一种利用脱氮硫杆菌的同步脱硫反硝化新工艺研究

Thiobacillus denitrificans, a kind of autotrophic facultative bacteria, can oxidize sulfide into elemental sulfur or sulfate when nitrate was adopted as its electron accepter and carbon dioxide as its carbon resource under anoxic or anaerobic environment. In this way, nitrate is converted into nitrogen. In addition, ThiobaciWus denitrificans can accumulate sulfur extracellularly. In this study, in a process of simultaneous desulfurization and denitrification, a strain of Thiobacillus denitriificans is employed as sulfur-producer in the treatment of wastewater containing sulfide and nitrate. The key factors affecting this process are investigated through batch tests. The experimental results indicate that the sulfide concentration and the ratio of sulfide to nitrate (S2-/NO3-) in the influent are the key factors, and their suitable values are suggested to be 5/3 and no more than 300mg·L-1, respectively, in order to achieve high conversion of sulfur.     

硅橡胶复合膜渗透汽化分离硫/汽油混合物

Worldwide environment has resulted in a limit on the sulfur content of gasoline. It is urgent to investigate the desulfurization of gasoline. The polydimethylsiloxane (PDMS)/polyetherimide (PEI) composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope (SEM). The membranes were used for sulfur removal from gasoline by pervaporation. The effects of feed temperature, sulfur content in the feed and PDMS layer thickness on membrane performance were investigated, and an activation energy of permeation was obtained. Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor. The total flux varied little with the increase of sulfur content in the feed, but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline, and then the variation was little. The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor. The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.     

Cathodic Hydrogen as Electron Donor in Enhanced Reductive Dechlorination

In situ capping is an attractive and cost-effective method for remediation of contaminated sediments, but few studies on enhancing contaminant degradation in sediment caps have been reported, especially for chlorinated benzenes. Electrically enhanced bioactive barrier is a new process for in situ remediation for reducible compounds in soil or sediments. The primary objective of this study is to determine if electrodes in sediment could create a redox gradient and provide electron acceptor/donor to stimulate degradation of chlorinated contaminant. The results demonstrate that graphite electrodes lead to sustainable evolution of hydrogen, displaying zero-order kinetics in the initial stages with different voltages. The constant rates of hydrogen evolution at 3, 4, and 5 V are 1.05, 2.54, and 4.3 nmol·L 1·d 1, respectively. Even higher voltage can produce more hydrogen, but it could not keep long time because the over potentials on electrode surfaces prevent its function. The study shows that 4 V is more appropriate for hydrogen evolution. The measured and evaluated concentration of 1,2,3,5-tetrachlorobenzene in pore water of sediment and concentration of sulfate show that dechlorination is inhibited at higher concentration of sulfate.     

Major Trends in Refractories Industry at the Beginning of the 21st Century

An analysis of the present and of the future of the refractories industry is being presented,considering some improtant techincal,economical,human and environmental issues,on a worldwide basis,Refractories still needed as confinement materials to prevent heat and mass transfer losses in many diverse manufacturing industries,and will remain so ,but the main challenges,this industry do need to neet,are to adjust to and overcapacity production ,to cope with new needs of the customers,in particular the “outsourcing“,which is a new custome/supplier rela-tionship being adopted by many of them,and more compet-itive arena.Among the direct consequences,are the need to keep the education world in refractory engineering training aliver and to cope with macro and micro projects to change the image of the Refractories,from a commodity material to a sophisticated “high-tech“ compostie material.Some suggestions are provided in the text.     

Demand Increases for New Fungicides for Rice

<正> After June this year China's regions growingmiddle and late rice had widespread blastand sheath/culm blight.Such diseasesplagued 19.2 million hectares.Starting fromJuly the market for new fungicides that cancontrol blast and sheath/culm blight for ricewas more and more active.Makers of traditional pesticides for thecontrol of blast have to contend with fiercecompetition from new pesticides in marketthis year.Kitazine,iprobenfos,isoprothiolane and tricyclazole,oftenused by farmers in the past,are graduallybeing replaced by new varieties with high     

定位贡献方法计算有机物熔点

A new method is proposed based on the position group contribution additivity for the prediction of melting points of covalent compounds. The characteristics of this method are the use of position distribution function, which could distinguish between most isomers including cis or trans structure of organic compounds. Contributions for hydrocarbons and hydrocarbon derivatives containing oxygen, nitrogen, chlorine, bromine and sulfur, are given. Results are compared with those by the most commonly used estimating methods. The average derivation for prediction of normal melting temperature of 730 compounds is 14.46 K, compared to 29.33 K with the method of Joback, and 27.81 K with the method of Constantinou-Gani. The present method is not only more accurate, but also much simpler and more stable.     

Speciation and thermal transformation of sulfur forms in high-sulfur coal and its utilization in coal-blending coking process:A review

The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources, and sulfur removal from high-sulfur coal is the most important issue. This paper reviews the speciation, forms and distribution of sulfur in coal, the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis, and the sulfur regulation during coal-blending coking of high organic-sulfur coals. It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization, which raises the need of a combination of current or newly adopted characterization methods. Different from the removal of inorganic sulfur from coal, the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property, particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes. Based on the interactions among the sulfur radicals, sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char, regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is, the high volatile coals with an appropriate releasing temperature range of CH_4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals, and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals. Wherein, the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.     

离子液体在6号溶剂油改质中的应用

A new method of upgrading 6# solvent oils using different ionic liquids as catalysts in a continuous apparatus is studied in this paper. The results show that aromatics, olefins and small quantity of sulfurs can be removed simultaneously. Using complex ionic liquid modified with CuCl as catalyst, olefins are removed completely, the mass concentrations of aromatics and sulfurs in solvent oil are 0.36% and 0.0058%, respectively, and the bromic index is zero. The sulfur removal rate decreases gradually with increasing of running time. The refined 6# solvent oil is corresponded to the quality standards of GB16629-1996, which request that the mass concentrations of aro-matics, sulfurs and bromic index are 1%, 0.012% and 1000, respectively. The loss of solvent oil is less than 3%.     

PTFE多孔膜气体渗透数学模型和膜孔结构的影响

Membrane-based separation processes are new technology combined membrane separation with conventional separation. Hydrophobic porous membranes are often used in these processes. The structure of hydrophobic porous membrane has significant effect on mass transfer process. The permeabilities of five kinds of gas, He, N2,O2, CO2 and water vapor, across six polytetrafluoroethylene(PTFE) fiat membranes were tested experimentally.Results indicated that the greater the membrane mean pore size and the wider the pore size distribution are, the higher the gas permeability. A gas permeation model, including the effects of membrane structure parameter and gas properties, was established. A comprehensive characteristic parameter (including porosity, thickness and tortuosity) was found more effective to express the influence of membrane structure in gas permeation process. The predicted permeation coefficients were in good agreement with experimental data.     

含反应节点过程数据校正的扩展独立物流法

Among the techniques developed for bilinear data reconciliation problems, the method based on independent flows is well known in terms of both accuracy and efficiency. However, the independent flow method is not effective when reactor units are present in the process. In this paper, an extended independent flow method is proposed for the data reconciliation of the process with chemical reaction. By the new method, the independent flows finding algorithm is adjusted to avoid the difficulties caused by the reactors in the process, and the reaction constraints are introduced into the objective function of data reconciliation. As a result, the new method can be applied to the process with chemical reaction while retaining high solution accuracy. To test the performance, the new method and the most typical Crowe‘s projection method are used in the data reconciliation of a typical industrial process. The results show that the new method can effectively accomplish the data reconciliation of the muhicomponent process with chemical reaction and gives more accurate estimates than the Crowe‘s method.     

负载金属氧化物分子筛催化氧化模拟汽油的脱硫研究

A simulated gasoline consisting of model sulfur compounds of thiophene （C4H4S） and 3-methythiophene （3-MC4H4S） dissolved in n-heptane was tested for the oxidative desulfurization in the hydrogen peroxide （H202） and formic acid oxidative system over metal oxide-loaded molecular sieve. The effects of the oxidative system, loaded metal oxides, phase transfer catalyst, the addition of olefin and aromatics on sulfur removal were investigated in details. The results showed that the sulfur removal rate of simulated gasoline in the H202/formic acid system was higher than in other oxidative systems. The cerium oxide-loaded molecular sieve was found very active catalyst for oxidation of simulated gasoline in this system. The sulfur removal rates of C4H4S and 3-MC4H4S were enhanced when phase transfer catalyst （PTC） was added. However, the sulfur removal rate of simulated gasoline was reduced with the addition of olefin and aromatics.     

催化裂化汽油中特征硫化物噻吩的催化氧化脱硫

以负载金属铈的分子筛为催化剂,在H2O2-HCOOH体系中,对催化裂化（FCC）汽油中特征硫化物噻吩（C4H4S）的正庚烷溶液进行了氧化脱硫研究。考察了氧化剂用量、溶剂、氧化时间、氧化温度、相转移剂等因素对噻吩脱除效果的影响,并对对噻吩的氧化反应历程进行了初步的探讨。实验结果表明：以负载金属铈的分子筛为催化剂,在反应温度50℃,反应60min, H2O2：S＝10：1（mol/mol）,H2O2：HCOOH＝1：1（V/V）的条件下,正庚烷溶液C4H4S的脱除率达到了78.2％,加入乳化剂OP可使C4H4S的脱硫率达到94.5％,但四丁基溴化胺（TBAB）的加入使氧化后的样品中出现了噻吩的溴代产物。     

活性炭担载金属氧化物用于热煤气脱硫

以热煤气脱硫并回收单质硫为目的,考察了活性炭担载金属氧化物(M/AC)在中温范围150—250℃内,催化氧化硫化氢生成单质硫的研究。担载量1%(质量分数)的M/AC通过等体积浸渍法制得,在固定床上评价了其脱硫活性,并考察了温度、反应气氛等工艺条件对脱硫效果的影响。M/AC脱硫的活性顺序为:Mn/ACCu/ACCe/ACFe/ACCo/ACV/AC。通过DTG分析,硫化氢选择性氧化的主要产物是单质硫。M/AC上金属氧化物起主要的催化作用,催化硫化氢和氧气反应生成单质硫,生成的单质硫被吸附在活性炭的孔道中。     

中孔硅胶负载浓硝酸脱除柴油中的硫化物

采取中孔硅胶负载浓硝酸脱除1 000×10~(-6)的4,6-二甲基二苯并噻吩模型柴油中的硫化物,考察反应温度、酸负载量、剂油质量比和吸附剂目数对脱硫效果的影响,并通过红外光谱分析和N_2等温吸附法对硅胶进行表征。结果表明,中孔硅胶具有较大的比表面积、孔体积和合适的孔径;浓硝酸可以负载于中孔硅胶上并将4,6-二甲基二苯并噻吩氧化为砜后吸附在硅胶上。在反应温度45℃、(40~60)目硅胶和硅胶与浓硝酸质量比为1∶0.75条件下脱硫效果最好,剂油质量比为1∶7.5时,脱硫率达93.7%,脱硫后的模型柴油硫含量达到国Ⅴ标准。     

氧化法脱除重油催化裂化柴油中的硫化物

采用双氧水-甲酸对重油催化裂化柴油进行氧化,然后使用N,N-二甲基甲酰胺萃取剂萃取脱硫。研究了在反应体系中氧化时间、氧化温度以及双氧水与甲酸的加入量对氧化脱硫率的影响,并考察了加入分散剂Span-80的效果。最终得到双氧水-甲酸-Span-80体系最佳氧化条件：分散剂Span-80为2.0%,双氧水为36%,甲酸为32%,氧化温度为60 ℃,氧化时间为50 min。分散剂Span-80的加入可以大大提高双氧水-甲酸体系对重油催化裂化柴油的氧化脱硫能力。在双氧水-甲酸体系最佳条件下氧化萃取脱硫率为85.58%,双氧水-甲酸-Span-80体系脱硫率高达98.27%,重油催化裂化柴油的硫含量由12 500 mg/L降至216 mg/L。气相色谱结果显示,氧化脱硫后重油催化裂化柴油中的噻吩、苯并噻吩及其衍生物基本被脱除,有少量二苯并噻吩及其衍生物需要进一步脱除。     

微波诱导催化氧化处理二乙基次膦酸铝废水

采用微波诱导活性炭负载铁铜(Fe_3O_4-CuO-AC)催化H_2O_2、Na_2S_2O_8处理二乙基次膦酸铝(AlPi)废水,探究了两种体系下pH、催化剂投加量、氧化剂投加量、温度等因素对废水中总磷去除率的影响,对比了双氧化体系(MW/Fe_3O_4-CuO-AC/Na_2S_2O_8+H_2O_2)与两种单一氧化体系(MW/Fe_3O_4-CuO-AC/Na_2S_2O_8、MW/Fe_3O_4-CuO-AC/H_2O_2)对AlPi的氧化效果。结果表明,双氧化体系对AlPi模拟废水和工业废水中总磷的去除率可分别达到85.47%、71.43%,显著高于单一氧化体系。     

Dynamic catalytic adsorptive desulfurization of real diesel over ultra‐stable and low‐cost silica gel‐supported TiO2

To develop dynamic ultra‐deep catalytic adsorptive desulfurization (CADS) of real diesel using ultra‐stable and low‐cost silica gel‐supported TiO₂ is the aim of the work. A two‐stage dynamic breakthrough model was built to describe the CADS process, varied with H/R ratio and O/S ratio. The desulfurization capacity reached 1.3 mg‐S/g‐A at the breakthrough concentration of 5 ppm‐S. Various types of silica gel were screened as the substrate for TiO₂, and the textural/acidic properties and CADS capacity were correlated in high relevancy. The effectiveness of diverse oxidants on CADS and the oxidation path were elucidated via combined experiment/simulation. Adsorption enthalpy derived from fitted isotherm data was calculated as 33.4 kJ/mol. The TiO₂/silica gel‐based sorbent demonstrated remarkable recyclability/stability in 10 cycles. An effective and economic route to eliminate the trace amount of stubborn sulfur compounds in low‐sulfur diesel is provided, which can be potentially implemented as the final polishing step for ultra‐clean diesel production. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2146–2159, 2018     

催化裂化柴油氧化吸附脱硫脱氮工艺研究

通过单因素考察了催化裂化柴油氧化脱硫脱氮效果。结果表明,选用甲酸和30%H2O2作为氧化体系,以磷钨酸为催化剂,糠醛为萃取剂,在氧化温度为60℃,反应时间60min,V（氧化体系）/V（焦化柴油）为0.32,V（甲酸）/V（双氧水溶液）为0.5,磷钨酸用量为0.20g/L,采用二级萃取的优化工艺条件下,可将焦化柴油中硫的质量分数由1339.641μg/g降至19.37μg/g,氮质量分数由750.33μg/g降至7.5μg/g。     

Ca2+,Al3+对不含Na+硅酸体系聚合行为的影响

为排除Na+对硅酸聚合的影响,用酸解水淬硅酸钙制备了不含金属离子的硅酸溶液及含Ca2+, Al3+的硅酸溶液,研究了加入Ca2+, Al3+对体系聚合行为的影响. 结果表明,加入Ca2+后体系pH值略微降低,加入Al3+后体系pH值显著降低. 初始pH≤2时,Al3+对硅酸聚合起促凝作用,初始pH>2时,Al3+起缓凝作用. Ca2+对硅酸聚合影响不大. 硅酸凝胶后,含Al3+硅酸体系中形成Al?O?Si键,阻碍了凝胶结构水脱附;Ca2+则阻碍凝胶的晶化转变过程,且凝胶中的结构水变少. 不含金属离子、含Ca2+、含Al3+体系的化学式分别为SiO2×0.52H2O, SiO2×0.36H2O, SiO2×1.50H2O.     

聚酰胺-胺树状分子锡配合物催化性能研究

通过固相合成的方法将聚酰胺-胺树状大分子PAMAM担载于大孔硅胶上,并对其外围分别用对羟基苯甲醛、2,4-二羟基苯甲醛和邻羟基苯甲醛进行修饰,再与SnCl2.2H2O反应形成三类共计9种不同代数树状高分子锡配合物。将该类配合物用作质量分数30%双氧水氧化酮的Baeyer-Villiger(B-V)反应的催化剂,考察其催化活性,结果表明,在该类配合物作用下,2-金刚烷酮、环戊酮、环己酮、4-甲基环己酮、4-叔丁基环己酮、3-甲基-2-戊酮和4-甲基-2-戊酮都可以发生B-V氧化反应而转化为相应的酯和内酯,底物的转化率(75%～99%)和产物选择性(95%～100%)都较高。比较了不同载体(氯球、纤维素、壳聚糖、硅胶)、不同配体的金属锡配合物对B-V催氧化反应的催化效果,研究发现,载体、配体和金属担载量对配合物的催化活性均有不同程度的影响。其中,硅胶为最好的载体,而邻羟基苯甲醛为最好的配体。