苯甲酸生产废水的处理与资源化

为有效地回收甲苯液相氧化法生产苯甲酸的工业废水中的苯甲酸和乙酸,并配合废水生物降解的末端处理技术,研究了20%,30%和50%磷酸三丁酯(TBP)/煤油的混合溶剂、正辛醇和甲苯萃取苯甲酸稀溶液特性,以及对工业废水处理的实验.结果表明,TBP对苯甲酸稀溶液具有良好的萃取作用,而纯溶剂体系与溶剂的极性有关,正辛醇的萃取能力与30%TBP相当;残液中的COD_Cr值由萃取剂在水中的溶解和苯甲酸自身的COD_Cr值组成,其中残液中溶剂溶解导致的COD_Cr值随其中苯甲酸浓度变化不明显,且COD_Cr值的大小为:50%TBP≈30%TBP>正辛醇>20%TBP>甲苯.针对工业废水中主要含有苯甲酸和乙酸的工况,提出了废水资源化的处理工艺流程,即首先采用甲苯进行废水中苯甲酸的回收,之后,再利用三烷基氧磷/煤油为萃取剂回收废水中的醋酸,进一步生产绿色化学品乙酸钙镁盐.     

络合萃取法处理金刚烷胺制药废水

采用络合萃取法处理金刚烷胺制药废水,考察了初始pH、络合剂种类、稀释剂配比、油/水相比和反应温度等对废水中金刚烷胺萃取效率的影响,并对萃取剂中金刚烷胺进行了反萃取分离回收. 结果表明:采用V(P₂₀₄)〔P₂₀₄为二(2-乙基己基磷酸)〕∶V(正辛醇)为3∶2的复配萃取剂处理金刚烷胺制药废水,在初始pH为8.0、油/水相比为1∶1和温度为25 ℃的条件下,能够去除废水中99.7%以上的金刚烷胺;在反萃取过程中,V(P₂₀₄)∶V(正辛醇)为1∶4的复配萃取剂可以获得更高的反萃取效率,以1.0 mol/L的HCl溶液为反萃取剂,当油/水相比为1∶1时,可将51.7%的金刚烷胺从萃取剂中反萃分离,回收得到的金刚烷胺盐酸盐溶液可以回用到生产工艺中,P₂₀₄-正辛醇复配萃取剂可在萃取和反萃取过程中多次重复使用.      

溶剂萃取法回收4-溴-2-氟碘苯萃余废水中的碘

研究了4-溴-2-氟碘苯萃余废水中碘的回收方法。25℃下,测定了苯、环己烷等7种萃取剂对碘萃取的分配常数及环己烷对碘萃取的分配曲线。研究选用了萃取率与分配常数相对较高,毒性相对较低的环己烷为萃取剂,并探讨了萃取剂、反应时间、溶液pH值、温度、反萃剂等因素对碘单质去除率的影响。结果表明在室温20℃,不调节废水pH值,相比为1:5、萃取时间10 min的条件下,碘的萃取率可达到88%。在室温20℃,相比为4:5的条件下,采用0.1 mol/L的氢氧化钾为反萃剂,碘的单级反萃率可达到90%。     

络合萃取法处理模拟金刚烷胺制药废水

采用络合萃取法处理模拟金刚烷胺制药废水,比较了苯、CCl4和P204等11种萃取剂对水溶液中金刚烷胺的萃取效果,考察了溶液初始pH值、稀释剂的类型、萃取剂与稀释剂的配比和油/水比等因素对萃取效率的影响,并对萃取液进行了反萃取分离研究.结果表明,在水溶液中金刚烷胺浓度为1000 mg·L-1,溶液初始pH值为8.0~10.0,油/水比为1∶1的条件下,采用P204与正辛醇体积比3∶2的复配萃取剂进行萃取分离,金刚烷胺萃取率可以达到99.0%以上,当金刚烷胺浓度增加至10.0 g·L-1时,萃取率仍可以保持在97.0%以上;以2.0 mol·L-1的HCl溶液为反萃取剂,按照油/水比为1∶1可将51.1%的金刚烷胺从萃取剂中反萃分离.     

三种土壤中土霉素浸提方法的比较研究

以棕壤、褐土和红壤为研究对象,比较了不同浸提方法,不同浸提剂对土壤中土霉素的浸提效率.结果表明,在所用的3种方法中,采用振荡浸提方法,以及Na2EDTA-McIlvaine缓冲液对土霉素具有稳定、高效的浸提回收率.土霉素形态初步分析连续浸提步骤为:以H2O、0.1mol/L CaCl2、和Na2EDTA-McIlvaine缓冲液为浸提剂依次浸提可分别得到水溶态、可交换态、吸附态和固定态土霉素.3种土壤中土霉素形态呈现吸附态>可交换态>水溶态的规律.     

丁辛醇缩合废水处理方法探讨

丁辛醇装置在生产过程中产生的丁醛缩合废水,COD质量浓度高达40 000 mg/L。采用酸化萃取法处理此股高浓度有机废水,探讨了不同废水pH值、温度、萃取剂及萃取剂用量对萃取效果的影响。实验结果表明:以辛醇、辛醇精馏残液和辛烯醛加氢残液作为萃取剂,在废水pH值为1～3、萃取剂与废水的体积比为1∶(1～12)、温度为25～60℃条件下,对丁辛醇废水进行萃取处理,得到较好的处理效果,COD去除率可达83%～94%。     

废弃电子元器件酸性浸出液中铜的萃取研究

利用国产新型铜萃取剂DZ988,以PEG-NO2/H2SO4混酸溶液氧化浸取废弃电子元器件得到的酸浸液为萃取原液(含铜浓度CCu=3.132 g/L),进行铜的萃取研究,考察各因素对铜的萃取及反萃取的影响。试验结果表明,铜的萃取率随萃取剂浓度、O/A比、萃取温度及pH的提高而提高;在萃取剂浓度设定为25%,萃取料液浓度用氨水调至pH=2,油水比O/A=1:1,常温的条件下,对废弃电子元器件的PEG-NO2/H2SO4混酸浸出液中的铜的萃取率可达99.45%,铜、铁分离系数达1 151;以硫酸作反萃剂,对负载铜的萃取剂进行反萃取研究,在硫酸溶液浓度为250 g/L,相比O/A=1:1时,铜的反萃率接近100%。同时,DZ988基本不萃取Co、Ni,后续可从铜萃余液中继续回收Co、Ni。     

Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China

Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu^2 +) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu^2 + sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu^2 + sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu^2 + sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu^2 + (R² > 0.97), and it was still good under different pH values (R² > 0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu^2 + sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu^2 + sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu^2 + sorption. It indicated that aluminum dissolution is associated with non-specific sorption.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Simultaneous determination of ten taste and odor compounds in drinking water by solid-phase microextraction combined with gas chromatography-mass spectrometry

Taste and odor （T＆O） problems in drinking water frequently occur because of many compounds present in the water, of which trans-1,10-dimethyl-trans-9-decalol （geosrnin） and 2-methylisoborneol （MIB） are well-known. In this study, a fast and effective method was established for simultaneous determination of 10 T＆O compounds, including geosmin, MIB, 2,4,6-trichloroanisole （TCA）, 2-methylbenzofuran, 2-isopropyl-3-methoxypyrazine （IPMP）, 2-isobutyl-3-methoxypyrazine （IBMP）, cis-3-hexenyl acetate, trans,trans-2,4-heptadienal, trans, cis-2,6-nonadienal, and trans-2-decenal in water samples by headspace solid-phase microextraction （SPME） coupled with gas chromatography-mass spectrometry. An orthogonal array experimental design was used to optimize the effects of SPME fiber, extraction temperature, stirring rate, NaC1 content, extraction time, and desorption time. The limits of detection ranged from 0.1 to 73 ng/L were lower than or close to the odor threshold concentrations （OTCs）. All the 10 T＆O compounds were detected in the 14 water samples including surface water, treatment process water and tap water, taken from a waterworks in Lianyungang City, China. MIB and geosmin were detected in most samples at low concentration. Six T＆O compounds （IPMP, IBMP, trans,cis-2,6-nonadienal, 2-methylbenzofuran, trans-2-decenal, and TCA） were effectively decreased in water treatment process （sedimentation and filtration） that is different from cis-3-hexenyl acetate, MIB and geosmin. It is noted that the TCA concentrations at 15.9-122.3 ng/L and the trans,cis-2,6-nonadienal concentrations at 79.9-190.1 ng/L were over 10 times higher than their OTCs in tap water. The variation of the analytes in the all water samples, especially distribution system indicated that distribution system cannot be ignored as a T＆O compounds source.     

城市污泥中Cu回收研究：生物沥浸-溶剂萃取-电积沉Cu技术

城市污泥通常含有大量有机质但也存在数量不等有害金属,在不影响污泥有益成分的基础上,去除和回收污泥中金属,既使污泥无害化又产生经济效益,意义重大.针对苏州某工业园区污泥重金属含量较高,研究利用生物沥浸-溶剂萃取-电积技术回收城市污泥中重金属Cu的工艺,并探讨了采用5-壬基水杨醛肟萃取剂M5640从城市污泥生物沥浸液中萃取分离Cu和Fe的最佳工艺参数.结果表明,经过生物沥浸处理72 h后,城市污泥中重金属Cu溶出率高达90%.当最佳工艺条件为:萃取剂体积分数为2%,相比(有机相与水相体积比,以O/A表示)为1/3,沥浸液pH为2.0时,沥浸液中Cu的一级萃取率达到95%以上,而Fe的共萃率低于10%;反萃取试验结果表明,在反萃取相比为2/1的条件下用1.5 mol/L硫酸溶液进行反萃取,Cu的一级反萃取率达到80.07%;反萃取后的富集Cu溶液作为电解液,在槽电压为2.1 V、电解温度为55℃条件下电积6 h,Cu回收率达到90%以上.在整个工艺中萃余液和反萃液均可循环利用无废液排放,对含Cu高的污泥,利用生物沥浸-溶剂萃取-电积技术回收有良好的应用前景.     

Removal of organic contaminants from water or wastewater with liquefied gases

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3-甲基-3-丁烯基-1-醇与硫酸/过氧化氢混合溶液的吸收反应研究

应用配置有湿式流动反应管的真空紫外激光单光子电离飞行时间质谱研究了3-甲基-3-丁烯基-1-醇气体在硫酸/过氧化氢混合溶液表面的吸收反应,实验中首次测得了反应的摄取系数,并根据气相产物信息推测了其反应机制.3-甲基-3-丁烯基-1-醇与硫酸/过氧化氢混合溶液的吸收反应速率很快,在ω（H2SO4）为40%～60%范围,摄取系数为2.52×10-4～1.05×10-2.在反应过程的气相收集物中检测出3种气相产物：乙醛、丙酮和3-甲基-3,4-环氧-1-丁醇,由此推测了3-甲基-3-丁烯基-1-醇与H2 SO4/H2 O2混合溶液的非均相反应机制.3-甲基-3,4-环氧-1-丁醇可以经过多步转化形成多羟基化合物,同时生成的醛酮化合物在酸性溶液中可进一步反应,这些对大气二次有机气溶胶的形成起着重要作用.因此,3-甲基-3-丁烯基-1-醇的非均相催化氧化过程可能对二次有机气溶胶的形成有重要贡献.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of >10 nm new particles.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of > 10 nm new particles.     

Bio-remediation of acephate–Pb(II) compound contaminants by Bacillus subtilis FZUL-33

Removal of Pb~(2+)and biodegradation of organophosphorus have been both widely investigated respectively. However, bio-remediation of both Pb~(2+)and organophosphorus still remains largely unexplored. Bacillus subtilis FZUL-33, which was isolated from the sediment of a lake, possesses the capability for both biomineralization of Pb~(2+)and biodegradation of acephate. In the present study, both Pb~(2+)and acephate were simultaneously removed via biodegradation and biomineralization in aqueous solutions.Batch experiments were conducted to study the influence of p H, interaction time and Pb~(2+)concentration on the process of removal of Pb2+. At the temperature of 25°C, the maximum removal of Pb~(2+)by B. subtilis FZUL-33 was 381.31 ± 11.46 mg/g under the conditions of p H 5.5, initial Pb~(2+)concentration of 1300 mg/L, and contact time of 10 min. Batch experiments were conducted to study the influence of acephate on removal of Pb~(2+)and the influence of Pb2+on biodegradation of acephate by B. subtilis FZUL-33. In the mixed system of acephate–Pb2+, the results show that biodegradation of acephate by B. subtilis FZUL-33 released PO43+, which promotes mineralization of Pb2+. The process of biodegradation of acephate was affected slightly when the concentration of Pb2+was below 100 mg/L. Based on the results, it can be inferred that the B. subtilis FZUL-33 plays a significant role in bio-remediation of organophosphorus-heavy metal compound contamination.     

氨基苯酚类废水的络合萃取

以P2 0 4 (二 (2 乙基己基 )磷酸 )为络合剂 ,煤油为稀释剂 ,正辛醇为助溶剂 ,通过萃取 反萃取的方式 ,对氨基苯酚类废水进行处理。研究了萃取剂浓度、废水pH值和油水比O/W ,以及反萃剂浓度、反萃油水比和反萃温度对萃取效率的影响。结果表明可将原废水的CODcr值降低至 1 / 7,使之满足其它末端处理的要求 ,而且反萃工艺简单易行 ,溶剂可重复使用     

不同反胶束体系萃取纤维素酶的条件优化对比研究

采用3种不同的表面活性剂双(2-乙基己基)磺基琥珀酸钠AOT、十六烷基三甲基溴化铵CTAB及鼠李糖脂RL)溶于正己醇/异辛烷相构建不同的反胶束体系,并对比研究了不同反胶束体系萃取纤维素酶的优化条件.分别探讨了水相pH值、表面活性剂浓度、离子强度和离子种类对纤维素酶萃取效率的影响.实验结果如下:在实验条件下,AOT、CTAB和RL 3种反胶束体系水相最佳pH值分别为3.0、8.0和3.0;表面活性剂最佳浓度依次为:AOT 23.7mmol/L、CTAB 15mmol/L和RL 2.75mmol/L;水相中NaCl浓度会影响纤维素酶的萃取率,3种表面活性剂构建的反胶束体系萃取纤维素酶的萃取率均随着盐离子浓度的增大而降低;水相中离子种类也会影响纤维素酶的萃取率.比较不同反胶束体系在最佳条件下萃取纤维素酶的最佳萃取率:CTAB>AOT>RL.     

Chemical forms of cobalt and nickel extracted by M1, M3 and CaCl2 DTPA

Mehlich 1(M1), mehlich 3(M3) and CaCl₂ DTPA have been used to predict the available micronutrient in soil. However, the forms of micronutrient extractable by these extractants are not known. In the present study, ten soils, collected from five provinces and the capital of China, representing a wide range of chemical and physical properties, were analyzed by sequential extraction to isolate five forms of cobalt and nickel, they are exchangeable, carbonate bound, Fe Mn oxide bound, organically bound and residual forms. The chemical forms extracted by M1, M3 and CaCl₂ DTPA were also investigated. The results show strong correlation between the carbonate bound or organically bound forms of Co or Ni and the amounts of extractable by any of the above three extractants. The main forms extracted by these extractants are carbonate and organically bound forms. The ranking of these three extractants for extraction of Co and Ni are M1>M3=CaCl₂ DTPA and M1=M3>CaCl₂ DTPA, respectively.     

络合萃取技术在苯胺-硝基苯废水处理中的应用研究

选用20％三烷基胺 80％加氢煤油作为萃取荆，进行四级萃取实验，探讨络合萃取技术处理苯胺-硝基苯废水工业化的可能性。实验结果表明，采用三烷基胺一加氢煤油混合溶剂对苯胺-硝基苯废水进行萃取，具有相当高的COD去除率。