Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.     

焙烧温度对催化剂Cu-Ni-Ce/SiO2性能的影响

采用浸渍法在不同焙烧温度下制备了用于湿式H202降解吡虫啉农药废水的Cu-Ni-Ce/SiO2催化剂,利用TG、BET、XRD和XPS等对其进行了表征,研究了焙烧温度对催化剂表面结构的影响以及催化剂表面结构与活性及稳定性之间的关系.结果表明:降低焙烧温度,cu、Ni、ce之间的相互作用使得催化剂晶粒尺寸减小,比表面积增加,Cu、Ni固溶体量和催化剂表面化学吸附氧量增加.湿式H,O,降解吡虫啉农药废水时,600℃下焙烧获得的Cu-Ni-Ce/Si02催化剂活性最高;在催化剂用量10 g·L-1、反应温度为110℃、双氧水用量为理论需用量、进水pH为9.0、反应时间为60 min的条件下,COD去除率为91.5%,活性组分溶出量较小.研究结果表明,焙烧温度对CuO、NiO、CeO,及Cu、Ni固溶体之间的相瓦作用有较大影响,从而影响了催化剂湿式降解吡虫啉农药废水的活性和稳定性.     

双氧水爆炸事故机理分析及预防措施研究

为了对双氧水引起的爆炸事故的机理进行分析,用加速量热仪对双氧水进行了热危险性测试.通过对数据校正和分析,得到了浓度为30%的双氧水初始热分解温度为34.5 ℃,热分解可达到的最高温度为246 ℃,最大温升速率时间为100 min.结果表明,双氧水极易发生爆炸,并且爆炸威力很大.针对双氧水的爆炸危险,提出采取适当的预防措施,如冷却水法,以避免爆炸事故的发生.     

辉光放电等离子体处理印染废水的实验研究

用辉光放电等离子体技术印染废水降解进行了研究,通过测定CODcr、BOD和pH值的变化初步探讨了降解机理。结果表明:在辉光放电降解印染废水的过程中,发现仅是采用辉光放电水处理技术时,因为过氧化氢的生成导致废水CODcr有一定的升高,而废水的BOD几乎没有变化,说明辉光放电对印染废水几乎没有降解效果;而在亚铁离子的加入后,印染废水出现明显的降解效果,当亚铁离子加入量为50 mg时,印染废水的CODcr和BOD的去除率分别为41.2%和46.2%,降解率得到了很大的提高。     

Effect of crystalline structure on terbuthylazine degradation by H2O2-assisted TiO2 photocatalysis under visible irradiation

Various methods for shifting the optical response of TiO₂ into the visible (Vis) range have been reported. Herein, we reported the application of a TiO₂/H₂O₂/Vis process and the effects of TiO2 crystalline structure on the degradation of terbuthylazine. The results indicated that TiO₂ crystalline structure and H₂O₂ addition had significant effects on terbuthylazine degradation: its degradation rate could be increased from 7% to 70% with H₂O₂ addition after 180?min of reaction, the synergistic degradation of terbuthylazine by TiO₂-Fe^{3 +} was substantially accelerated, with the degradation rate reaching up to 100% after 20?min of reaction, and rutile TiO₂ showed better photocatalytic activity and a more obvious synergistic effect than anatase TiO₂. The addition of free-radical scavengers (tert-butyl alcohol or methanol) inhibited the degradation efficiency of rutile TiO₂, but had a relatively minor effect on anatase TiO₂. Fluorescence spectrophotometry analysis indicated that hydroxyl free radicals could be continuously produced when using rutile TiO₂ as the photocatalyst. Degradation of terbuthylazine catalyzed by rutile TiO₂ occurred mainly in solution, but occurred on the particle surface of the photocatalyst when catalyzed by anatase TiO₂. This study provides new insight into the role of TiO₂ crystalline structure on the degradation of terbuthylazine and its photocatalytic degradation mechanism.     

氢氧直接合成过氧化氢反应研究进展

重要化工原料过氧化氢的绿色、高效、安全制备工艺一直是研究热点之一。由氢气和氧气直接化合制备过氧化氢法(DSHP)具有过程简单、成本低等优点,受到了广泛关注。本文从原子层面反应机理、催化剂中贵金属的选取和复配效应、载体的组成和空间构型、反应介质的组成以及反应器中的流动控制等5个方面,总结近十年在利用微反应器实现DSHP反应方面的进展,并对该工艺的发展方向做出展望。     

核电厂含高浓度联氨废水处理方法研究

核电厂含高浓度联氨(N2H4)废水主要来源包括工艺系统含联氨冲洗水、保养水、疏排水、含联氨泄露水等.本文通过实验对比分析多种化学添加剂对含高浓度联氨废水处理的有效性,最终推荐紧急处理含高浓度联氨废水时加入4.55倍联氨质量的次氯酸钠;非紧急时,推荐加入1.76倍联氨质量的过氧化氢,另需添加适量(废水中硫酸铜浓度为500 μg/kg)硫酸铜.     

CaO2@FA复合材料富集磷效能及其回收物对土壤改良作用

为实现污水中磷和工业废弃物粉煤灰的资源化利用,通过表面沉淀法将纳米CaO₂负载于粉煤灰（FA）表面以及孔隙中,制备出一种高效除磷的复合材料（CaO₂@FA）.结果表明,粉煤灰表面负载CaO₂后,其具有更大的比表面积和孔隙率,比表面积增加至4.641 m² ·g^-1,总孔容增大至0.025 cm³ ·g^-1;CaO₂@FA对磷的吸附过程符合Langmuir等温吸附模型,其最大吸附容量为185.776 mg ·g^-1（20℃）,吸附机制为化学沉淀,主要是形成羟基磷酸钙.CaO₂@FA复合材料对磷的富集效率显著高于粉煤灰,并随着投加量增加,对磷的富集效率增加.共存离子中HCO^3-和CO₃^2-对复合材料吸附磷有一定的负面作用.当CaO₂@FA复合材料投加量为2.0 g ·L^-1时,对生活污水中磷的富集率可达93%,回收沉淀物中的有效磷含量达到1.658 mg ·g^-1.土壤改良实验表明,加入回收的沉淀物可使土壤中有效磷含量增加102.9%,该复合材料回收100 mg磷酸盐的运行成本则低至0.76元.     

Evaluation of alternative landfill cover soils for attenuating hydrogen sulfide from construction and demolition (C&D) debris landfills

Hydrogen sulfide (H(2)S) generated from C&D debris landfills has emerged as a major environmental concern due to odor problems and possible health impacts to landfill employees and surrounding residents. Research was performed to evaluate the performance of various cover materials as control measures for H(2)S emissions from C&D debris landfills. Twelve laboratory-scale simulated landfill columns containing gypsum drywall were operated under anaerobic conditions to promote H(2)S production. Five different cover materials were placed on top of the waste inside duplicate columns: (1) sandy soil, (2) sandy soil amended with lime, (3) clayey soil, (4) fine concrete (particle size less than 2.5 cm), and (5) coarse concrete (particle size greater than 2.5 cm). No cover was placed on two of the columns, which were used as controls. H(2)S concentrations measured from the middle of the waste layer ranged from 50,000 to 150,000 ppm. The different cover materials demonstrated varying H(2)S removal efficiencies. The sandy soil amended with lime and the fine concrete were the most effective for the control of H(2)S emissions. Both materials exhibited reduction efficiencies greater than 99%. The clayey and sandy soils exhibited lower reduction efficiencies, with average removal efficiencies of 65% and 30%, respectively. The coarse concrete was found to be the least efficient material as a result of its large particle size.     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。