重钙装置改产DAP的工程实践

介绍瓮福重钙装置采用混合工艺改产 DAP的技术改造及试车概况、试车中出现的问题及解决措施。     

N,N,N-三甲基-2,3-二(硬脂酰氧基)丙基氯化铵(CDESA)的生物降解性

采用活性环氧中间体失水甘油基三甲基氯化铵合成了一种阳离子双酯表面活性剂——N,N,N-三甲基-2,3-二(硬脂酰氧基)丙基氯化铵(CDESA),来代替传统的难降解的表面活性剂型柔软剂,如目前国内仍在大量使用的双十八烷基二甲基氯化铵(D1821)。对CDESA的好氧降解性能进行了研究:以天然环境中的生活沉降污泥作为微生物源,用河水稀释,经培养、驯化后用于测试降解时间和半衰期,并与D1821的好氧降解性能作了对比。结果表明,CDESA的半衰期为3 d,容易降解,而D1821半衰期为7 d,较难降解,CDESA生物降解性能优于D1821。     

Optimising P2O5 availability for fertilizer use,by direct treatment of apatite with hydrochloric or nitric acids

Hydrochloric and nitric acid treated apatite is not directly used as a fertilizer because of the hygroscopic character of the products. Another problem arises from the volatility of these acids and that acidulated product undergo reversions during drying with loss of the acid. We have found that apatite beneficiated with hydrochloric and nitric acids dried at an optimum temperature ~120°C has high available phosphorous. The products can be stored in the solid form in sealed polythene bags.Sumanasekara Chair in Natural Science     

Phosphate availability in calcareous Vertisols and Inceptisols in relation to fertilizer type and soil properties

The availability to plants of fertilizer phosphorus (P) applied to soil, as measured by chemical extraction, is used to estimate P fertilizer needs. We studied the availability of P, applied as monocalcium phosphate (MCP) powder, ordinary superphosphate (OSP) granules and diammonium phosphate (DAP) granules in 24 calcareous Vertisols and Inceptisols of Andalusia, Spain, by using laboratory incubation techniques. The soils differed widely in their P adsorption- and Ca-phosphate precipitation-related properties. For MCP, availability (defined as the proportion of added P that is recovered by extraction with NaHCO₃ or is isotopically exchangeable) decreased markedly with incubation time and increasing addition rate. The mean recoveries after 180 d of incubation at field capacity at a rate of 246 mg P kg^–1 soil were 17% for Olsen P, 38% for Colwell P, and 16% for isotopically exchangeable P (IEP). Increasing the application rate to 2460 mg kg^–1 resulted in recoveries of 6% for Olsen P, 25% for Colwell P, and 4% for IEP. While IEP-based recovery was not significantly correlated to any soil property, that based on Olsen P (and, to a lesser extent, Colwell P) decreased sharply with increase in the ratio of clay (or Fe oxides) to total (or active) calcium carbonate equivalent. Accordingly, Olsen P might overestimate P availability in those soils relatively rich in carbonate and poor in clay and Fe oxides. On the other hand, recovery of applied P from soils containing more clay and Fe oxides, by a sequential extraction (with H₂O, two 0.5M NaHCO₃ treatments, 0.5M HCl), was lower than 100%, thereby suggesting phosphate occlusion by Fe oxides or clay.Availability of the fertilizers tested 90 d after application was found to decrease in the following order: MCP powder (rate, 246 mg kg^–1) > DAP granules (rate, 547 mg kg^–1) > MCP powder (rate, 738 mg kg^–1) > OSP granules (rate, 308 mg kg^–1). Differences between fertilizers tended to increase with increasing carbonate content in the soil. This may have been due to precipitation of Ca phosphates caused by the presence of Ca in the fertilizer and the high Ca- supplying capacity of the more calcareous soils.     

Chemical interactions between soil N and alkaline-hydrolysing N fertilizers

Chemical interactions between soil N and alkaline-hydrolysing N fertilizers labelled with¹⁵N were studied in the laboratory using twelve-irradiated soils. Fertilizer was recovered in the soil organic N fraction via the process of NH₃ fixation. NH₃ fixation at day 7 varied from 1.8 to 4.6% of the N added as aqua ammonia at 1000 mg kg^–1 soil. The amount of NH₃ fixed increased with increasing rates of application of NH_3(aq) and urea. The rate of NH₃ fixation decreased with time, with more than 55% of the total NH₃ fixation in 28 days occurring in the first week following application of 2000 mg urea-N kg^–1 soil. Soil pH and NH₃ fixation varied in response to N source, and increased in the order of di-ammonium phosphate 3 fixation, resulting in the release of unlabelled ammonium (deamination) and a real added nitrogen interaction in all but two of the soils studied. The release of NH ₄ ⁺ initially increased up to a pH of 7.5, was inhibited between pH 8.5 and 9.0, but increased thereafter. The balance (N_bal) between NH₃ fixation and deamination was either positive or negative, depending on the pH of the fertilized soil, which was directly related to N source and concentration for a given soil.     

Reaction products of ammonium nitrate phosphate fertilizers of varying water-soluble phosphorus content in different Indian soils

Studies were undertaken on the isolation and identification of reaction products of ammonium nitrate phosphate (ANP) fertilizers containing 30, 50 and 70 per cent water-soluble phosphorus (WSP) of total phosphorus in representative soils of the vertisol, oxisol, alfisol, entisol, mollisol and aridisol groups of India. ANP fertilizers were applied in solid form to soil, and reaction products formed at and around the site of ANP fertilizer placement were identified after six weeks incubation in moist soils by X-ray diffraction technique. DCPD (dicalcium phosphate dihydrate- CaHPO₄ · 2H₂O) was the major reaction product of ANP fertilizers containing 30 and 50 per cent WSP in vertisol, entisol, aridisol, mollisol, oxisol and alfisol, and of ANP containing 70 per cent WSP in vertisol, entisol, alfisol, aridisol and mollisol. DCP (dicalcium phosphate-CaHPO₄) was detected with ANP of 30 and 50 per cent WSP in the vertisol, alfisol, entisol, mollisol and aridisol groups of soils. In addition to DCPD, FePO₄ · 2H₂O (metastrengite) and AlPO₄ · 2H₂ O-monoclinic (metavariscite) were formed in alfisol and oxisol soils with ANP of 30 and 50 per cent WSP. FePO₄ · 2H₂O and AlPO₄ · 2H₂O (metavariscite) were identified in alfisol and oxisol soils while AlPO₄ · 2H₂O-orthorhombic (variscite) was formed in alfisol soils with ANP of 70 per cent WSP.     

钒钼酸铵分光光度法快速测定磷酸二铵中有效五氧化二磷

为了快速测定磷铵中P2O5含量,将0.1mol/LEDTA预热至80±2℃作为DAP有效P2O5的提取液,提取时间25min以上。鉴于正磷酸根在酸性介质中与钼酸盐及偏钒酸盐生成稳定的黄色化合物,在400nm波长下,利用示差法测定P2O5仅需50～55min。该方法的相对标准偏差(RSD)为0.13%～0.28%,回收率99.1%～101.1%,精密度和准确度好。     

Crystallization kinetics of low‐density polyethylene and polypropylene melt‐blended with a low‐Tg tin‐based phosphate glass

The nonisothermal and isothermal crystallizations of low‐density polyethylene (LDPE) and polypropylene (PP) in phosphate glass (Pglass)–polymer hybrid blends were studied through differential scanning calorimetry (DSC). As the Pglass volume fraction was increased, the percentage crystallinity decreased. The half‐time for crystallization decreased as the propagation rate constant rose, for both of the polymer matrices, with increasing Pglass concentrations. The Pglass was observed to be a nucleating agent for formation of two‐ or three‐dimensional spherulites in the hybrids. Tensile modulus improved for both of the Pglass–polymer hybrids up to 40% Pglass, but the energy to break decreased. Tensile strength changed slightly with the addition of Pglass to the LDPE matrix, exhibiting a larger value than that of pure LDPE at 30%. The tensile strength decreased as more Pglass was added to the PP matrix. The observed differences between tensile properties of the Pglass–PP and Pglass–LDPE hybrids at identical Pglass volume concentration were found to be consistent with that of the crystallization behavior of the hybrids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3445–3456, 2003     

碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a。生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法。我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法。DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚。     

A discussion of the methods for comparing the relative effectiveness of phosphate fertilizers varying in solubility

Because various phosphate (P) fertilizers differ widely in their solubility, it is commonly observed that crop response to P fertilizers varies under the same soil and crop conditions. Furthermore, a major problem encountered in the methods for determining the relative effectiveness (RE) of water-insoluble P fertilizer (e.g., phosphate rock) with respect to water-soluble P fertilizers, e.g., single superphosphate (SSP) and triple superphosphate (TSP), is that their growth response curves are usually nonlinear and often do not share a common maximum yield. In this paper, we review and discuss the advantages and disadvantages of the three most commonly used methods for calculating the RE of phosphate rock with respect to TSP (or SSP). The three methods are vertical comparison, horizontal (substitution rate) comparison, and linear-response comparison.