化学沉淀法去除稀土湿法冶炼废水中钙与高浓度氨氮研究

离子型稀土湿法冶炼过程中会产生大量氨氮废水,由于废水中含有大量Ca2+,而Ca2+是影响磷酸铵镁沉淀法脱氮效率的重要因素.向废水中投入Na2CO3固体生成CaCO3沉淀物,去除废水中的Ca2+,再利用磷酸铵镁(MAP)沉淀法去除废水中的氨氮.实验采用响应面实验设计方法中的中心复合设计法,利用响应面分析法对磷酸铵镁沉淀法反应参数进行优化,得到最优反应条件及最优反应条件下沉淀产物.利用扫描电子显微镜(SEM)及X射线衍射(XRD)对最优反应条件下两种沉淀物进行分析.结果表明,当n(Ca2+)∶n(CO23-)=1∶1.05,搅拌速率为1 500 r.min-1,反应时间为30 min时,Ca2+去除率接近100%;对除钙后废水进行磷酸铵镁法脱氮处理的最优反应条件为:pH=9.03,n(Mg)∶n(N)=1.20,n(P)∶n(N)=1.1,反应时间为30 min,搅拌速率为1 000 r.min-1,氨氮去除率达到95.40%,剩余总磷浓度为5.65 mg.L-1;沉淀物分别为纯净的CaCO3及MgNH4PO4.6H2O.     

氨水混合吸收剂脱除CO2实验研究

氨水作为一种很有应用前景的CO2化学吸收剂,存在吸收速率慢的问题.使用湿壁塔实验台,考察了不同种类的添加剂(MEA、PZ、1-MPZ、2-MPZ)对氨水吸收CO2速率的影响.结果表明,4种添加剂均能明显提高氨水吸收CO2的速率,其中PZ具有最好的促进效果.0、0.1、0.3和0.5 mol·mol-1负荷下,3 mol·L-1NH3+0.3 mol·L-1PZ溶液的总传质系数(KG)分别是3 mol·L-1NH3溶液在相应负荷下的3、3.2、3.2和2.9倍.改变反应温度、添加剂量、PZ浓度等条件对基于NH3/PZ混合吸收剂吸收CO2的反应过程进行实验,得到了其在不同条件下的KG,初步探讨CO2吸收的反应机制,并计算出准一级反应速率常数为42.7 m3·(mol·s)-1.     

茶园土壤水溶性氟含量的模拟调控

以湖北英山、大悟、竹山、赤壁和浙江杭州茶园土壤为研究对象,通过施加一定量的CaCO3、CaO、Ca3(PO4)2、CaCl2和CaSO4来调控土壤中水溶性氟含量,结果表明：英山、大悟和竹山茶园土壤中施加一定量的CaCl2或CaSO4均可降低土壤中水溶性氟含量,英山和大悟茶园土壤中可施加1～2 g·kg-1的CaCl2或...     

Effect of calcium on adsorption capacity of powdered activated carbon

We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca²⁺, were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca²⁺ was doped into HA. Also, HA and Ca²⁺ taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca²⁺ concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca²⁺, pH had a small rise, but the extent of pH of later solution was bigger.     

Effect of calcium on adsorption capacity of powdered activated carbon

We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca²⁺, were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca²⁺ was doped into HA. Also, HA and Ca²⁺ taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca²⁺ concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca²⁺, pH had a small rise, but the extent of pH of later solution was bigger.     

Absorption characteristics of new solvent based on a blend of AMP and 1,8-diamino-p-menthane for CO2 absorption

Aqueous 1,8-diamino-p-menthane (KIER-C3) and commercially available amine solutions were tested for CO₂ absorption. A 2-amino- 2-methyl-1-propanol (AMP) solution with an addition of KIER-C3 showed 9.3% and 31.6% higher absorption rate for CO₂ than the AMP solution with an addition of monoethanolamine (MEA) and ammonia (NH₃), respectively. The reaction rate constant for CO₂ absorption by the AMP/KIER-C3 solution was determined by the following equation: k_2,AMP/C3 = 7.702×10⁶ exp (-2248.03/T). A CO₂ loading ratio of the AMP/KIER-C3 solution was also 2 and 3.4-times higher than that of the AMP/NH3 solution and the AMP/MEA solution, respectively. Based on the experimental results, KIER-C3 may be used as an excellent additive to increase CO₂ absorption capability of AMP.     

黄绵土中碳酸钙含量和有机肥施用对土壤有机碳组分及CO2排放的影响

为探讨碳酸钙(CaCO_3)和有机肥对土壤有机碳矿化和CO_2排放的影响,本研究通过向一种黄绵土中分别添加0、30、50 g·kg~(-1)CaCO_3模拟陕西省境内具有不同CaCO_3含量(9%~15%)的黄绵土,随后再添加0、20 g·kg~(-1)有机肥(M),交互组合设L0、L0-M、L30、L30-M、L50和L50-M等6个处理进行室内培养试验(105 d),测定了土壤pH、微生物量碳(MBC)、水溶性有机碳(DOC)、颗粒碳(POC)、易氧化有机碳(ROC)和CO_2释放量.结果表明:未施用有机肥时,土壤pH和MBC含量随CaCO_3含量的增加而增加,但CaCO_3含量对DOC、POC、ROC和有机碳氧化稳定性(Kos)无显著影响,其差异亦不会对土壤CO_2排放产生显著影响.当施用有机肥后,随着土壤CaCO_3含量增加,土壤pH上升、活性有机碳(MBC、DOC、POC和ROC)含量增加、Kos降低,土壤CO_2排放也随之增加.CaCO_3不仅能促进有机肥的矿化分解,而且它和有机肥会对土壤CO_2排放产生显著的交互效应,其效果与CaCO_3含量密切相关.低量CaCO_3和有机肥对土壤CO_2的释放具有负的表观交互效应,但高量CaCO_3和有机肥对其产生正的表观交互效应.因此,CaCO_3对土壤有机碳转化的影响不能一概而论,它与土壤中CaCO_3含量密切相关.在农业管理中,根据土壤CaCO_3含量合理施用有机肥对土壤碳素循环和温室气体(CO_2)排放都具有重要意义.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

高钙废水颗粒污泥中古菌菌群结构变化的分析

为了解高浓度Ca~(2+)与颗粒污泥中古菌菌群结构的关系,利用高通量测序分析IC(Internal Circulation)反应器(以废纸造纸废水为处理对象)内不同高度处颗粒污泥中古菌菌群组成,并利用SEM(Scanning Electron Microscope)和EDS(Energy Dispersive X-ray Spectroscopy)分析颗粒污泥的形态结构和元素组成,同时借助红外光谱和XRD(X-ray diffraction)分析不同高度处颗粒污泥化学结构中各官能团的分布情况和无机成分.结果表明,随着反应器高度的增加,颗粒污泥中的无机成分CaCO_3也随着增加,而种泥中钙含量只有1.81%.种泥和ICR反应器内的颗粒污泥中古菌在门分类水平上主要包括Euryarchaeota和Bathyarchaeota,两者之和占90%以上.在属分类水平上,主要包括Methanosaeta、Methanoregula、Methanobacterium、Methanosarcina、Methanolinea、Methanospirillum等.种泥中古菌的物种多样性要明显高于IC反应器中,在IC反应器中不同高度处古菌生物多样性由高到低的顺序是5 m2 m7 m,5 m处的古菌物种更加丰富.随着反应器高度的增加,乙酸营养型甲烷菌的相对丰度呈现递增趋势,氢营养型甲烷菌则呈现递减趋势,而种泥中氢营养型甲烷菌相对丰度较大.这表明颗粒污泥在高钙废水的长期作用下,氢营养型甲烷菌的相对丰度减少,乙酸营养型甲烷菌的相对丰度增多,系统中古菌物种的相对丰度和多样性有所下降.CaCO_3沉淀使颗粒污泥的产甲烷活性降低,主要表现为其对氢营养型甲烷菌具有较大的抑制作用.     

Use of zeolitized coal fly ash in the simultaneous removal of ammonium and phosphate from aqueous solution

Discharge of wastewater containing nitrogen and phosphate can cause eutrophication. Therefore, the development of an efficient material for the immobilization of the nutrients is important. In this study, a low calcium fly ash and high calcium fly ash were converted into zeolite using the hydrothermal method. The removal of ammonium and phosphate that coexist in aqueous solution by the synthesized zeolites were studied. The results showed that zeolitized fly ash could efficiently eliminate ammonium and phosphate at the same time. Saturation of zeolite with Ca²⁺ rather than Na⁺ favored the removal of both ammonium and phosphate because the cation exchange reaction by the NH₄ ⁺ resulted in the release of Ca²⁺ into the solution and precipitation of Ca²⁺ with PO₄ ³⁻ followed. An increase in the temperature elevated the immobilization of phosphate whereas it abated the removal of ammonium. Nearly 60% removal efficiency for ammonium was achieved in the neutral pH range from 5.5 to 10.5, while the increase or decrease in pH out of the neutral range lowered the adsorption. In contrast, the removal of phosphate approached 100% at a pH lower than 5.0 or higher than 9.0, and less phosphate was immobilized at neutral pH. However, there was still a narrow pH range from 9.0 to 10.5 favoring the removal of both ammonium and phosphate. It was concluded that the removal of ammonium was caused by cation exchange; the contribution of NH₃ volatilization to immobilization at alkaline conditions (up to pH level of 11.4) was limited. With respect to phosphate immobilization, the mechanism was mainly the formation of precipitate as Ca₃(PO₄)₂ within the basic pH range or as FePO₄ and AlPO₄ within acidic pH range.     

钙法解吸并固定乙醇胺富液中CO2

针对醇胺类吸收剂富液中CO_2的解吸及后续处置所存在的不足,提出一种新型解吸方案——钙法.通过CO_2负荷试验和Ca(OH)_2投加量试验确定了该法理想处理负荷为0.84 mol·L-1,理想投加比例为C∶Ca=1∶1(摩尔比),此条件下反应15 min和30 min的解吸率达到52.17%和55.02%,这表明钙法矿化解吸乙醇胺富液中CO_2是可行的.在此基础上,进一步研究了pH、温度和搅拌强度对CO_2解吸固定效果的影响.试验结果表明,CO_2解吸率随着pH和搅拌强度的增加而增大,但当pH和搅拌强度增大到一定程度后,解吸率增长放缓甚至出现下降.较高的解吸温度尽管解吸率更大,但高温条件下无法达到矿化固定CO_2的目的.CO_2二次吸收负荷试验表明经钙法解吸后的MEA再生液具有良好的可重复使用性.     

Vaporization reduction characteristics of aqueous ammonia solutions by the addition of ethylene glycol, glycerol and glycine to the CO2 absorption process

Aqueous ammonia (NH₃) solution can be used as an alternative absorption for the control of CO₂ emitted from flue gases due to its high absorption capacity, fast absorption rate and low corrosion problem. The emission of CO₂ from iron and steel plants requires much attention, as they are higher than those emitted from power plants at a single point source. In the present work, low concentration ammonia liquor, 9 wt.%, was used with various additives to obtain the kinetic properties using the blast furnace gas model. Although a solution with a high ammonia concentration enables high CO₂ absorption efficiency, ammonium ions are lost as ammonia vapor, resulting in reduced CO₂ absorption due to the lower concentration of the ammonia absorbent. To decrease the vaporization of ammonia, ethylene glycol, glycerol and glycine, which contain more than one hydroxyl radical, were chosen. The experiments were conducted at 313 K similar to the CO₂ absorption conditions for the blast furnace gas model.     

树脂基固态胺吸附剂室温下对低浓度CO2的吸附性能研究

以大孔甲基丙烯酸酯吸附树脂为载体,聚乙烯亚胺(PEI)为有机胺,采用液相浸渍法制备出固态胺吸附剂,并研究了其在室温下对低浓度CO2的吸附行为.同时,利用氮气吸附、热重分析和扫描电镜表征了材料的物理化学性质,并采用热重法和固定床吸附法考察了材料的CO2吸附性能.结果表明,大孔树脂担载50%PEI(质量分数)时吸附性能最佳,对纯CO2的最大吸附量为175 mg·g-1;CO2的吸附行为由扩散动力学与吸附热力学共同决定,低温有利于提高吸附容量;吸附剂对400 ppm~15%浓度的CO2都具有优异的动态吸附性能,其中对400 ppm CO2的吸附量达到86 mg·g-1,对15%CO2的吸附量达到150 mg·g-1;湿度对吸附起促进作用,相对湿度为10%时,对400 ppm CO2的吸附量提高至139mg·g-1;吸附剂具有优异的循环性能,具有直接空气捕集CO2的潜力.     

污泥烧结轻骨料调质影响研究

研究了污泥添加不同比例的SiO₂,Al₂O₃,CaCO₃和Na₂CO₃后的烧结体建材性能,并从晶体相反应机理角度讨论了添加剂改变烧结体建材性能的作用机理.结果表明,添加硅、铝能显著提高烧结体的抗压强度,硅是玻璃体成陶组分,对提高烧结体的抗压强度主要发挥物理作用;铝主要与污泥中的磷反应生成类似石英结构的AlPO₄高强晶体. 添加钠能增加烧结体的熔融液相,降低烧结体的吸水率,但烧结体变脆抗压强度降低. 添加钙增大吸水率,降低抗压强度. 此外,硅、铝会导致烧结体烧结温度提高,钠则能显著降低烧结温度.      

贵州喀斯特水库红枫湖、百花湖P(CO2)季节变化研究

针对贵州喀斯特地区富营养水库（红枫湖、百花湖）表层水中的CO₂分压P(CO₂)进行为期1 a的监测,分析了影响两湖P(CO₂)季节变化的因素并阐明了两湖P(CO₂)季节变化的机理.不同于北部温带地区水库,两湖出现明显的季节变化特征：夏季表层水中CO₂欠饱和,其他季节CO₂过饱和.通过对物理、化学及生物因素与P(CO₂)之间的相关性分析. 结果表明,两湖P(CO₂)与Chla之间存在的显著负相关,是由于浮游植物光合作用与细菌呼吸作用共同影响的结果,也是两湖P(CO₂)出现季节变化的主要原因.水温与P(CO₂)之间的显著负相关,主要是由于水温影响浮游植物生长引起的.降雨量与P(CO₂)之间的显著负相关,主要是由于降雨量影响水库中营养盐的输入和浮游植物生长引起的.NO^-₃、NO^-₂与P(CO₂)之间的显著正相关,是藻类吸收与有机质降解、硝化反应等共同作用的结果.SiO^{2-₃与P(CO₂)之间的显著负相关,是SiO2-₃受降雨输入及藻类吸收共同影响的结果.而两湖DOC与P(CO₂)相关性的差异可能与两湖DOC来源不同有关.}     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.     

Biomineralization in plants as a long-term carbon sink

Carbon sequestration in the global carbon cycle is almost always attributed to organic carbon storage alone, while soil mineral carbon is generally neglected. However, due to the longer residence time of mineral carbon in soils (10²–10⁶ years), if stored in large quantities it represents a potentially more efficient sink. The aim of this study is to estimate the mineral carbon accumulation due to the tropical iroko tree (Milicia excelsa) in Ivory Coast. The iroko tree has the ability to accumulate mineral carbon as calcium carbonate (CaCO₃) in ferralitic soils, where CaCO₃ is not expected to precipitate. An estimate of this accumulation was made by titrating carbonate from two characteristic soil profiles in the iroko environment and by identifying calcium (Ca) sources. The system is considered as a net carbon sink because carbonate accumulation involves only atmospheric CO₂ and Ca from Ca-carbonate-free sources. Around one ton of mineral carbon was found in and around an 80-year-old iroko stump, proving the existence of a mineral carbon sink related to the iroko ecosystem. Conservation of iroko trees and the many other biomineralizing plant species is crucial to the maintenance of this mineral carbon sink.     

砷酸钙化合物的溶解度及其稳定性随pH值的变化

通过混合沉淀和溶解实验详细研究了pH值和Ca/As摩尔比对石灰沉淀法处理高浓度含砷废水的影响.沉淀后溶液中的As浓度随pH值的变化趋势与混合液的Ca/As摩尔比有关,在Ca/As=1·50和1·67时,沉淀后溶液中的As浓度在pH=7附近达到最低,然后随pH值的升高而呈现出增大的趋势;在Ca/As=2·00和4·00时,沉淀后溶液中的As浓度随pH值的升高而降低,且2种Ca/As摩尔比条件下的实验结果基本一致.混合沉淀过程中生成的砷酸钙化合物的组成与结构取决于溶液的Ca/As摩尔比和pH值.在低pH值和低Ca/As摩尔比条件下形成的沉淀物要比在高pH值和高Ca/As摩尔比条件下形成的沉淀物的颗粒要大,而且结晶程度要好.在Ca/As摩尔比为1·0~4·0和不同pH值条件下,主要生成Ca_3(AsO_4)_2·3H_2O、Ca_3(AsO_4)_2·2·25H_2O、Ca_5(AsO-4)_3OH和Ca_4(OH)-2(AsO_4)2·4H_2O,溶度积分别等于10~(-21·14)、10~(-21·40)、10~(-40·12)和10~(-27·49).     

以粉煤灰为原料制备低温CO2吸附剂的工艺参数优化

利用高铝粉煤灰预脱硅液作为载体原料,通过使用胺基化合物对载体改性制备低温CO_2吸附剂.应用6 sigma中的工具,对制备工艺进行优化,得到理想的吸附剂,并对吸附剂样品进行表征.结果表明制备的CO_2吸附剂表现出良好的CO_2吸附性能.此类CO_2吸附剂具有吸附容量高(160 mg·g~(-1))、吸附速率快、对设备腐蚀低、成本低廉等特点,是一种极具工业应用潜力的CO_2吸附剂.     

Comparison of absorption rates and absorption capacity of ammonia solvents with MEA and MDEA aqueous blends for CO2 capture

In this work we present the experimental results of absorption rates and absorption capacity for the CO₂ absorption by ammonia (NH₃) aqueous solutions. Experiments are carried out in a thermoregulated Lewis-type cell reactor and are achieved in temperature and concentration ranges of 278–303 K and 2–5wt.% NH₃ respectively. The obtained values for absorption kinetic rates and absorption capacity are compared with those available for alkanolamine solvents, commonly used to absorb CO₂. In order to achieve this comparison, data available in studies about alkanolamine solvents at 303–333 K and 5–50wt.% for alkanolamines solutions were considered. Results show that CO₂ absorption by NH₃ is faster than the one carried out by MDEA, except for 2wt.% NH₃ at 288 K. At 278 K and using aqueous solutions of 3wt.% NH₃, the absorption rate is almost identical to the one reached with MDEA solvent. The highest absorption capacity, also compared with alkanolamine solution, is reached with aqueous solutions of 5wt.% NH₃ at 278 K and 303 K.