High-performance SSZ-13 membranes prepared using ball-milled nanosized seeds for carbon dioxide and nitrogen separations from methane

SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.

Hydrogen-bonded metal-nucleobase frameworks for highly selective capture of ethane/propane from methane and methane/nitrogen separation

The separation of light hydrocarbons,including C_(2)H_(6)and C_(3)H_(8),is essential to natural gas upgrading.Meanwhile,N_(2)removal from CH_(4)is also crucial to concentrating low-quality coalbed methane,but the adsorption process is challenging because of the close kinetic diameter.This work reports two hydrogen-bonded metal-nucleobase frameworks(HOF-ZJU-201 and HOF-ZJU202)capable of efficiently separating C_(3)H_(8)/CH_(4),C_(2)H_(6)/CH_(4),and CH_(4)/N_(2).Due to strong affinity for C_(3)H_(8)and C_(2)H_(6),the lowpressure capacity for C_(3)H_(8)(5 kPa)and C_(2)H_(6)(10 kPa)of HOF-ZJU-201a exceeds most adsorbents.The ideal adsorbed solution theory(IAST)selectivity of C_(3)H_(8)/CH_(4)and C_(2)H_(6)/CH_(4)is 119 and 45 at ambient conditions.According to density functional theory calculations,surface polarization environments formed by electron-rich anions and electron-deficient purine heterocyclic rings contribute to the selective capture of C_(3)H_(8)and C_(2)H_(6)with greater polarizability.Furthermore,the high CH_(4)adsorption capacity(1.73 mmol/g for HOF-ZJU-201a and 1.50 mmol/g for HOF-ZJU-202a at 298 K and 1.0 bar)and excellent CH_(4)/N_(2)selectivity(6.0 for HOF-ZJU-201 at 298 K),as well as dynamic breakthrough experiments of binary CH_(4)/N_(2)gas mixture implied their efficacy in the concentration of low-quality coalbed methane.

Sponge Effect on Coal Mine Methane Separation Based on Clathrate Hydrate Method

The findings were presented from laboratory investigations on the hydrate formation and dissociation processes employed to recover methane from coal mine gas.The separation process of coal mine methane(CMM) was carried out at 273.15K under 4.00 MPa.The key process variables of gas formation rate,gas volume stored in hydrate and separation concentration were closely investigated in twelve THF-SDS-sponge-gas systems to verify the sponge effect in these hydrate-based separation processes.The gas volume stored in hydrate is calculated based on the measured gas pressure.The CH4 mole fraction in hydrate phase is measured by gas chromatography to confirm the separation efficiency.Through close examination of the overall results,it was clearly verified that sponges with volumes of 40,60 and 80 cm 3 significantly increase gas hydrate formation rate and the gas volume stored in hydrate,and have little effect on the CH4 mole fraction in hydrate phase.The present study provides references for the application of the kinetic effect of porous sponge media in hydrate-based technology.This will contribute to CMM utilization and to benefit for local and global environment.

Optimization strategy and procedure for coal bed methane separation

Coal bed methane （CBM） has a huge potential to be purified to relieve the shortage of natural gas meanwhile to weaken the greenhouse effect. This paper proposed an optimal design strategy for CBM to obtain an integrated process configuration consisting of three each single separation units, membrane, pressure swing absorption, and cryogenics. A superstructure model was established including all possible network configurations which were solved by MINLP. The design strategy optimized the separation unit configuration and operating conditions to satisfy the target of minimum total annual process cost. An example was presented for the separation of CH4/N2 mixtures in coal bed methane （CBM） treatment. The key operation parameters were also studied and they showed the influence to process configurations.

Synergistic Effects of Nitrogen Amendments and Ethylene on Atmospheric Methane Uptake under a Temperate Old-growth Forest

An increase in atmospheric nitrogen （N） deposition can promote soil acidification, which may increase the release of ethylene （C2H4） under forest floors. Unfortunately, knowledge of whether increasing N deposition and C2H4 releases have synergistic effects on soil methane （CH4） uptake is limited and certainly deserves to be examined. We conducted some field measurements and laboratory experiments to examine this issue. The addition of （NH4）2SO4 or NH4Cl at a rate of 45 kg N ha-1 yr-1 reduced the soil CH4 uptake under a temperate old-growth forest in northeast China, and there were synergistic effects of N amendments in the presence of C2H4 concentrations equal to atmospheric CH4 concentration on the soil CH4 uptake, particularly in the NH4Cl-treated plots. Effective concentrations of added C2H4 on the soil CH4 uptake were smaller in NH＋4 -treated plots than in KNO3-treated plots. The concentration of ca 0.3 μl C2H4 L-1 in the headspace gases reduced by 20% soil atmospheric CH4 uptake in the NH4Cl-treated plots, and this concentration was easily produced in temperate forest topsoils under short-term anoxic conditions. Together with short-term stimulating effects of N amendments and soil acidification on C2H4 production from forest soils, our observations suggest that knowledge of synergistic effects of NH＋4 , rather than NO3- , amendments and C2H4 on the in situ soil CH4 uptake is critical for understanding the role of atmospheric N deposition and cycling of C2H4 under forest floors in reducing global atmospheric CH4 uptake by forests. Synergistic functions of NH4＋ -N deposition and C2H4 release due to soil acidification in reducing atmospheric CH4 uptake by forests are discussed.

Effects of Nitrogen Fertilizer,Soil Moisture and Temperature on Methane Oxidation in Paddy Soil

Effects of nitrogen fertilizer,soil moisture and temperature on methane oxidation in paddy soil were investigated under laboratory conditions. Addition of 0.05 g N kg-1 soil as NH4Cl strongly inhibited methane oxidation and addition of the same rate of KCl also inhibited the oxidation but with more slight effect,suggesting that the inhibitory effect was partly caused by increase in osmotic potential in microorganism cell.Not only NH but also NO greatly affected methane oxidation.Urea did not affect methane oxidation in paddy soil in the first two days of incubation,but strong inhibitory effect was observed afterwards.Methane was oxidized in the treated soil with an optimum moisture of 280 g kg-1, and air-drying inhibited methane oxidation entirely.The optimum temperature of methane oxidation was about 30℃in paddy soil,while no methane oxidation was observed at 5℃or 50℃

The effects of nitrogen fertilizer application on methane and nitrous oxide emission/uptake in Chinese croplands

The application of nitrogen（N） fertilizer to increase crop yields has a significant influence on soil methane（CH_4） and nitrous oxide（N_2O） emission/uptake.A meta-analysis was carried out on the effect of N application on（i） CH_4 emissions in rice paddies,（ii） CH_4 uptake in upland fields and（iii） N_2O emissions.The responses of CH_4 emissions to N application in rice paddies were highly variable and overall no effects were found.CH_4 emissions were stimulated at low N application rates（〈100 kg N ha^（-1）） but inhibited at high N rates（〉200 kg N ha^（-1）） as compared to no N fertilizer（control）.The response of CH_4 uptake to N application in upland fields was 15%lower than control,with a mean CH_4 uptake factor of-0.001 kg CH_4-C kg^（-1） N.The mean N_2O emission factors were 1.00 and 0.94%for maize（Zea mays） and wheat（Triticum aestivum）,respectively,but significantly lower for the rice（Oryza sativa）（0.51%）.Compared with controls,N addition overall increased global warming potential of CH_4 and N_2O emissions by 78%.Our result revealed that response of CH_4 emission to N input might depend on the CH_4concentration in rice paddy.The critical factors that affected CH_4 uptake and N_2O emission were N fertilizer application rate and the controls of CH_4 uptake and N_2O emission.The influences of application times,cropping systems and measurement frequency should all be considered when assessing CH_4 and N_2O emissions/uptake induced by N fertilizer.

A continuous and high-efficiency process to separate coal bed methane with porous ZIF-8 slurry:Experimental study and mathematical modelling

Coal bed methane has been considered as an important energy resource.One major difficulty of purifying coal bed methane comes from the similar physical properties of CH_4 and N_2.The ZIF-8/water-glycol slurry was used as a medium to separate coal bed methane by fluidifying the solid adsorbent material.The sorption equilibrium experiment of binary mixture(CH_4/N_2)and slurry was conducted.The selectivity of CH_4 to N_2 is within the range of 2-6,which proved the feasibility of the slurry separation method.The modified Langmuir equation was used to describe the gas-slurry phase equilibrium behavior,and the calculated results were in good agreement with the experimental data.A continuous absorption-adsorption and desorption process on the separation of CH_4/N_2 in slurry is proposed and its mathematical model is also developed.Sensitivity analysis is conducted to determine the operation conditions and the energy performance of the proposed process was also evaluated.Feed gas contains 30 mol%of methane and the methane concentration in product gas is 95.46 mol%with the methane recovery ratio of 90.74%.The total energy consumption for per unit volume of product gas is determined as 1.846 kWh Nm^(-3).Experimental results and process simulation provide basic data for the design and operation of pilot and industrial plant.

Fracture evolution in coalbed methane reservoirs subjected to liquid nitrogen thermal shocking

Thermal shocking effect occurs when the coalbed methane(CBM)reservoirs meet liquid nitrogen(LN2)of extremely low temperature.In this study,3D via X-ray microcomputer tomography(μCT)and scanning electron microscope(SEM)are employed to visualize and quantify morphological evolution characteristics of fractures in coal after LN2 thermal shocking treatments.LN2 thermal shocking leads to a denser fracture network than its original state with coal porosity growth rate increasing up to 183.3%.The surface porosity of theμCT scanned layers inside the coal specimen is influenced by LN2 thermal shocking which rises from 18.76%to 215.11%,illustrating the deformation heterogeneity of coal after LN2 thermal shocking.The cracking effect of LN2 thermal shocking on the surface of low porosity is generally more effective than that of high surface porosity,indicating the applicability of LN2 thermal shocking on low-permeability CBM reservoir stimulation.The characteristics of SEM scanned coal matrix in the coal powder and the coal block after the LN2 thermal shocking presented a large amount of deep and shallow progressive scratch layers,fracture variation diversity(i.e.extension,propagation,connectivity,irregularity)on the surface of the coal block and these were the main reasons leading to the decrease of the uniaxial compressive strength of the coal specimen.

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOR PERMEATION

This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...

Nickel nanoparticles supported on nitrogen-doped carbon nanotubes are a highly active,selective and stable CO_(2) methanation catalyst

CO_(2) methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route.Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation,calcination and reduction and characterized by elemental analysis,X-ray powder diffraction,H_(2) temperature-programmed reduction,CO pulse chemisorption and transmission electron microscopy.The Ni/NCNT catalysts were highly active in CO_(2) methanation at atmospheric pressure,reaching over 50% CO_(2) conversion and over 95% CH_(4) selectivity at 340℃ and a GHSV of50,000 mL g^(-1) h^(-1) under kinetically controlled conditions.The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs.The optimum loading of 30 wt%-40 wt% Ni was found to result in the highest Ni surface area,the highest degree of conversion and the highest selectivity to methane.A constant TOF of 0.3 s^(-1) was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt%to 50 wt% Ni loading.Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream.

Screening and design of COF-based mixed-matrix membrane for CH_(4)/N_(2) separation

Membrane separation is a high-efficiency,energy-saving,and environment-friendly separation technology.Covalent organic framework(COF)-based mixed-matrix membranes(MMMs)have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification.Herein,a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH_(4)/N_(2) separation.General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready,experimental COFs.From our database containing 471,671 generated COFs,5 COF membrane materials were screened with excellent membrane selectivities,which were then used as the filler of MMMs for separation performance evaluation.Among them,BAR-NAP-Benzene_CF_(3) combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH_(4) permeability of 4.43×10^(-13) mol·m·s^(-1)·Pa^(-1)·m^(-2) and high CH_(4)/N_(2) selectivity of 9.54,respectively.The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH_(4)/N_(2).

Coupled δ^(15)N_(TN) and δ^(13)C_(TOC) Insights into Methane Seepage Activities in Bulk Marine Sediments of the Qiongdongnan Basin, South China Sea

Recently,methane seepage related to the dissociation of natural gas hydrates has attracted much attention,which has a significant impact on the study of the global carbon and nitrogen cycles.Based on the detailed geochemical analyses of sediments(core Q6)from the Qiongdongnan Basin,South China Sea,three methane seepage activities were identified and the exact horizons of anaerobic oxidation of methane(AOM)were defined.Furthermore,organic carbon isotopic(δ^(13)C_(TOC))levels ranged from−23.6‰–−20.6‰PDB;nitrogen isotopes(δ^(15)N_(TN))of the same sedimentary samples ranged from 1.8‰–5.3‰.We also found obvious simultaneous negative excursions of organic carbon isotopes(δ^(13)C_(TOC))and nitrogen isotopes(δ^(15)N_(TN))in the horizons of methane seepages.Compared with the normal sediments,their maximum negative excursions were 2.6‰and 2.5‰,respectively.We discuss in detail the various characteristics ofδ^(15)N_(TN) andδ^(13)C_(TOC) levels in sediments and their coupling responses to methane seepage activities.We believe that the methane seepage events changed the evolution trajectory ofδ^(15)N_(TN) andδ^(13)C_(TOC) levels in sediment records,which resulted in the simultaneous negative excursions.This phenomenon is of great significance to reveal the historical dissociation of natural gas hydrates and their influence on the deep-sea carbon and nitrogen pool.

NOX -Catalyzed Gas-Phase Activation of Methane: the Formation of Hydrogen

NO_x-catalyzed oxidation of methane without a solid catalyst wasinvestigated, and a hydrogen selectivity of 27% was obtained with an overall methane conversion of34% and a free O_2 concentration of 1.7% at 700℃.

Facile preparation of Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3) heterojunction for enhanced performance in catalytic nitrogen fixation via photocatalysis and piezo-photocatalysis

In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.

Oxygen defect modulating the charge behavior in titanium dioxide for boosting photocatalytic nitrogen fixation performance

Extremely high-temperature and high-pressure requirement of Haber-Bosch process motivates the search for a sustainable ammonia synthesis approach under mild conditions.Photocatalytic technology is a potential solution to convert N2 to ammonia.However,the poor light absorption and low charge carrier separation efficiency in conventional semiconductors are bottlenecks for the application of this technology.Herein,a facile synthesis of anatase TiO_(2)nanosheets with an abundance of surface oxygen vacancies(TiO_(2)-OV)via the calcination treatment was reported.Photocatalytic experiments of the prepared anatase TiO_(2)samples showed that TiO_(2)-OV nanosheets exhibited remarkably increased ammonia yield for solar-driven N2 fixation in pure water,without adding any sacrificial agents.EPR,XPS,XRD,UV-Vis DRS,TEM,Raman,and PL techniques were employed to systematically explore the possible enhanced mechanism.Studies revealed that the introduced surface oxygen vacancies significantly extended the light absorption capability in the visible region,decreased the adsorption and activation barriers of inert N2,and improved the separation and transfer efficiency of the photogenerated electronhole pairs.Thus,a high rate of ammonia evolution in TiO_(2)-OV was realized.This work offers a promising and sustainable approach for the efficient artificial photosynthesis of ammonia.

A Simple and Effective Method to Fabricate Separation Membranes for Dehydration of Natural Gas

PBT/PEG_(1000)composite membranes were prepared by the phase inversion method and were used to dehydrate natural gas.In this study,evaporation time,coagulation bath concentration,and additives in casting solution were investigated,respectively,on the selectivity and permeability of separation membranes,and optimal conditions were found to include an evaporation time of 30 sec,an 100%PEG400-containing coagulation bath and 2%of PVA used as the additive.The H_(2)O/CH_(4)selectivity reached over 3600,which is about 20 times more selective than the original membrane.It provides a simple and effective preparation method to fabricate membranes for dehydration of methane gas.

Modulating the CO methanation activity of Ni catalyst by nitrogen doped carbon

Nitrogen doping has been proved to be an effective way to modify the properties of graphene and other carbon materials. Herein, we explore a composite with nitrogen doped carbon overlayers wrapping Si C substrate as a support for Ni（Ni/CN-Si C） and evaluate its effects on the methanation activity. The results show that both the activity and stability of Ni are enhanced. Characterization with STEM, XRD, XPS, Raman and H2-TPR indicates that nitrogen doping generates more defects in the carbon overlayers, which benefit the dispersion of Ni. Furthermore, the reduction of Ni is facilitated.

The Effects of Microwave Pretreatment of Dairy Manure on Methane Production

This study was undertaken to evaluate the efficiency of a liquid-solids separation process and microwave pretreatment, as well as anaerobic biodegradability of microwave pretreated dairy manure. Liquid-solids separation of raw dairy manure resulted in solid and liquid fractions having different properties, with the solid fractions richer in total and volatile solids content and liquid fractions richer in nutrients and metal ions. Substantial amounts of soluble chemical oxygen demand and nutrients were released into the solution after the microwave treatment. The microwave pretreated dairy manure was also subjected to anaerobic digestion. The kinetic parameters of methane production potential, maximum methane production rate and lag time were determined using the modified Gompertz equation. Anaerobic digestion of liquid manure, without microwave treatment, outperformed the sets with microwave treatment. The microwave-treated liquid dairy manure, without acid addition had better results in terms of methane potential and methane production, than with acid addition. Thermophilic digestion exhibited a higher maximum methane production rate than that of mesophilic digestion, but lower methane yields. The microwave pretreatment of dairy manure resulted in high soluble chemical oxygen demand;however, methane yield was not increased.

不同水分条件下氨基酸添加对温带暗棕壤碳氮含量和甲烷排放的影响

【目的】解析土壤pH值与土壤氮以及CH_(4)排放速率与土壤碳氮含量间的相互关系,为明确碳氮转化及温室气体排放规律、优化温带森林暗棕壤的水分管理提供依据。【方法】以温带森林暗棕壤为研究对象,采用室内培养法,设置水分条件为土壤饱和持水量(WHC)的40%、60%、90%,通过向温带暗棕壤中添加两种不同性质的氨基酸,探讨其对土壤碳氮含量及CH_(4)排放的潜在影响,运用Pearson相关分析法分析土壤碳氮含量、pH值及CH_(4)排放速率间的相关性。【结果】(1)氨基酸处理显著增加了土壤可溶性有机碳(DOC)含量、铵态氮(NH_(4)^(+)-N)含量及CH_(4)排放速率。亮氨酸处理使DOC、NH_(4)^(+)-N含量分别升高21.39%、45.10%,CH_(4)排放速率较CK升高3.20倍,甲硫氨基酸使DOC、NH_(4)^(+)-N含量分别升高21.39%、72.71%,CH_(4)排放速率较CK升高7.00倍;(2)不同氨基酸对土壤硝态氮(NO_(3)^(-)-N)含量的影响存在差异。亮氨酸处理使土壤NO_(3)^(-)-N含量升高了8.41%,但其对于土壤硝化作用的影响可能存在滞后性,而甲硫氨基酸能够显著抑制土壤硝化作用,NO_(3)^(-)-N含量显著降低了37.90%;(3)土壤不同水分条件对土壤DOC、NH_(4)^(+)-N、NO_(3)^(-)-N含量及CH_(4)排放速率均存在显著影响。90%WHC使DOC含量升高11.95%~19.91%,使NH_(4)^(+)-N升高19.83%~35.46%,使NO_(3)^(-)-N降低10.05%~23.79%,使CH_(4)排放速率升高至另外两种水分条件的1.48~2.06倍。60%WHC条件使NH_(4)^(+)-N升高13.05%,使NO_(3)^(-)-N含量升高24.62%。60%WHC可能是温带暗棕壤硝化作用的最适含水量,90%WHC条件有利于DOC积累,同时对NO_(3)^(-)-N的产生存在明显抑制作用;(4)土壤pH与N H4+-N含量呈极显著正相关,与NO_(3)^(-)-N含量呈正相关。CH_(4)排放速率与NO_(3)^(-)-N含量呈极显著负相关,与NH_(4)^(+)-N含量呈负相关,与DOC含量呈极显著正相关。【结论】不同性质氨基酸添加在温带森林暗棕壤碳氮含量及CH_(4)排放中发挥的作用不尽相同。一定范围内,土壤水分含量的升高有利于土壤NH_(4)^(+)-N、NO_(3)^(-)-N、DOC的积累及CH_(4)的排放,但土壤高含水量条件对NO_(3)^(-)-N的产生具有抑制作用。因此,在研究温带森林暗棕壤碳含量、CH_(4)排放及氮转化机制时,建议关注不同氨基酸的差异性作用,同时考虑水分的变化。