二氧化碳回收技术进展

CO2的过量排放对全球的气候变暖有着不可推卸的责任,同时CO2又是一种重要的碳资源,对它的回收和利用将具有很大的经济效益和社会效益。CO2回收的方法主要是膜吸收法、变压吸附法、化学吸收法和低温分离法,特别是离子液体对CO2的吸收,为CO2的减排提供了良好的手段。     

CO2 removal using membrane gas absorption

The objective of this study is to investigate the potential process for the removal of carbon dioxide (CO₂) from flue gas using fundamental membrane contactor, which is a membrane gas absorption (MGA) system. The experiments consisted of microporous polyvinylidenefluoride (PVDF) flat sheet membrane with 0.1 μm (as module I) and 0.45 μm (as module II) pore size. 2-Amino-2-methyl-1-propanol (AMP) solution was employed as the liquid absorbent. The effect of AMP concentration was studied with variation in the range 1–5 M. In addition, the experiments were carried out with 10%, 20%, 30% and 40% gas ratio of CO₂ to N₂ and pure CO₂ as well. Through contact angle measurement, membranes for module I and module II were obtained with CA values of around 130.25° and 127.77°, respectively. The mass transfer coefficients for module II are lower than those of module I for 1–5 M of AMP. Furthermore, the increase in CO₂ concentration in the feed gas stream enhanced the CO₂ flux as the driving force of the system was increased in sequence from 1 M to 5 M of AMP. However, after the particular percentage (40%) of CO₂ inlet concentration, the CO₂ fluxes seem saturated. The combination of AMP as liquid absorbent and PVDF microporous membrane in MGA system has shown the potential to remove the CO₂ from flue gas. In addition, the higher AMP concentration gave higher mass transfer coefficient at low liquid flow rates.     

TETA对CO_2的吸收及其动力学参数的推导

为了提高CO2的吸收量,选用含四个氮原子的三乙烯四胺(简写为TETA)为吸收剂,在常压下,采用搅拌式反应器对TETA吸收CO2进行了研究。得到TETA吸收CO2的最佳温度为308K、最佳浓度为1.0mol/L,并与常用的醇胺吸收剂一乙醇胺(简写为MEA)、二乙醇胺(简写为DEA)、三乙醇胺(简写为TEA)的吸收效果进行比较,实验结果显示:TETA是一种性能优良的CO2吸收剂。同时分析了各吸收剂对二氧化碳的吸收机理;应用化学动力学理论计算了不同温度下TETA吸收CO2反应的级数,速率常数及反应的平均活化能。计算结果表明,在最佳温度308K时,反应的速率常数最大,反应速率最快,反应级数n=1.6,速率常数k′=0.172,平均活化能Ea=132kJ/mol。     

Carbon dioxide capture and recovery by means of TSA and/or VSA

Experimental work is performed with a 5A zeolite on a small laboratory column with heating from the wall. Carbon dioxide adsorption occurs at atmospheric pressure and different CO₂ concentrations in nitrogen. Comparisons of different methods of desorption by heating, purge and/or vacuum are studied. Desorption by heating only leads to almost pure CO₂ (around 99% purity) and a recovery nearly linear to the heating temperature, ranging from 45% at 130 °C to 79% at 210 °C. Recovery can be subsequently increased with a nitrogen purge to more than 98% but the recovered carbon dioxide is diluted due to the dispersive character of the desorption wave and the operation time is long. Increasing the flow rate decreases the desorption time but has no effect on the purity because the total purge volume remains about the same. Substitution of the purge step with a vacuum step leads to pure CO₂ and almost total recovery. Desorption under vacuum only without heating leads to pure CO₂ (around 99% purity) but limited recovery (85% in the present work).Desorption under vacuum seems to be more simple for large-scale applications. When using a water liquid ring pump, the temperature of the ring must be kept as low as possible to provide a high operating capacity.     

迪那2气田液化气无水冷却工艺研究

迪那2气田液化气生产设计采用空冷加水冷工艺,存在能耗大和水冷器易腐蚀结垢等安全隐患。利用HYSYS软件对迪那2气田轻烃回收工艺进行分析,并增设液化气后冷器,利用脱乙烷塔气相对液化气进行冷却,通过醇烃液分离压力、后冷器及空冷器冷却能力等参数的模拟计算和优化,将醇烃液三相分离器压力由常规的2.5MPa提高至5MPa,取消醇烃液导热油加热和液化气水冷,降低了装置能耗,年节水1.44×104m3,节电1.45×105 kW.h,杜绝了水冷器腐蚀穿孔的安全隐患,最终提出了醇烃液高压分离+空冷器+后冷器的液化气无水冷却工艺。     

Mineralization of soil-aged isoproturon and isoproturon metabolites by Sphingomonas sp. strain SRS2

The aim of the study was to determine the effect of aging of the herbicide isoproturon and its metabolites monodesmethyl-isoproturon and 4-isopropyl-aniline in agricultural soil on their availability to the degrading bacterium Sphingomonas sp. strain SRS2. The 14C-ring-labeled isoproturon, monodesmethyl-isoproturon, and 4-isopropyl-aniline were added to sterilized soil and stored for 1, 49, 71, or 131 d before inoculation with strain SRS2. The availability of the compounds was estimated from the initial mineralization and the amount of 14CO2 recovered after 120 d of incubation. Aging in soil for 131 d reduced the initial mineralization of isoproturon and monodesmethyl-isoproturon and, in the case of isoproturon, also reduced the recovery of 14CO2. Initial mineralization and recovery of 14CO2 from aged 4-isopropyl-aniline were slightly reduced, but less 14CO2 was generally produced than with isoproturon or monodesmethyl-isoproturon. Thus, recovery of 14CO2 from 14C-isoproturon and 14C-monodesmethyl-isoproturon was 50.7 to 64.4% of the initially added 14C, while recovery from 14C-4-isopropyl-aniline was only 11.7 to 17.0%. Sorption measurements revealed similar Freundlich constants (K(f)) for isoproturon and monodesmethyl-isoproturon, whereas K(f) for 4-isopropyl-aniline was more than fivefold greater. The findings imply that in soil, partial degradation of isoproturon to 4-isopropyl-aniline may lead to reduced mineralization of the herbicide due to sorption of the aniline moiety.     

Separation and recovery of carbon dioxide by a membrane flash process

A novel process for carbon dioxide (CO₂) separation, which was named a membrane flash process, was developed to realize an energy-saving technology and to substitute it for a conventional regenerator. The electric energy for CO₂ recovery in a membrane flash process using aluminum oxide and diethanolamine was lower than the thermal energy of the conventional chemical absorption process. Flashing at elevated temperature by the low temperature energy significantly reduced the electric energy and required much less membrane area. This process has potentiality of low cost capture of CO₂ when the low temperature energy, which is not available for other purposes, can be utilized to elevate flashing temperature.     

有机溶剂回收技术的研究

本文对有机溶剂的回收方法，如吸附法、吸收法、冷凝法和膜分离法等的研究进展与应用进行了综述。其中，吸附法在工业上的应用最为广泛，本文着重介绍了吸附法的工艺以及吸附剂的研究。而膜分离法作为最有发展前景的一种回收方法，主要问题为提高膜的通量和选择性。     

The effect of heating technologies on CO(2) and energy efficiency of Dutch greenhouse firms

This paper uses Data Envelopment Analysis to compute measures of the efficiency (relative to a frontier) in terms of the use of all inputs as well as for single inputs like CO(2) and energy for a sample of greenhouse firms in the Netherlands over the period 1991-1995. These efficiency measures are generated for different firms specialised in production of vegetables, flowers, and potplants and with different heating technologies. The empirical results indicate that firms use energy quite efficiently and are less efficient in terms of CO(2) emissions. Firms using conventional heating are overall less efficiently using energy and CO(2) than firms using more advanced heating technologies. Most differences in efficiency between firm types and firms using different heating technologies are statistically significant. Scale adjustments can provide an important contribution to further efficiency improvements.     

流动分析法测定空气和废气中氨的研究

建立流动分析法测定吸收液中氨的方法,用稀硫酸溶液吸收空气中的氨气,吸收液作为样品进入流动分析系统,采用在线蒸馏,实行自动分析,与国家标准方法比对,无明显差异,可用于空气中氨的定量检测。     

Optimal Absorbent Evaluation for the CO2 Separating Process by Absorption Loading,Desorption Efficiency,Cost, and Environmental Tolerance

The CO₂ absorption capacities of potassium glycinate, potassium sarcosinate (choline, proline), mono-ethanolamine (MEA), and tri-ethanolamine were evaluated to find the optimal absorbent for separating CO₂ from gaseous products by a CO₂ purification process. The absorption loading, desorption efficiency, cost, and environmental tolerance were assessed to select the optimal absorbent. MEA was found to be the optimum absorbent for separating the CO₂ and H₂ mixture in gaseous product. The maximum absorption loading rate was 0.77 mol CO₂ per mol MEA at temperature of 20°C and absorbent concentration of 2.5 mol/L, whereas desorption efficiency was 90% by heating for 3 h at 130°C. MEA was found to be an optimal absorbent for the purification process of CO₂ during gaseous production.     

Carbon and nitrogen mineralization rates after application of organic amendments to soil

The objective of this study was to quantify C and N mineralization rates from a range of organic amendments that differed in their total C and N contents and C quality, to gain a better understanding of their influence on the soil N cycle. A pelletized poultry manure (PP), two green waste-based composts (GWCa, GWCb), a straw-based compost (SBC), and a vermi-cast (VER) were incubated in a coarse-textured soil at 15 degrees C for 142 d. The C quality of each amendment was determined by chemical analysis and by 13C nuclear magnetic resonance (NMR). Carbon dioxide (CO2-C) evolution was determined using alkali traps. Gross N mineralization rates were calculated by 15N isotopic pool dilution. The CO2-C evolution rates and gross N mineralization rates were generally higher in amended soils than in the control soil. With the exception of GWCb all amendments released inorganic N at concentrations that would be high enough to warrant a reduction in inorganic N fertilizer application rates. The amount of N released from PP was high indicating that application rates should be reduced, or alternative amendments used, to minimize leaching losses in regions where ground water quality is of concern. There was a highly significant relationship between CO2-C evolution and gross N mineralization (R2= 0.95). Some of the chemically determined C quality parameters had significant relationships (p < 0.05) with both the cumulative amounts of C and N evolved. However, we found no significant relationships between 13C NMR spectral groupings, or their ratios, and either the CO2-C evolved or gross N mineralized from the amendments.     

活性炭在膜生物反应器中的应用研究进展

活性炭是一种非常优良的吸附剂，具有物理吸附和化学吸附的双重特性。本文介绍了近年来向膜生物反应器中投加活性炭的应用研究进展，表明投加活性炭可以提高膜生物反应器的处理效果，同时对改善膜污染有很好的效果。     

Effect of cattle slurry separation on greenhouse gas and ammonia emissions during storage

Storage of cattle slurry leads to emissions of methane (CH(4)), nitrous oxide (N(2)O), ammonia (NH(3)), and carbon dioxide (CO(2)). On dairy farms, winter is the most critical period in terms of slurry storage due to cattle housing and slurry field application prohibition. Slurry treatment by separation results in reduced slurry dry matter content and has considerable potential to reduce gaseous emissions. Therefore, the efficiency of slurry separation in reducing gaseous emissions during winter storage was investigated in a laboratory study. Four slurry fractions were obtained: a solid and a liquid fraction by screw press separation (SPS) and a supernatant and a sediment fraction by chemically enhanced settling of the liquid fraction. Untreated slurry and the separated fractions were stored in plastic barrels for 48 d under winter conditions, and gaseous emissions were measured. Screw press separation resulted in an increase of CO(2) (650%) and N(2)O (1240%) emissions due to high releases observed from the solid fraction, but this increase was tempered by using the combined separation process (CSP). The CSP resulted in a reduction of CH(4) emissions ( approximately 50%), even though high emissions of CH(4) (46% of soluble C) were observed from the solid fraction during the first 6 d of storage. Screw press separation increased NH(3) emissions by 35%, but this was reduced to 15% using the CSP. During winter storage greenhouse gas emissions from all treatments were mainly in the form of CH(4) and were reduced by 30 and 40% using SPS and CSP, respectively.     

Numerical parametric study on CO2 capture by indirect thermal swing adsorption

Post-combustion CO₂ capture remains one of the most-challenging issue to lower CO₂ emissions of existing power plants or heavy industry installations because of strong economy and energy efficiency aspects. The major issue comes from CO₂ dilution (4% for NGCC and 14% for PC) and the high flow rates to be treated. Furthermore, CO₂ purity has to be higher than 95% with recovery at 90%, to match the transportation/injection requirements.The MEA absorption process remains the reference today but its energy consumption (about 3 MJ/kg_CO2) and the amine consumption are still challenging drawbacks.The interest of CO₂ capture by indirect TSA (Temperature Swing Adsorption) was demonstrated experimentally in a previous work. The aim of this paper is to present the results of a numerical parametric study. Two main parameters are explored: the desorption temperature (100–200 °C) and the purge flow rate (0.1–0.5 Ndm³ min⁻¹). Four performance indicators are evaluated: CO₂ purity, recovery, productivity and specific energy consumption.Results show that purity above 95% can be achieved. Keeping the 95% target, it is possible to achieve recovery at 81% with productivity at 57.7 g_CO2/kg_ads h and a specific energy consumption of 3.23 MJ/kg_CO2, which is less than for the reference MEA process.Comparison with other adsorption processes exhibits that this process has good potential especially since some improvements are still expected from further research.     

微滤膜技术及应用研究*

随着膜制造技术的发展,微滤膜在油田采出水处理中具有越来越大的优势。文章对微滤膜的特点和过滤分离原理进行了阐述,对比分析了有机高分子微滤膜、无机陶瓷微滤膜和复合微滤膜各自的优缺点、制备工艺以及在油田中的应用情况,针对微滤膜在采油污水处理中膜通量下降快,使用周期短等弱点提出了防止膜污染和膜清洗的措施,并对微滤膜的发展及今后在油田中的应用提出了建议和展望。     

Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.     

Effects of Forest Composition and Spatial Patterns on Storm Flows of a Small Watershed1

Abstract: The PRMS_Storm model was built as a storm event, distributed hydrological model for studying the hydrological effects of forest composition and spatial distribution on storm‐flow volume and peakflow rates in the Xiangshuixi Watershed in the Three Gorges Reservoir Area, in the Yangtze River Basin in southwestern China. We developed three simulation scenarios based on forest composition and their spatial arrangements across the watershed, including all mixed conifer‐evergreen broadleaf forests (Scenario 1), all mixed evergreen broadleaf forests (Scenario 2), and mixed conifer + evergreen broadleaf + shrub forests (Scenario 3). We examined 11 storm events observed during 2002‐2005. Compared with the existing forest covers, modeling results suggested that the amount of overland flow was reduced by 21, 23, and 22%, and the interflow increased by 16, 88, and 30%, for Scenarios 1, 2, and 3, respectively. During the same time, peakflow rates were reduced by 20.8, 9.6, and 18.9%, respectively. The reduction of peakflow rates was most significant when rainfall intensity exceeded 0.8 mm/min and events with a short duration and effect was minor when rainfall intensity was below 0.5 mm/min. In general, we found that Scenarios 1 and 3 were preferred for reducing storm‐flow volume and peakflow rates due to their higher interception rates, large soil water holding capacity, and higher soil infiltration capacity. The modeled results suggested soil properties are important in affecting the flow processes and thus forest composition and forest spatial distributions will affect storm‐flow volume and peakflow rates at the watershed scale. To maximize flood reduction functions of a watershed, high priority should be given to those forest types (Scenarios 1 and 3) in reforestation practices in the study region. This study suggests both forest composition and spatial pattern are important reforestation designs for flood reduction in the Three Gorges Reservoir Area.     

Particulate and dissolved phosphorus chemical separation and phosphorus release from treated dairy manure

In confined animal feeding operations, liquid manure systems present special handling and storage challenges because of the large volume of diluted wastes. Water treatment polymers and mineral phosphorus (P) immobilizing chemicals [AI2(SO4)3 x 18H2O, FeCl3-6H2O, and Class C fly ash] were used to determine particulate and dissolved reactive phosphorus (DRP) reduction mechanisms in high total suspended solid (TSS) dairy manure and the P release from treated manure and amended soils. Co-application exceeded the aggregation level achieved with individual manure amendments and resulted in 80 and 90% reduction in metal salt and polymer rates, respectively. At marginally effective polymer rates between 0.01 and 0.25 g L(-1), maximal aggregation was attained in combination with 1 and 10 g L(-1) of aluminum sulfate (3 and 30 mmol Al3+ L(-1)) and iron chloride (3.7 and 37 mmol Fe3+ L(-1)) in 30 g L(-1) (TSS30) and 100 g L(-1) TSS (TSS100) suspensions, respectively. Fly ash induced particulate destabilization at rates > or = 50 g L(-1) and reduced solution-phase DRP at all rates > or = 1 g L(-1) by 52 and 71% in TSS30 and TSS100 suspensions, respectively. Aluminum and Fe salts also lowered DRP at rates < or = 10 g L(-1) and higher concentrations redispersed particulates and increased DRP due to increased suspension acidity and electrical conductivity. The DRP release from treated manure solids and a Typic Paleudult amended with treated manure was reduced, although the amendments increased Mehlich 3-extractable P. Therefore, the synergism of flocculant types allowed input reduction in aggregation aid chemicals, enhancing particulate and dissolved P separation and immobilization in high TSS liquid manure.     

Carbon monoxide from composting due to thermal oxidation of biomass

Emissions of carbon monoxide (CO) were observed from decomposing organic wastes and litter under laboratory, pilot composting plant, and natural conditions. Field studies included air from inside a compost heap of about 200 m3, emissions from composting of livestock wastes at a biologically operating farm, and leaf litter pile air samples. The concentration of CO was up to 120 micromol mol(-1) in the compost piles of green waste, and up to 10 micromol mol(-1) in flux chambers above livestock waste windrow composts. The mean CO flux rates were approximately 20 mg CO m(-2) h(-1) for compost heaps of green waste, and varied from 30 to 100 mg CO m(-2) h(-1) for fresh dung windrows. Laboratory studies using a temperature and ventilation-controlled substrate container were performed to elucidate the origin of CO, and included hay samples of fixed moisture content at temperatures between 5 and 65 degrees C, including nonsterilized as well as sterilized samples. The concentration of CO was up to 160 micromol mol(-1) in these experiments, and Arrhenius-type plot analyses resulted in activation energies of 65 kJ mol(-1) for thermochemically produced CO from the nonsterilized compost substrate. Sterilized samples showed dramatically reduced CO2 but virtually unchanged CO emissions, albeit at a slightly lower activation energy, likely a result of the high-temperature sterilization. Though globally and regionally these CO emissions are only a minor source, thermochemically produced CO emissions might affect local air quality in and near composting facilities.