Low-Temperature Synthesis of Nano-AlN Based on Solid Nitrogen Source by Plasma-Assisted Ball Milling

Plasma-assisted ball milling was carried out on the Al+C3H6N6 system and Al+C_(4)H_(4)N_(4) system,respectively.The phase structure,functional groups and synthesis mechanism were analyzed by XRD and FT-IR,and the differences in the synthesis process of nano-AlN with different solid nitrogen sources were discussed.The results show that C3H6N6 has a stable triazine ring structure,and its chemical bond is firm and difficult to break,so AlN cannot be synthesized directly by solid-solid reaction at room temperature.However,there are a large number of nitrile groups(-CN)and amino groups(-NH_(2))in C_(4)H_(4)N_(4) molecules.Under the combined action of plasma bombardment and mechanical energy activation,C_(4)H_(4)N_(4) molecules undergo polycondensation and deamination,so that the ball milling tank is filled with a large number of active nitrogen-containing groups such as N=,≡N,etc.These groups and ball milling activated Al can synthesize nano-AlN at room temperature,with a conversion rate of 92%.SEM,DSC/TG analysis showed that the powder obtained by ball milling was formed by soft agglomeration of many fine primary particles about 50–80 nm.The surface morphology of the powder was loose and porous,and it had strong activity.After annealing at 800℃,the conversion rate of the Al+C_(4)H_(4)N_(4) system reached 99%.

Thermal decomposition of magnesium ammonium phosphate and adsorption properties of its pyrolysis products toward ammonia nitrogen

High-purity magnesium ammonium phosphate （MAP） was precipitated by controlling pH value of the reaction system of 9.0-9.5. The thermal decomposition behavior of MAP and the adsorption properties of its pyrolysis products toward ammonia-nitrogen were also studied by XRD, SEM, TGA-DTA and FT-IR methods. The results indicated that high-purity MAP was obtained at pH value of 9.0-9.5. Upon heating to 100-120℃ for 120 min, MAP was thermally decomposed, losing water and ammonia concomitantly with a reduction in grain size and crystallinity. The capacity of pyrolysis products for ammonia nitrogen adsorption reached 72.5 mg/g, with a removal rate of up to 95% from an 800 mg/L solution. The characteristic diffraction peaks corresponding to MAP mainly appeared in their XRD patterns after adsorption of ammonia nitrogen. The pyrolysis products of MAP at 100-120 ℃ could be recycling-used as the chemical treatment regents of ammonia nitrogen in the practical application.

Twice-split phosphorus application alleviates low-temperature impacts on wheat by improved spikelet development and setting

Extreme low-temperature incidents have become more frequent and severe as climate change intensifies.In HuangHuai-Hai wheat growing area of China,the late spring coldness occurring at the jointing-booting stage(the anther interval stage)has resulted in significant yield losses of winter wheat.This study attempts to develop an economical,feasible,and efficient cultivation technique for improving the low-temperature(LT)resistance of wheat by exploring the effects of twice-split phosphorus application(TSPA)on wheat antioxidant characteristics and carbon and nitrogen metabolism physiology under LT treatment at the anther interval stage using Yannong 19 as the experimental material.The treatments consisted of traditional phosphorus application and TSPA,followed by a-4℃ LT treatment and natural temperature(NT)control at the anther interval stage.Our analyses showed that,compared with the traditional application,the TSPA increased the net photosynthetic rate(P_(n)),stomatal conductance(Gs),and transpiration rate(T_(r))of leaves and reduced the intercellular carbon dioxide concentration(C_(i)).The activity of carbon and nitrogen metabolism enzymes in the young wheat spikes was also increased by the TSPA,which promoted the accumulation of soluble sugar(SS),sucrose(SUC),soluble protein(SP),and proline(Pro)in young wheat spike and reduced the toxicity of malondialdehyde(MDA).Due to the improved organic nutrition for reproductive development,the young wheat spikes exhibited enhanced LT resistance,which reduced the sterile spikelet number(SSN)per spike by 11.8%and increased the spikelet setting rate(SSR)and final yield by 6.0 and 8.4%,respectively,compared to the traditional application.The positive effects of split phosphorus application became more pronounced when the LT treatment was prolonged.

Oxygen adsorption/desorption behavior of YBaCo4O7+δ and its application to oxygen removal from nitrogen

A new medium-temperature (200-400 °C) adsorbent material for oxygen removal and air separation, YBaCo4O7+δ, was prepared by the solid-state reaction method. This new adsorbent could adsorb a large quantity of oxygen in the temperature range of 200-370 °C. Adsorbed oxygen could be released by raising temperature over 400 °C or by switching the atmosphere from oxygen to nitrogen. This oxygen adsorption and desorption process had good reproducibility. Taking advantage of this unique oxygen intake/release behavior, a nitrogen purification process was investigated. The results showed that YBaCo4O7+δ material was a promising candidate for the oxygen sorption process and could be used to produce high-purity nitrogen or to remove trace oxygen from other gases.

A high-performance biochar produced from bamboo pyrolysis with in-situ nitrogen doping and activation for adsorption of phenol and methylene blue

Nitrogen doping is a promising method for the preparation of functional carbon materials.In this study,a nitrogen-doped porous coral biochar was prepared by using bamboo as raw material,urea as nitrogen source,and KHCO3 as green activator through in-situ pyrolysis.The structure of the obtained biochar was characterized by various techniques including nitrogen adsorption and desorption,Raman spectroscopy,X-ray photoelectron spectrometer,and etc.The adsorption properties of nitrogen-doped biochar were evaluated with phenol and methylene blue probes.The results showed that the nitrogen source ratio had a significant effect on the evolution of pore structure of biochar.Low urea addition ratio was beneficial to the development of pore structures.The optimum specific surface area of nitrogen-doped biochar could be up to 1693 m^2·g^-1.Nitrogen doping can effectively improve the adsorption capacity of biochar to phenol and methylene blue.Biochar prepared at 973.15 K with low urea addition ratio exhibited the highest adsorption capacity for phenol and methylene blue,and the equilibrium adsorption capacity was 169.0 mg·g^-1 and 499.3 mg·g^-1,respectively.By comparing the adsorption capacity of various adsorbents in related fields,it is proved that the nitrogen-doped biochar prepared in this study has a good adsorption effect.

Preparation of Clay/Biochar Composite Adsorption Particle and Performance for Ammonia Nitrogen Removal from Aqueous Solution

This study aimed to present a novel clay/biochar composite adsorption particle, which made from abandoned reed straw and clay to remove ammonia nitrogen(NH4^+-N) from micro-contaminated water. The removal performance of NH4^+-N by composite adsorption particle was monitored under different raw material proportions and initial NH4^+-N concentration. Besides, adsorption kinetics and adsorption isotherms were investigated to reveal the adsorption mechanisms. The results showed that NH4^+-N was effectively removed under optimal proportion of biochar, foaming agent and crosslinker with 20%, 3%, and 3%, respectively. The optimal contact time was 150 min and the best removal efficiency was 88.6% at initial NH4^+-N concentration of 20 mg L^-1. The adsorption performance was well described by the second order kinetic model and Freundlich model. The novel clay/biochar composite adsorption particle in this study demonstrated a high potential for NH4^+-N removal from surface water.

Multifractal characteristics of shale and tight sandstone pore structures with nitrogen adsorption and nuclear magnetic resonance

Based on the experiments of nitrogen gas adsorption(N_2 GA) and nuclear magnetic resonance(NMR),the multifractal characteristics of pore structures in shale and tight s andstone from the Chang 7 member of Trias sic Yanchang Formation in Ordos Basin,NW China,are investigated.The multifractal spectra obtained from N2 GA and NMR are analyzed with pore throat structure parameters.The results show that the pore size distributions obtained from N2 GA and NMR are different,and the obtained multifractal characteristics vary from each other.The specific surface and total pore volume obtained by N2 GA experiment have correlations with multifractal characteristics.For the core samples with the similar specific surface,the value of the deviation of multifractal spectra Rd increases with the increase in the proportion of large pores.When the proportion of macropores is small,the Rd value will increase with the increase in specific surface.The multifractal characteristics of pore structures are influenced by specific surface area,average pore size and adsorption volume measured from N2 GA experiment.The multifractal characteristic parameters of tight sandstone measured from NMR spectra are larger than those of shale,which may be caused by the differences in pore size distribution and porosity of shale and tight sandstone.

Improved analytic methods for coal surface area and pore size distribution determination using 77 K nitrogen adsorption experiment

77 K nitrogen adsorption was the most widely used technique for determining surface area and pore size distribution of coal. Brunauer–Emmett–Teller(BET) and Barrett–Joyner–Halenda(BJH) model are commonly used analytic methods for adsorption/desorption isotherm. A Chinese anthracite coal is tested in this study using an improved experimental method and adsorption isotherm analyzed by three adsorption mechanisms at different relative pressure stages. The result shows that the micropore filling adsorption predominates at the relative pressure stage from 6.8E 7 to 9E 3. Theoretically, BET and BJH model are not appropriate for analyzing coal samples which contain micropores. Two new analytic procedures for coal surface area and pore size distribution calculation are developed in this work. The results show that BET model underestimates surface area, and micropores smaller than 1.751 nm account for 35.5% of the total pore volume and 74.2% of the total surface area. The investigation of surface area and pore size distribution by incorporating the influence of micropore is significant for understanding adsorption mechanism of methane and carbon dioxide in coal.

Nitrogen release and re-adsorption dynamics on crop straw residue during straw decomposition in an Alfisol

Returning crop straw to the field not only improves the nitrogen(N) supplying capacity and N retention of soil but also decreases the amount of rural organic waste and prevents air pollution. Therefore, understanding the mechanisms of the N release and re-adsorption dynamics on crop straw residue during straw decomposition in agricultural soil is important, and this understanding can help us strengthen N fertilizer management during the crop growth period. An on-farm incubation experiment was conducted in the Jianghan Plain in Central China under flooded conditions using the nylon mesh bag method. Results showed that the decomposition rate of crop straw was much faster at the beginning of the incubation stage, whereas it was steady during the later stage with no observed differences among the three types of crop straw. After 120 d of incubation, the cumulative decomposition proportion of rice straw, wheat straw and rape straw was 72.9, 56.2, and 66.9%, respectively. The proportion of N that released from the three crop straws was 52.0, 54.4 and 54.9%, respectively. The zeta potentials and Brunauer, Emmett and Teller(BET) surface area of the rice, wheat and rape straw residues increased gradually as the decomposition period progressed. The water adsorption capacity of the rice straw was significantly affected during the decomposition period. The saturated water adsorption capacity of rice straw was the highest at 30 d of decomposition(4.17 g g^–1) and then decreased slightly. The saturated water adsorption of wheat and rape straws reached the lowest value at 30 d and then gradually increased and became stable. All the results demonstrated that crop straw and straw residue can re-adsorb NH4^+ ions from the surrounding solution. The re-adsorption was affected by the decomposition period and concentration of exogenous NH4^+ and was independent of the crop species via the combined efforts of physical and chemical adsorption, ion exchange and water retention on residue surfaces. Future studies will focus on straw returning and N fertilizer application at different levels of moisture content of the soil reduce potential negative effects such as water-logging and excess N caused by the straw substrate.

A DFT Study on the Adsorption Behavior of Sulfur and Nitrogen Compounds on the NiMoS Phase

The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.

Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach

To characterize the pore features of outburst coal samples and investigate whether outburst coal has some unique features or not, one of the authors, working as the member of the State Coal Mine Safety Committee of China, sampled nine outburst coal samples(coal powder and block) from outburst disaster sites in underground coal mines in China, and then analyzed the pore and surface features of these samples using low temperature nitrogen adsorption tests. Test data show that outburst powder and block coal samples have similar properties in both pore size distribution and surface area. With increasing coal rank, the proportion of micropores increases, which results in a higher surface area. The Jiulishan samples are rich in micropores, and other tested samples contain mainly mesopores, macropores and fewer micropores. Both the unclosed hysteresis loop and force closed desorption phenomena are observed in all tested samples. The former can be attributed to the instability of the meniscus condensation in pores,interconnected pore features of coal and the potential existence of ink-bottle pores, and the latter can be attributed to the non-rigid structure of coal and the gas affinity of coal.

Kinetic of Adsorption of Urea Nitrogen onto Chitosan Coated Dialdehyde Cellulose under Catalysis of Immobilized Urease

The adsorption of urea nitrogen onto chitosan coated dialdehyde cellulose (CDAC) under catalysis of immobilized urease in gelatin membrane (IE) was studied in batch system. The pseudo first-order and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model.

AN APPROACH TO CALCULATE THE SURFACE TENSION OF THE LIQUID NITROGEN FILM ON SOLIDS FROM AN ADSORPTION ISOTHERM

The equations, used in this paper to calculate the surface tension of the liquid nitrogen film formed by the physical adsorption on many different model solids (e.g. spherical partiele, plane particle and spherical cavity pores or cylindrical pores at the openings of both ends in solid bodies), have been derived on the thermodynamie principle. The calculated results have shown that the surface tension (γ) of the adsorbed liquid nitrogen film on most of non-porous solid surfaces diminishes with the rise of the nitrogen gas pressure (p) or of the adsorbed layers (n) at 77.3K; when p reaches the vapour pressure (p_s) of the bulk liquid nitrogen, y turns into the surface tension (γ_o) of the bulk liquid nitrogen; whgn p /p, 【0.98, there is an obvious difference between γ and γ_O.

PREPARATION OF UREA NITROGEN ADSORBENT OF COMPLEX TYPE AND ADSORPTION CAPACITY OF UREA NITROGEN ONTO THE ADSORBENT

The urea nitrogen adsorbent of complex type, which consists of chitosan coated dialdehyde cellulose （CDAC） and immobilized urease in gelatin membrane （IE）, was prepared. The cellulose, the dialdehyde cellulose （DAC） and the CDAC were characterized by scanning electronic microscope. The results indicate that the cellulose C2-C3 bond was broken under the oxidation of periodate and it was oxidated to DAC. The DAC was coated with chitosan and the CDAC was obtained. The adsorption of urea nitrogen onto the adsorbent in Na2HPO4-NaH2PO4 buffer solution was studied in batch system. The effects of the experiment parameters, including degree of oxidation of CDAC, initial urea nitrogen concentration, pH and temperature, on the adsorption capacity of urea nitrogen onto the adsorbent at CDAC/IE weight ratio 10：1 were investigated. The results indicate that these parameters affected significantly the adsorption capacity. The adsorption capacity of urea nitrogen onto the adsorbent was 36.7 mg/g at the degree of oxidation of CDAC 88%, initial urea nitrogen concentration 600 mg/L, pH 7.4 and temperature 37℃.

Adsorption and Desorption Characteristics of Nitrogen and Phosphorus in Paddy Soils from Different Parent Materials

Reddish clayey soil(HH),alluvial sandy soil(HS),granitic sandy soil(MS)and purple clayey soil(ZS)were used as the test materials to reveal the adsorption-desorption characteristics of nitrogen and phosphorus nutrients in paddy soils from different parent materials.The results showed that the nitrogen desorption amount of each soil was greater than the nitrogen adsorption amount in the low nitrogen concentration range of 0~10 mg/L;in the high nitrogen concentration range of 20~50 mg/L,the soil nitrogen desorption rate gradually decreased with the increase of nitrogen concentration of the equilibrium liquid;when the soil nitrogen adsorption amount was-57.267~352.400 mg/kg,the nitrogen adsorption capacity of the paddy soils from different parent materials was HS>ZS>HH>MS;when the nitrogen desorption amount was 8.367~37.833 mg/kg,the nitrogen desorption capacity of the paddy soils from different parent materials was HH>HS>MS>ZS;the nitrogen adsorption isothermal curves of HH,MS,HS and ZS fitted the Linear model,the correlation coefficients were 0.928~0.978.At the same time,in the range of low phosphorus concentration(0~10 mg/L),the phosphorus adsorption amounts of 4 paddy soils were greater than their phosphorus desorption amounts.When the phosphorus concentration of the equilibrium solution exceeded 10 mg/L,phosphorus fixation capacities of 4 paddy soils weakened,meanwhile their phosphorus desorption increased,but their adsorption amounts were still greater than their desorption amounts.When phosphorus adsorption and desorption amounts of 4 paddy soils were-110.312~534.961 and 0.188~14.320 mg/kg respectively,the phosphorus adsorption and desorption capacities of 4 paddy soils were HS>HH>ZS>MS and ZS>MS>HS>HH,respectively.The phosphorus adsorption isothermal curves of 4 paddy soils fitted the Langmuir and Freundlich models,the correlation coefficient were 0.945~0.995.In general,paddy soils developed from different parent materials in Hunan Province have different adsorption and desorption characteristics for nitrogen and phosphorus.Purple clayey soil has the strongest nitrogen fixation capacity due to its stronger viscosity,which can reduce the risk of nitrogen loss by effectively holding nitrogen in the soil solution.On the contrary,being of strong sandy property,granitic sandy soil has the worst nitrogen fixation capacity and higher risk of nitrogen loss.The four paddy soils have strong adsorption capacity and low desorption rate of phosphorus,which indicates that the main paddy soils in Hunan Province have strong adsorption capacity for phosphorus and relatively small loss risk.

Reactive adsorption of thiophene on Ni/ZnO adsorbent:Effect of ZnO textural structure on the desulfurization activity

To better understand the nature of reactive adsorption of thiophene on Ni/ZnO adsorbent,the effect of ZnO textural structure on the desulfurization activity was investigated.ZnO materials were synthesized by low-temperature solid-state reaction and the corresponding Ni/ZnO adsorbents were prepared by incipient impregnation method.The analysis results showed that the crystalline sizes of ZnO as-synthesized as well as the BET surface areas varied obviously with the calcination temperature.The activity evaluations indicated that the Ni/ZnO adsorbents prepared with ZnO possessed a favorable textural structure as active component exhibited good activity of removing thiophene.The evolutions of the main crystalline phases of Ni/ZnO adsorbents before and after reaction confirmed that ZnO played a crucial role in taking up S element and converting it into ZnS in the reactive adsorption process.It was concluded that ZnO with larger surface area and smaller crystal particles resulted in better desulfurization activity,which may be the main reason for the different activities of the Ni/ZnO adsorbents prepared with ZnO calcined at different temperatures.

Distribution characteristics and oil mobility thresholds in lacustrine shale reservoir:Insights from N_(2)adsorption experiments on samples prior to and following hydrocarbon extraction

The pore structure and oil content of shales have an important influence on the oil mobility and enrichment.In this study,the lacustrine shale samples from the Qingshankou Formation(Q1)of Songliao Basin were selected.TOC,pyrolysis,XRD and nitrogen adsorption were performed on the original and extracted shale samples.Then the influence of mineral composition and organic matter(OM)on the development of nano-scale pore,the oil phase states and mobility were analyzed.The Q1 shale samples can be sub-divided into three types according to the isotherm characteristics.Type A samples are characterized by high kerogen content,with oil mainly existing in the free phase state.Type B samples are characterized by medium kerogen content,oil mainly exists in the absorbed phase state.Type C samples are characterized by low kerogen content,with trace oil found in the absorbed phase state.Nano-scale organic pores are well developed in the Q1 Formation.Oil is primarily found in the pore spaces with diameters less than 10 nm,this being the pore size threshold for mobile shale oil.When TOC>2.0 wt%and EOM>1.0 wt%,Q1 Formation shale oil mobility is high,resulting in prospective drilling targets.

Experimental Research on Pore Structure and Gas Adsorption Characteristic of Deformed Coal

The pore structure and gas adsorption property of deformed coal with different degrees of metamorphism were tested by low-temperature nitrogen adsorption and isothermal adsorption experiments. The fractal theory and the Langmuir adsorption theory were used to analyze the experimental data. The test results showed that the deformed coal had more heterogeneous pore structures and open pores, and its specific surface area(SSA) and fractal dimension(D) were higher. There is a polynomial relationship between D and specific surface area as well as gas adsorption capacity(VL). The gas adsorption capacity of deformed coal is influenced by pore structure, coal rank, deformation and stress together, among which the pore structure is the main influencing factor for the adsorption capacity of deformed coal. The test pressure could affect the accuracy of the adsorption constants a and b, so the highest experiment pressure should be greater than the actual pressure of coal seam in order to reduce the deviation of adsorption constants.

Ammonium Ion Adsorption and Settleability Improvement Achieved in a Synthetic Zeolite-Amended Activated Sludge

Municipal wastewater treatment plants typically exhibit two classic problems： high ammonium concen- tration in water after conventional biological treatment and, in some cases, poor activated sludge sediment ability. Potential solutions to these problems were investigated by adding a synthetic zeolite obtained from coal fly ash to different steps of activated sludge treatment. The experimental results for ammonium removal fit well with the theoretical adsorption isotherms of the Freundlich model with a maximum adsorption capacity of 13.72 mg.g-＇. Utiliza- tion of this kind of zeolite to improve activated sludge sediment ability is studied for the first time in this work. It is found that the addition of the zeolite （1 g. L-1） to an activated sludge with settling problems significantly enhances its sediment ability and comoact ability. This is confirmed by the sludge volume index （SVI）, which was reduced from 163 ml.g-1 to 70 ml.g-r, the V60 value, which was reduced from 894 ml.L-1 to 427 ml.L-1, and the zeta poten- tial （0, which was reduced from -19.81 mV to -14.29 mV. The results indicate that the addition of this synthetic zeolite to activated sludge, as an additional waste management practice, has a positive impact on both ammonium removal and sludge settleability.

An Experimental Study on the Adsorption Behavior of Gases Crossing the Critical Temperature

Adsorption equilibria of CH_4 and N_2 on activated carbon andsilica gel were measured for a wide temperature range covering thecritical point: 158-298 K for CH_4, and 103-298 K for N_2. Thedetermination of the compressibility factor is shown to haveconsiderable effect on isotherm behavior at conditions after theisotherm maximum. A change in adsorption mechanisms on crossing thecritical temperature was observed in all cases. The kind ofadsorbents and how far the equilibrium temperature to the criticalone are major factors affecting the Transition of isotherms from sub-to supercritical.