 0.198 and 0.556 wt.% N). The study revealed that electrochemically pre-charged hydrogen significantly reduced the pitting resistance of alloys conatining 0.015 and 0.198 wt.% nitrogen contents. In alloy with highest nitrogen content (0.556 wt.% N), an increase in the passive film current density with hydrogen was observed without affecting breakdown potential. Auger electron spectroscopy (AES) analysis of the passive film indicated the presence of nitrogen in the passive film. On other hand, for hydrogen charged samples, nitrogen was found to be significantly less in the passive film. In Electrochemical impedance spectroscopy (EIS) measurement, the decrease in semi-circle radius of Nyquist plot, and the polarization resistance, R_P associated with the resistance of the passive film was observed with hydrogen, indicating that hydrogen decreased the stability of the passive film. The present investigation indicated that precharged hydrogen deteriorated the passive film stability and pitting corrosion resistance in these alloys, and the increase in nitrogen content of the alloy offsets the deleterious effect of precharged hydrogen.     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

Effects of timing of nitrogen and sulphur fertilizers on yield, nitrogen, and sulphur contents of Tef (Eragrostis tef (Zucc.) Trotter)

Nitrogen use efficiency (NUE) of tef, a major staple crop in Ethiopia, is very low, either caused by untimely use of nitrogen (N) fertilizers or lack of other essential nutrients like sulphur (S). The average grain yield of this crop is low, averaging <0.8 Mg ha⁻¹ in farmer’s fields of the semi-arid conditions. Therefore, the present study was conducted to see the effect of the timing of combined N and S fertilization on the yield, yield components, and N and S concentration in the plant parts of the crop. A factorial combination of three rates of N (0, 70, and 105 kg ha⁻¹) with four rates of S (0, 16, 32, and 48 kg ha⁻¹) was applied in randomized complete blocks in three replications. The experiment was carried out in the 2004 and 2005 cropping seasons in the Cambisols of the semi-arid area of Ethiopia. The crop responded significantly (P < 0.05) to both split (one-third at planting and two-thirds at late tillering) and whole (all at planting) N and S applications and years. Combined N and S fertilization increased the dry matter (DM) and grain yields on average by 1.7 and 0.3 Mg ha⁻¹, compared with the control. Similarly, S fertilization increased the NUE of the tef crop by 36%. Nitrogen concentration of shoots was found to significantly increase with S application (P < 0.05), with strong positive interactions both in the split and whole applications. The sulphur increase in grains was significant with N rates for both applications, with significant interaction effects observed for the split application in both cropping seasons. Split application resulted in 0.9 and 0.3 Mg ha⁻¹ significant increase in DM and grain yields, averaged for both years and treatments compared with the whole application. Similar significant increases were observed for panicle yield, NUE, and shoot and grain N and S concentrations. The average N:S ratio in grains was 10.6:1. Significant (P < 0.05) yearly variations were also observed. Dry matter and grain yields of 2005 were higher on average by 2.10 and 0.32 Mg ha⁻¹ than those of the 2004 cropping season. The percentage of N and S concentrations of grains, averaged for both applications, were higher by 13 and 9% in 2004; even though the N and S uptakes of 2005 were higher on average by 5.0 and 0.5 kg ha⁻¹ than those of the 2004 cropping season. This work showed that the yield response and NUE of the tef crop could be improved with split N and S fertilizer applications, with tef-producing farmers benefitting from the application of S-containing N fertilizers to soils deficient in these nutrients.