直流电场对红串红球菌NCC-1脱硫效率的影响及电刺激机理的初探

研究了脱硫菌--红串红球菌NCC-1在直流电场作用下的生长及脱硫状况,以及实际柴油体系中的脱硫效率,并对外加弱电流加速脱硫菌生长的机理进行了初探。 实验表明,水相适宜范围的电流密度可以提高脱硫菌的脱硫效率,脱硫菌脱硫的最佳电流密度为0.72 A/m²,该条件下,铂电极培养体系菌体比不加电培养体系提前48 h完全降解0.2 mmol/L二苯并噻吩（DBT）。 比相同电流密度钛电极培养体系菌体提前24 h。 铂电极最佳电流密度下菌体对实际柴油的脱硫率可以达到67.4％,比钛电极培养体系菌体高11.7%,高于不加电24.6%。 经验证,发现引起这种变化的主要原因是水的阴极电解产物吸附氢和氢气的比例不同,其中氢气对摇瓶培养菌体促进作用显著。     

π络合脱硫吸附剂Cu(I)-Y的生物再生

吸附与生物技术的耦合是实现燃料油品清洁生产的新发展方向,提出了一种吸附剂生物再生循环使用的新耦合方法,首先用吸附剂吸附脱除油品中的含硫化合物,然后用微生物脱附吸附剂表面吸附的硫化物,实现吸附剂再生.利用Y型分子筛通过离子交换再用He保护自动还原的方法制备了π络合吸附剂吸附Cu(I)-Y,以DBT为模型化合物考察了吸附剂的吸附性能.以选择性脱硫菌德氏假单胞菌(Pseudomonasdelafieldii)R-8为生物催化剂,考察了细胞浓度、油相体积、水相/吸附剂比对吸附剂脱附率的影响.加入油相可以大大提高DBT脱附量和生成2-HBP的量.增加水相中脱硫菌R-8的浓度、增大水相/吸附剂比,可以实现DBT脱附,促进DBT转化为2-HBP.在水相脱硫菌株R-8浓度为75g·L?1、水相/吸附剂比为300mL/g、油相/水相比1/3(V/V)的条件下,脱附的DBT在6h内转化率达到89%,24h内转化率为100%.生成2-HBP的量主要由吸附剂吸附硫化物的量、水相中微生物细胞的浓度、油相/水相体积比、水相/吸附剂比决定.吸附剂经过正辛烷洗涤、100℃下干燥24h、He保护450℃还原活化3h,再生吸附剂的吸附能力为新鲜吸附剂的95%.     

π络合脱硫吸附剂Cu(Ⅰ)-Y的生物再生

吸附与生物技术的耦合是实现燃料油品清洁生产的新发展方向, 提出了一种吸附剂生物再生循环使用的新耦合方法, 首先用吸附剂吸附脱除油品中的含硫化合物, 然后用微生物脱附吸附剂表面吸附的硫化物, 实现吸附剂再生. 利用Y型分子筛通过离子交换再用He保护自动还原的方法制备了(络合吸附剂吸附Cu(Ⅰ)-Y, 以DBT为模型化合物考察了吸附剂的吸附性能. 以选择性脱硫菌德氏假单胞菌(Pseudomonas delafieldii)R-8为生物催化剂, 考察了细胞浓度、油相体积、水相/吸附剂比对吸附剂脱附率的影响. 加入油相可以大大提高DBT脱附量和生成2-HBP的量. 增加水相中脱硫菌R-8的浓度、增大水相/吸附剂比, 可以实现DBT脱附, 促进DBT转化为2-HBP. 在水相脱硫菌株R-8浓度为75 g·L-1、水相/吸附剂比为300 mL/g、油相/水相比1/3(V/V)的条件下, 脱附的DBT在6 h内转化率达到89%, 24 h内转化率为100%. 生成2-HBP的量主要由吸附剂吸附硫化物的量、水相中微生物细胞的浓度、油相/水相体积比、水相/吸附剂比决定. 吸附剂经过正辛烷洗涤、100℃下干燥24 h、He保护450℃还原活化3 h, 再生吸附剂的吸附能力为新鲜吸附剂的95%.     

专一性脱硫菌的分离与鉴定

以二苯并噻吩(DBT)为模型化合物, 从自然界分离得到一株能专一性脱除DBT中硫元素的微生物. HPLC对代谢产物的分析表明该菌能选择性地脱除DBT中的硫, 生成2-羟基联苯. 该菌的16SrDNA序列分析、胞壁化学组分分析、生理生化特征及形态学特征表明该菌属于红球菌属(Rhodococcus)进化分枝, 形态特征: 基内菌丝生长良好, 有初级分枝、横隔并断裂成杆状或球状小体, 表面光滑; 无气生菌丝体. 胞壁化学组分中含有枝菌酸, 胞壁属于IV型, 部分抗酸, 其与红平红球菌(Rhodococcus erythropolis)同源性最高. 该菌能在DBT浓度小于10 mmol/L的基础培养基上生长, 最佳生长所需的DBT浓度是1 mmol/L, 在DBT浓度为0.5 mmol/L时脱硫活性最高. 该菌同时能脱除苯并噻吩、苯硫醚和4, 6-二甲基二苯并噻吩中的硫.     

πp络合脱硫吸附剂Cu(I)-Y的生物再生

吸附与生物技术的耦合是实现燃料油品清洁生产的新发展方向, 提出了一种吸附剂生物再生循环使用的新耦合方法, 首先用吸附剂吸附脱除油品中的含硫化合物, 然后用微生物脱附吸附剂表面吸附的硫化物, 实现吸附剂再生. 利用Y型分子筛通过离子交换再用He保护自动还原的方法制备了π络合吸附剂吸附Cu(I)-Y, 以DBT为模型化合物考察了吸附剂的吸附性能. 以选择性脱硫菌德氏假单胞菌(Pseudomonas delafieldii)R-8为生物催化剂, 考察了细胞浓度、油相体积、水相/吸附剂比对吸附剂脱附率的影响. 加入油相可以大大提高DBT脱附量和生成2-HBP的量. 增加水相中脱硫菌R-8的浓度、增大水相/吸附剂比, 可以实现DBT脱附, 促进DBT转化为2-HBP. 在水相脱硫菌株R-8浓度为75 g·L^-1、水相/吸附剂比为300 mL/g、油相/水相比1/3(V/V)的条件下, 脱附的DBT在6 h内转化率达到89%, 24 h内转化率为100%. 生成2-HBP的量主要由吸附剂吸附硫化物的量、水相中微生物细胞的浓度、油相/水相体积比、水相/吸附剂比决定. 吸附剂经过正辛烷洗涤、100℃下干燥24 h、He保护450℃还原活化3 h, 再生吸附剂的吸附能力为新鲜吸附剂的95%.     

一株红球菌脱硫菌株脱硫特性的研究

从炼油厂污水排放口取得的土样中筛选到一株能降解二苯并噻吩 (DBT)的菌株 ,用GC/MS方法 ,证明其降解DBT走硫专一脱除途径 ,即“4S途径” .该菌株被命名为SDUZAWQ ,用微生物生理生化实验及 16SrDNA序列分析初步鉴定为红球菌属 (Rhodococcussp .) .实验结果表明 ,红球菌SDUZAWQ可有效降解苯并噻吩 (BT)和DBT及其甲基衍生物 .在 2d内 ,BT与DBT可同时完全降解 ,0 .5mmol·L-1的BT在 1d内可降解掉 86% ,降解速度高于DBT的降解 .5 MBT的降解率也高于 4,6 DMDBT和 4 MDBT .4 MDBT较 4,6 DMDBT更难降解 ,在 2d内 ,红球菌SDUZAWQ可降解 62 %的 4,6 DMDBT ,而相同条件下 ,4 MDBT仅能被降解 3 6% .     

超声协同TiO_2光催化脱除燃料油中有机硫的研究

采用溶胶凝胶法制备纳米TiO2光催化剂,引入超声作用,以空气中的氧气为氧化剂,正辛烷为模拟油品对燃料油中硫化物的脱除进行了研究。考察了光照强度、催化剂用量、反应时间、二苯并噻吩(DBT)初始浓度、超声功率等因素对TiO2光催化二苯并噻吩溶液降解效率的影响。结果表明,引入超声后DBT的降解率提高了10%左右,并在TiO2用量为2 g/L,通气量为800 mL/min,光照距离20 cm,DBT初始浓度为600 mg/L,反应时间为150 min,超声功率为500 W的条件下,DBT降解率达到了72.6%。     

核黄素光敏化氧化二苯并噻吩的研究

以二苯并噻吩(DBT)的正辛烷溶液模拟柴油、水为溶剂、空气中的O<,2>为氧化剂和核黄素(RF)为光敏剂,研究了DBT在15 W紫外杀菌灯照射下的光化学氧化.结果表明,反应的最佳条件为:核黄素浓度20mg/L,空气流速80-100 mL/min.在该反应条件下反应2 h后,DBT的脱硫率为60%.核黄素是通过O<,2>...     

纳米二氧化钛对水中Sn(Ⅱ)、Sn(Ⅳ)和二丁基锡吸附性能的研究

采用流动注射-氢化物发生-原子吸收光谱法研究纳米TiO2对Sn(Ⅱ)、Sn(Ⅳ)和二丁基锡(DBT)的吸附作用,探讨在不同pH值、吸附时间、试样浓度和试样体积下,不同用量的纳米TiO2的吸附效果以及试样的洗脱条件和效率。结果表明,Sn(Ⅱ)和Sn(Ⅳ)的浓度≤6.0μg/mL、体积≤500 mL、pH=3.0;DBT的浓度≤0.2μg/mL、体积≤50 mLp、H=4.0,30 mg纳米TiO2对Sn(Ⅱ)、Sn(Ⅳ)和DBT的吸附率≥90.0%。在25℃条件下,纳米TiO2对Sn(Ⅱ)、Sn(Ⅳ)和DBT的饱和吸附容量分别为23.6μg/mg、13.7μg/mg和0.628μg/mg,适用于无机锡和二丁基锡污染的吸附去除及对水中无机及丁基锡的定量富集。用4 mol/L HCl对吸附的Sn(Ⅱ)、Sn(Ⅳ)和DBT进行洗脱,洗脱率达到98%以上,可做为样品分析的前处理方法。     

MFC逆转化CO2合成甲醇研究

微生物燃料电池(MFC)反应器是利用附着在阳极上的产氢微生物,在吸收烟气CO2的同时将CO2逆转化合成高附加值的生物合成燃料的装置。试验选用从牛粪中分离筛选出的梭状芽孢菌(Clostridium.sp)作为合成生物燃料的合成菌,将MFC反应装置接入电化学工作站进行CV测试,当发生还原反应时,在-0.5 V时出现还原峰,利用直流稳压电源恒电压电解,检测到合成的生物燃料为甲醇。在24 h时甲醇的积累量达到最大3.13 mmol/L;当CO2气体比例为15%时甲醇积累量最大,为2.98 mmol/L。在细菌接种量为1 mL时,甲醇积累量达到最大,为2.76 mmol/L。,最适条件下的CO2转化率为7.5%。     

Biodesulfurization of a System Containing Synthetic Fuel Using Rhodococcus erythropolis ATCC 4277

The burning of fossil fuels has released a large quantity of pollutants into the atmosphere. In this context, sulfur dioxide is one of the most noxious gas which, on reacting with moist air, is transformed into sulfuric acid, causing the acid rain. In response, many countries have reformulated their legislation in order to enforce the commercialization of fuels with very low sulfur levels. The existing desulfurization processes cannot remove such low levels of sulfur and thus a biodesulfurization has been developed, where the degradation of sulfur occurs through the action of microorganisms. Rhodococcus erythropolis has been identified as one of the most promising bacteria for use in the biodesulfurization. In this study, the effectiveness of the strain R. erythropolis ATCC 4277 in the desulfurization of dibenzothiophene (DBT) was evaluated in a batch reactor using an organic phase (n-dodecane or diesel) concentrations of 20, 80, and 100 % (v/v). This strain was able to degrade 93.3, 98.0, and 95.5 % of the DBT in the presence of 20, 80, and 100 % (v/v) of dodecane, respectively. The highest value for the specific DBT degradation rate was 44?mmol DBT?·?kg DCW^?1?·?h^?1, attained in the reactor containing 80 % (v/v) of n-dodecane as the organic phase.     

Bio-regeneration of π-complexation desulfurization adsorbents

The coupling of adsorption desulfurization and biodesulfurization is a new approach to produce clean fuels. Sulfur compounds are firstly adsorbed on adsorbents, and then the adsorbents are regenerated by microbial conversion. п-Complexation adsorbent, Cu(l)-Γ, was obtained by ion exchanging Γ-type zeolite with Cu²⁺ and then by auto-reduction in helium at 450°C for 3 h. Dibenzothiophene (DBT) was used as a model compound. The effects of cell concentration, volume of oil phase, the ratio of aqueous phase to adsorbent on DBT desorption by a bacterium were studied. The amounts of DBT desorbed and 2-HBP produced can be apparently increased with addition of n-octane. BDS activity can be improved by increasing cell concentration and the ratio of water-to-adsorbent. 89% of DBT desorbed from the adsorbents can be converted to 2-HBP within 6 h and almost 100% within 24 h, when the volume ratio of oil-to-water was 1/5 mL/mL, the cell concentration was 60 g·L^-1, and the ratio of adsorbent-to-oil was 0.03 g- mL^-1. The amount of 2-HBP produced was strongly dependent on the volume ratio of oil-to-water, cell concentration and amount of adsorbent. Adsorption capacity of the regenerated adsorbent is 95% that of the fresh one after being desorbed with Pseudomonas delafieldii R-8, washed with n-octane, dried at 100°C for 24 h and auto-reduced in He.     

Desulfurization of dibenzothiophene, benzothiophene, and other thiophene analogs by a newly isolated bacterium, Gordonia alkanivorans strain 1B

A novel bacterium, Gordonia alkanivorans strain 1B, was isolated from hydrocarbon-contaminated soil. Assessment of the biodegradation of distinct organic sulfur-compounds, such as dibenzothiophene (DBT), benzothiophene (BT), DBT sulfone, and alkylated tiophenic compounds, as the sole source of sulfure was investigated. G. alkanivorans strain 1B was able to remove selectively the sulfur from DBT while keeping intact the remaining carbon-carbon structure. Orthophenyl phenol (2-hydroxybiphenyl) was the only detected metabolic product. The bacterial desulfurization activity was repressed by sulfate. G. alkanivorans straini 1B consumed 310 μM DBT after 120 h of cultivation, corresponding to a specific desulfurization rate of 1.03 μmol/(g of dry cells·h). When an equimolar mixture of DBT/BT was used as a source of sulfur in the growth medium, G. alkanivorans strain 1B assimilated both compounds in a sequential manner, with BT as the preferred source of sulfur. Only when BT concentration was decreased to a very low level was DBT utilized as the source of sulfur for bacterial growth. Thespecific desulfurization overall rates of BT and DBT obtained were 0.954 and 0.813 μmol/(g of dry cells·h), respectively. The newly isolated G. alkanivorans strain 1B has good potential for application in the biodesulfurization of fossil fuels.     

Iron promotion of V‐HMS mesoporous catalysts for ultra‐deep oxidative desulfurization

Bimetallic Fe‐V‐HMS (HMS, hexagonal mesoporous silica) catalysts with various molar ratios of iron to vanadium were synthesized using a co‐synthesis method, and investigated for oxidative desulfurization of dibenzothiophene (DBT) using tert‐butyl hydroperoxide as an oxidant. The catalysts were characterized using X‐ray diffraction, temperature‐programmed desorption of ammonia, Fourier transform infrared spectroscopy and N₂ physical adsorption–desorption techniques. The Fe‐V‐HMS catalyst with a 2:1 molar ratio of iron to vanadium exhibited the highest total acidity and the highest catalytic activity. DBT was almost completely oxidized to dibenzothiophenesulfone, a species with a higher polarity that could be subsequently adsorbed on the Fe‐V‐HMS, and therefore the Fe‐V‐HMS acts as both a catalyst and an adsorbent simultaneously. The desulfurization rate was 98.1%. A pseudo‐first‐order model was fitted to the experimental data, and the activation energy was found to be 38.79 kJ mol^?1. The encouraging performance of Fe‐V‐HMS offers the prospect of the design of a one‐pot oxidative desulfurization process without needing extraction of sulfones from fuel oil with a chemical solvent.     

Immobilization of phosphotungstic acid in an amino‐containing metal–organic framework for oxidative desulfurization

A composite material has been successfully synthesized using an amino‐containing metal–organic framework (NH₂‐MOF) and phosphotungstic acid (PTA). This composite was characterized using X‐ray diffraction, high‐resolution transmission electron microscopy, nitrogen adsorption–desorption measurements, Fourier transform infrared spectroscopy and X‐ray fluorescence. Characterization results confirmed the immobilization and good distribution of PTA in the NH₂‐MOF. The PTA/NH₂‐MOF was subsequently applied in the oxidative desulfurization of dibenzothiophene (DBT) with H₂O₂ as the oxidant in n‐octane under atmospheric conditions. Under optimal reaction conditions, the oxidative desulfurization conversion of DBT reached 100%, and there was no significant decrease of the catalytic activity after four recycles. Kinetic experiments were also performed for the reaction at various temperatures, which indicated that oxidative reaction rates followed pseudo first‐order kinetics, and the apparent activation energy for the desulfurization reaction was 34.1 kJ mol^?1. The results indicated that this material exhibited excellent catalytic performance for oxidative desulfurization of DBT. Copyright © 2016 John Wiley & Sons, Ltd.     

二苯并噻吩和吲哚在NiMoS/γ-Al2O3上加氢脱硫和加氢脱氮反应的相互影响

在固定床高压微反装置上考察了预硫化型NiMoS/γ-Al2O3催化剂上二苯并噻吩（DBT）加氢脱硫（HDS）反应和吲哚加氢脱氮（HDN）反应之间的相互影响。结果表明,吲哚对DBT的加氢脱硫反应具有抑制作用,其中对加氢路径（HYD）比对氢解路径（DDS）的抑制作用强,温度升高后,吲哚的抑制作用减弱。吲哚对DBT加氢脱硫反应的抑制作用源于吲哚及其HDN反应的中间产物在活性位上的竞争吸附。DBT和原位生成的H2S促进了催化剂表面硫阴离子空穴（CUS）向B酸位的转化,从而提高1,2-二氢吲哚（HIN）分子中C(sp3)—N键的断裂能力,使得吲哚的转化率和产物中邻乙基苯胺（OEA）的相对含量增大。HDN活性相的形成虽然需要硫原子的参与,但是活性相的保持并不需要大量的硫原子,较高含量硫化物存在时加氢活性位减少,不利于脱氮反应。     

Enantioselectivity of epoxide hydrolase catalysed oxirane ring opening: a 3D QSAR study

A 3D QSAR analysis (quantitative structure activity relationships) of a set of 2,2-disubstituted epoxides, substrates for epoxide hydrolases originating from four different organisms, was conducted by CoMFA (comparative molecular field analysis) and CoMSIA (comparative molecular similarity indices analysis), with respect to the enantioselective ring opening to the corresponding vicinal diol. Structural variations of the substrates include alkyl chains of different lengths, unsaturated moieties ((E)- and (Z)-alkenyl, alkinyl, aryl) and electronegative groups (ether oxygens, halogen atoms) at different locations within the 2-substituent group. Generally, all four organisms, namely Rhodococcus ruber NCIMB 11216, Rhodococcus ruber DSM 43338, Rhodococcus ruber DSM 44540 and Rhodococcus ruber DSM 44539, preferentially react with the (S)-enantiomer of the epoxide. Enantioselectivities (enantiomeric ratio, lnE values) show a rather large variation, ranging from almost no (lnE<1) to nearly complete selectivity (lnE>5.3). In addition, the response of the epoxide hydrolases stemming from the four organisms towards structural modifications of the substrate is different. Models for the enantioselectivity (enantiomeric ratio, ln E values) obtained by CoMFA and CoMSIA are of different but reasonable predictive power, e.g., q² _CV=0.701 and r²=0.937 for the CoMFA model of Rhodococcus ruber DSM 43338. Enantiomeric ratios for the test molecules can be well predicted. Plots of steric and electrostatic CoMFA (CoMSIA) fields allow conclusions to be drawn for the choice of the most suitable organism for a specific type of substrate.     

Biocatalytic Synthesis of Highly Enantiopure 1,4-Benzodioxane-2-carboxylic Acid and Amide

Catalyzed by Rhodococcus erythropolis AJ270, a nitrile hydratase and amidase containing microbial whole-cell catalyst, at 10 ℃ and with the use of methanol as a co-solvent, nitrile and amide biotransformations produce 2S-1,4-benzodioxane-2-carboxamide and 2R-1,4-benzodioxane-2-carboxylic acid in high yields with excellent enantioselectivity.     

Process Optimisation Studies and Aminonitrile Substrate Evaluation of Rhodococcus erythropolis SET1, A Nitrile Hydrolyzing Bacterium

A comprehensive series of optimization studies including pH, solvent and temperature were completed on the nitrile hydrolyzing Rhodococcus erythropolis bacterium SET1 with the substrate 3-hydroxybutyronitrile. These identified temperature of 25 °C and pH of 7 as the best conditions to retain enantioselectivity and activity. The effect of the addition of organic solvents to the biotransformation mixture was also determined. The results of the study suggested that SET1 is suitable for use in selected organo-aqueous media at specific ratios only. The functional group tolerance of the isolate with unprotected and protected β-aminonitriles, structural analogues of β-hydroxynitriles was also investigated with disappointingly poor isolated yields and selectivity obtained. The isolate was further evaluated with the α- aminonitrile phenylglycinonitrile generating acid in excellent yield and ee (>99 % (S) – isomer and 50 % yield). A series of pH studies with this substrate indicated pH 7 to be the optimum pH to avoid product and substrate degradation.