粒状硝酸铵钙造粒工艺的探讨

含有5Ca(NO3)2·NH4NO3·10H2O的硝酸铵钙母液蒸发提浓后可以用经过改造的复混肥造粒机进行造粒。最佳的硝酸铵钙母液造粒工艺条件为:溶液密度1.82～1.83g/cm3,温度140～146℃。这一工艺适合硝酸铵或者硝酸磷肥厂家转产粒状硝酸铵钙产品。     

硝酸铵钙的生产与市场概况

硝酸铵钙是一种性能优良的复合肥料。介绍硝酸铵钙的物化性能,采用硝铵熔融液与石灰石混合法生产硝酸铵钙的工艺技术;简述硝酸铵钙在农作物种植上的施用效果与市场前景。     

Nitrification and denitrification derived N2O production from a grassland soil under application of DCD and Actilith F2

The relative contribution of nitrification and denitrification to N₂O production was investigated by means of soil incubations with acetylene in a mixed clover/ryegrass sown sward 5 days after application of a mineral fertiliser (calcium ammonium nitrate) or an organic one (cattle slurry) with and without the addition of the nitrification inhibitor dicyandiamide (DCD) and the commercial slurry additive Actilith-F2. At this time, maximum field N₂O emissions were taking place. N₂O production by the slurry amended soil was twice as high as that of the mineral amended one. N₂O came in a greater proportion from nitrification rather than from denitrification in the slurry treatment, while for the mineral fertilisation most N₂O came from denitrification. The addition of DCD to slurry produced a decrease in N₂O production both from nitrification and denitrification. No reduction in N₂O losses was observed from addition of DCD to the mineral fertilisation, although DCD resulted effective in reducing the nitrification rate by 53% both in the slurry and the mineral fertilisation. Actilith F2 induced a high nitrification rate and N₂O production from denitrification was reduced while that from nitrification was not. This revised version was published online in August 2006 with corrections to the Cover Date.     

The comparative effect of a mixed urea,ammonium nitrate,ammonium sulphate granular formulation on the efficiency of N recovery by perennial ryegrass

The¹⁵N isotope was used to study the mode of action of individual nitrogen sources in a 30% urea:30% ammonium nitrate: 10% ammonium sulphate:30% filler (w/w) granular fertilizer for perennial ryegrass in a greenhouse pot experiment. The fertilizer consisted of two types of granules, one containing 80% urea and 20% filler and the second containing 48% ammonium nitrate (AN), 16% ammonium sulphate (AS) and 36% filler. In addition the effect of dolomite compared with silica as the filler was investigated on nitrogen recovery from the 30:30:10:30 formulation.Dolomite adversely affected the recovery of nitrate N from the system and evidence suggested that MgCO₃ was the active component. Granules containing dolomite resulted in a lower dry-matter yield than those containing silica, however the difference was not significant as nitrate contributed only 20% of the N in the formulation. AN gave the greatest DM yield and urea the lowest with AS being intermediate. The¹⁵N budget in shoots, roots and soil indicated that only 65% of the N from urea was recovered at the end of the experiment compared with 86% for AN and 91% for AS. The dry-matter yield of the 30:30:10:30 formulation using silica as the filler was intermediate between urea and AN; however, the apparent N recovery was significantly higher than expected from the sum of the individual components. The use of¹⁵N labelling indicated that using separate granules for ammonium N and urea the recovery of urea was improved by 11% in the triple N mixture when both AN and AS were present in the second granule compared to the recovery on its own. The enhanced recovery of urea appeared to be a function of AN and AS acting together as neither source in double combination with urea had any effect on urea N recovery.Urea enhanced the recovery of nitrate N by 10% but decreased the recovery of AS by 6% (in the 30:30:10:30 formulation) in comparison with the single sources on their own. The results indicate that interactions can occur between N sources even when they are physically separated by being in different granules.     

Transformation of calcium cyanamide and its inhibitory effect on urea nitrification in some tropical soils

Transformation of calcium cyanamide and its inhibitory effect on urea nitrification was studied in some tropical soils. Three soils, from Onne, Mokwa and Samaru, representing different agro-climatological zones of Nigeria were incubated with calcium cyanamide, urea or a mixture of both for eight weeks at 30 °C and at field capacity moisture content. The recovery of inorganic N (NH ₄ ⁺ plus NO ₂ ^- plus NO ₃ ^- )from calcium cyanamide varied from 64% to 87% in different soils. Most of the inorganic N accumulated was in NH ₄ ⁺ form. Nitrification of the accumulated NH ₄ ⁺ in all the soils was slow.Urea (75 mg N kg^–1 soil) was completely nitrified within a week in the Samaru and Mokwa soils whereas in the Onne soil the rate of nitrification was slow. Addition of CaCN₂ at the rate of 10 mg N kg^–1 soil generally delayed ammonification of urea and nitrification was severely inhibited in all the soils. Addition of CaCN₂ at the rate of 20 mg N kg^–1 soil further reduced the ammonification of urea and completely inhibited the nitrification. High recovery of inorganic N from calcium cyanamide and its effective reduction of nitrification of urea make it suitable source of N for plants in the tropics, provided it is managed to avoid phyto-toxicity.     

硝酸铈铵在有机合成中的应用

就近１０年来硝酸铈铵在硝化及硝酸酯化,氧化和催化氧化,引发加成和聚合等方面进行的应用进行了综述。     

The comparative effects of ammonium nitrate,urea or a combined ammonium nitrate/urea granular fertilizer on the efficiency of nitrogen recovery by perennial ryegrass

The comparative effects of ammonium nitrate (AN), urea or a combined 1:1 (w/w) AN/urea granular fertilizer with two different fillers (CaCO₃ or silica) were investigated on the efficiency of dry matter production and¹⁵N recovery by perennial ryegrass grown in pots under controlled environmental conditions.There was no significant difference between CaCO₃ and silica as the filler and therefore no indication that the presence of CaCO₃ in the pellet enhanced N loss from urea. Ammonium nitrate was the most efficient N source and urea the least efficient in terms of all the parameters studied. The¹⁵N budget in shoots, roots and soil indicated that only 60% of the nitrogen from urea was recovered at the end of the experiment compared with 95% for AN. However, the % recovery of¹⁵N from urea was increased by 17% in the presence of AN whereas the % recovery of AN was decreased by 19% in the presence of urea. The combined 1:1 (w/w) AN/urea source therefore gave intermediate yields between AN and urea alone. The results indicate that an interaction occurred between AN and urea in the granule.     

The effect of fertiliser type and application rate on denitrification losses from cut grassland in Northern Ireland

Denitrification losses were measured using the acetylene inhibition technique adapted for a coring procedure. Two soils under a cut ryegrass sward were used. One soil was a freely-drained clay loam receiving under 900 mm rainfall annually, the other soil being a poorly-drained silty clay receiving over 1100 mm rainfall annually. Swards at each site received up to 300 kg N ha^–1 yr^–1 of calcium ammonium nitrate (CAN), urea or a new fertiliser mixture GRANUMS (30% ammonium nitrate, 30% urea, 10% ammonium sulphate, 30% dolomite). For both soils the rate of denitrification exceeded 0.1 kg N ha^–1 day^–1 only when the air-filled porosity of the soil was < 30% v/v and soil nitrate was > 2 mg N kg^–1 in the top 10cm of the profile and when soil temperature at 10 cm was > 4°C. When the soils dried such that their air-filled porosity was > 30% v/v, denitrification rates decreased to < 0.08 kg N ha^–1 day^–1. Highest rates (up to 3.7 kg N ha^–1 day^–1) were observed on the clay soil following application of 94 kg N ha^–1 CAN to soil near field capacity in early summer 1986. Losses from CAN were approximately 3 times those from urea for a given application. Denitrification losses from the GRANUMS treatment were, overall, intermediate between those from CAN and urea but the daily losses more closely resembled those from the CAN treatment. The impeded drainage on the clay soil, where soil moisture contents remained close to field capacity throughout the year, showed denitrification losses roughly 3 times those observed on the more freely drained clay-loam for any given treatment. Over a 12-month period, N losses arising from denitrification were 29.0 and 10.0 kg N ha^–1 for plots receiving 300 kg N ha^–1 CAN and urea, respectively, on the well drained clay-loam and 79.0 and 31.1 kg N ha^–1 respectively, for identical plots on the poorly drained clay soil. Annual denitrification losses from control plots were < 1 kg N ha^–1 on both soils.     

Nitrogen leaching and uptake from calcium cyanamide in comparison to urea and calcium ammonium nitrate in an ultisol from the humid tropics

Leaching loss of N applied as calcium cyanamide (CaCN₂ — 19% N), urea and calcium ammonium nitrate (CAN — 26% N) to a coarse textured, kaolinitic ultisol profile was studied in the laboratory using undisturbed soil columns. The soil columns were leached with an amount of water equivalent to the annual rainfall of the sampling site (2420mm) using a rainfall simulator over a period of 42 days. The leachability of the three N fertilizers differed greatly and followed the order of CAN > urea > CaCN₂. Most of the N lost through leaching was in NO₃ form. Calcium cyanamide lost only 3% of applied N. Breakdown of CaCN₂ to NH₄ was incomplete (64%) and nitrification in the soil was inhibited resulting in negligible leaching loss. Nitrogen retained in the soil columns after the leaching cycle was mainly in ammoniacal form irrespective of source of N used.Effectiveness of CaCN₂ as a N source was also studied in a greenhouse experiment with maize (Zea mays) and upland rice (Oryza sativa) as testing crops. Calcium cyanamide applied one week before sowing of crops was as effective as CAN and urea under conditions of no N leaching. When applied at the time of planting and two or more weeks before planting gave lower dry matter yields and N uptake than CAN and urea.IITA Journal Paper no. 351     

A comparative study of urea hydrolysis rate and ammonia volatilization from urea and urea calcium nitrate

A comparing of urea hydrolysis and NH₃ volatilization from urea supergranules and urea calcium nitrate (UCN, a new fertilizer produced by Norsk Hydro A/S, Norway) was made on two different flooded soil types, a high-CEC clay loam (Ås) and an intermediate-CEC clay loam (Kinn).Nitrogen loss by ammonia volatilization was reduced from 17% by surface application of urea supergranules (USG) on flooded Ås soil to 3% and 6% by UCN briquettes at either the same urea or nitrogen concentration as USG. A significant reduction was even found with the surface application of prilled UCN, 12% and 18% N-loss for prilled UCN and urea, respectively. The floodwater pH and NH ₄ ⁺ content was lower with UCN than urea, which reduced the potential for ammonia volatilization.NH₃-loss (5%) was significantly less when USG was surface applied on Kinn soil, while NH₃-loss from UCN briquettes was independent of soil type. The reduction in NH₃-loss from USG on Kinn soil was due to a decrease in the pH and NH ₄ ⁺ content of the floodwater caused by a reduced rate of urea hydrolysis.The rate of urea hydrolysis was lower with UCN than USG in both soils, but the difference between UCN and USG was greater in the Ås soil than in the Kinn soil. Three days after deep placement (10 cm), 18% of UCN urea and 52% of USG urea were hydrolyzed in Ås soil, while only 12% UCN and 17% USG were hydrolyzed in the Kinn soil.The surface application of USG on flooded soil reduced the rate of urea hydrolysis as compared to deep placement. 30% and 17% of USG urea was hydrolyzed after four days on Ås and Kinn soil, respectively. During the first few days the rate of hydrolysis of UCN was more affected by the soil type than the application method. Four days after surface application 32% and 13% UCN urea was hydrolyzed on Ås and Kinn soil, respectively. The rate of urea hydrolysis exhibited a zero-order reaction when USG and UCN-briquettes were point placed in flooded soils.     

Ammonium transformation in paddy soils affected by the presence of nitrate

Coupled nitrification and denitrification is considered as one of the main pathways of nitrogen losses in paddy soils. The effect of NO₃ ^– on NH₄ ⁺ transformation was investigated by using the ¹⁵N technique. The paddy soils were collected from Wuxi (soil pH 5.84) and Yingtan (soil pH 5.02), China. The soils were added with either urea (18.57 mol urea-N enriched with 60 atom% ¹⁵N excess) plus 2.14 mol KNO₃-N (natural abundance) per gram soil (U+NO₃) or urea alone (U). The KNO₃ was added 6 days after urea addition. The incubation was carried out under flooded condition in either air or N₂ gas headspace at 25°C. The results showed that in air headspace, ¹⁵NH₄ ⁺ oxidization was so fast that about 10% and 8% of added ¹⁵N in the treatment U could be oxidized during the incubation period of 73 hours after KNO₃ addition in Wuxi and Yingtan soil, respectively. The addition of KNO₃ significantly inhibited ¹⁵NH₄ ⁺ oxidation (p<0.01) in air headspace, while it stimulated ¹⁵NH₄ ⁺ oxidation in N₂ gas headspace, although the oxidation was depressed by the N₂ gas headspace itself. Therefore, the accumulation of NO₃ ^– would inhibit further nitrification of NH₄ ⁺ at micro-aerobic sites in paddy soils, especially in paddy soils with a low denitrification rate. On the other hand, NO₃ ^– would lead to oxidation of NH₄ ⁺in anaerobic bulk soils.     

探讨影响硝酸铵钙转鼓流化床造粒的因素

运用硝酸铵钙产品开发试验数据,分析影响硝酸铵钙造粒过程的因素,并提出了最佳的操作参数。     

聚苯乙烯包覆硝酸铵改善吸湿性的研究

采用相分离法制备了聚苯乙烯(PS)包覆硝酸铵(AN),研究了甲苯和正己烷体积比、聚苯乙烯与硝酸铵质量比、混合溶剂与硝酸铵配比、沉淀剂加入速度等因素对聚苯乙烯包覆硝酸铵性能的影响。用吸湿降低率评价聚苯乙烯对硝酸铵包覆程度。结果表明,聚苯乙烯包覆硝酸铵的较佳工艺条件为甲苯与正己烷体积比为1∶3,混合溶剂/AN=3.5 mL/g,室温,沉淀剂滴速10滴/min。包覆60目硝酸铵,PS质量分数为1.54%,包覆AN吸湿降低率75%。硝酸铵目数增大,达到相同吸湿降低率,PS用量显著增大。     

流化床中硝酸钙晶体生长的实验研究

流态化结晶分离硝酸钙是改进硝酸磷肥工艺的关键技术。实验获得了流化床循环流动条件下的Ca(NO3)2-H2O二元体系溶液在6.5～24.5℃的第1过饱和曲线,其对应的拟介稳相区过饱和度Δw(Ca(NO3)2)=4.2%～4.5%。该条件下四水硝酸钙晶体在流化床中均匀生长,平均线性生长速率可达u=0.06mm/min。     

碳氮比与氨氮负荷对序批式活性污泥法同步硝化反硝化的影响

为了提高生物脱氮的效率,研究采用序批式活性污泥法(SBR工艺)考察碳氮质量比w(C/N)与氨氮负荷对同步硝化反硝化的影响。结果表明:当w(C/N)为5.6,氨氮负荷为0.024 g/(g.d),碳源快速消耗,SBR工艺较难实现同步硝化反硝化,同步硝化反硝化率只能够达到0.76%。当w(C/N)为10.5,氨氮负荷为0.024 g/(g.d)时,SBR系统能够实现同步硝化反硝化,同步硝化反硝化率达到97.6%,NH4+-N和COD去除率均接近100%;当w(C/N)为16.3,氨氮负荷为0.024 g/(g.d)时,同步硝化反硝化率为94.5%,增加外加碳源的成本。同步硝化反硝化可以取代二段独立的硝化和反硝化过程,节省运行费用。     

Frequency distributions and spatially dependent variability of ammonium and nitrate concentrations in soil under grazed and ungrazed grassland

The frequency distributions of soil NO ₃ ^- and NH ₄ ⁺ concentrations under grazed and ungrazed grassland were found to be lognormal, irrespective of time of year or soil depth. The variance and skewness of the sample values increased with stocking density and use of N fertilizer. An analysis of the spatial dependence of the variability using the semivariogram showed a high nugget variance, even when three sample values from each sampling point were averaged. Most of the variance was therefore short-range (occurring within a distance of 0.4 m), suggesting that the sample volume for soil mineral N measurement should be as large as is practicably possible. As an estimate of the average mineral N content, the geometric mean of the sample values consistently underestimated the true arithmetic mean of the population from which the same was drawn. The conventional estimate of the arithmetic mean for lognormally distributed samples values was satisfactory when the sample number was > 50 and the (log) variance < 0.75 (µg N cm^–3). However, for data with larger variances, high coefficients of skewness and fewer observations, Sichel's estimator was a more efficient measure of the true population mean.     

农用硝酸铵水溶液热爆炸机理研究

为了防止硝酸铵在生产过程中发生爆炸事故,利用自行设计的实验装置对硝酸铵水溶液的临界爆炸温度进行了实验研究,并从反应动力学的角度对其影响因素进行了分析。研究结果表明,硫酸及氯离子两者同时存在时,临界爆炸温度随着氯离子浓度的增加而降低,两者呈良好的指数关系;临界爆炸温度的对数与氯离子质量分数的倒数成线性关系,反应动力学可以较好地解释这一现象。研究结果对硝酸铵的安全生产有重要的指导意义。     

Effect of the nitrification inhibitors 1-amidino-2-thiourea and dicyandiamide in combination with urea and ammonium sulfate

The efficiency of the nitrification inhibitors dicyandiamide (DCD) and 1-amidino-2-thiourea (or guanylthiourea = GTU) in reducing losses from N fertilizers was investigated in two greenhouse experiments where leaching of nitrate-N was induced by percolation at 3 and 5 weeks after fertilization.At an application rate of 10% by weight of fertilizer-N (e.g. 10 kg GTU/ha), GTU in combination with ammonium sulfate (AS) had effects similar to those of DCD (e.g. 15 kg DCD/ha) with regard to nitrate leaching, plant yields and nitrogen uptake. However, in combination with urea (U), GTU was more effective than DCD when applied at the same ratio except with a humic sandy clay soil (pH 7.3, 4.4% organic C), where GTU did not perform as effectively. Nitrate leaching was reduced by as much as 50% using U/GTU instead of U/DCD, and plant yield increased by 30%.At temperatures between 17 and 25°C, the combination U/GTU could protect a high percentage of the nitrogen from being nitrified and leached over a 3 to 5 weeks period. The superiority of GTU over DCD was demonstrated especially in the treatments with 5 weeks of preincubation, despite the considerably lower application rate.     

The effect of nitrogenous fertilizers on the nitrification of forest soils

The effect of fertilization with urea and ammonium nitrate on nitrogen mineralization was studied in a series of laboratory incubation experiments. The samples (humus layer) were collected from field experiments with different applications of fertilizers during a period of 11–14 years. The nitrogen fertilization influenced some chemical properties of the humus layer such as pH, N-Kjeldahl content and the content of inorganic nitrogen, especially in the samples from North Sweden. Nitrate nitrogen was formed in humus samples classified as non-nitrifying in several cases, usually after urea fertilization.     

硝酸磷肥工艺中硝酸钙结晶的分离过程

结合十多年的生产经验 ,介绍硝酸磷肥装置硝酸钙结晶分离原理和流程 ,提出工艺指标的控制方法、常见故障的原因和处理方法。