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题名	吸附-微生物耦合深度脱硫工艺研究
作者	唐煌
学位类别	博士
答辩日期	2012-05-18
授予单位	中国科学院研究生院
导师	邢建民
关键词	π络合吸附 吸附剂再生 定向培育 深度脱硫 耦合工艺
其他题名	Studies on Integration of Adsorption and Biodesulfurization for Deep Desulfurization Technology
学位专业	生物化工
中文摘要	燃料油深度脱硫(S<10 ppm)工艺的开发是石油化工的重要研究方向。吸附—微生物耦合脱硫结合了吸附脱硫的高速率和微生物脱硫的高选择性，是一种高效的清洁燃料油品生产新工艺。本论文在实验室已有的研究基础上，提出了“吸附脱硫——洗脱再生——生物回收”的三步脱硫工艺，从吸附剂的合成和再生、吸附热力学、生物催化剂的活性优化及其大规模制备、耦合深度脱硫工艺的设计和应用等方面开展了研究。 首先，通过优化吸附剂的合成条件和过渡金属离子改性方法，得到了高效的脱硫吸附剂——金属负载型介孔硅铝酸盐(MAS)。离子交换法对吸附脱硫的改性效果不仅与吸附剂的载体类型有关，也与过渡金属离子的种类有关。为了使吸附剂具备重复使用的能力，采取溶剂洗脱的方法对吸附剂进行再生。通过比较不同溶剂的再生效率，及其对微生物脱硫活性的影响，选择了3%的异丙醇水溶液作为再生液。在液体流速为0.6 mL/min的条件下进行再生之后，吸附剂的脱硫能力得到完全恢复。 其次，为了提高金属负载型吸附剂的脱硫能力，研究了吸附的热力学性质。通过考察吸附剂的平衡吸附情况，用线性回归法对数据进行了分析，计算结果表明π络合吸附剂对硫化物的吸附与Langmuir吸附模型是完全吻合的。根据理论假设，进一步考察了吸附温度和过渡金属对吸附脱硫的影响。吸附温度从30 ℃提高到110 ℃时，Ag-MAS对二苯并噻吩(DBT)的饱和吸附量从0.030 mmol/g提高到了0.071 mmol/g；单位质量吸附剂生产的清洁油(S<10 ppm)体积从7 mL/g提高到了21 mL/g。通过改变预处理过程中的氢气还原条件，调节吸附剂中过渡金属元素的价态，Ni-Y和Ni-MAS吸附剂中的Ni2+全部被还原成Ni0之后，饱和吸附量分别提高了14.1%和65.2%，吸附选择性分别提高了41.4%和25.7%。 再次，在生物催化剂方面，通过定向培育的方法，使脱硫菌R-8获得了很好的汽柴油耐受性和较大的脱硫底物范围。通过高密度培养和改进固定化方法，实现了生物催化剂的大规模制备。在油水比为5:1的条件，固定化R-8细胞在模拟油中对噻吩(T)的脱除速率达到了33.3 μmol S/g DCW/ h，对DBT的脱除速率为20.0 μmol S/g DCW/ h，重复脱硫次数达17次以上，使用寿命达到450 h以上。对汽油的脱硫速率达到了16.2 μmol S/g DCW/ h，重复脱硫次数为12次，对加氢柴油的脱硫速率达到了13.1 μmol S/g DCW/ h，重复脱硫次数为16次，相比驯化之前都有大幅度的提高。 最后，设计和搭建了深度脱硫的装置，优化了耦合工艺，并考察了其对模拟油和柴油的深度脱硫效果。以1.0 g吸附剂处理60 mL的油(初始硫含量为100 ppm)，最终模拟油的回收体积为54 mL，硫含量为5.12 ppm；柴油的回收体积为51 mL，硫含量为8.92 ppm。根据实验得到的数据，对耦合深度脱硫工艺进行了初步经济性分析，与目前加氢精炼工艺的成本相比，具有较好的竞争力和应用前景。
英文摘要	Deep desulfurization (S<10 ppm) technology is an important direction of petro- chemistry. The integration of adsorption desulfurization and biodesulfurization, which combines the high speed of adsorption and the high selectivity of biodesulfurization, is a new efficient technology in the production of clean fuels. Based on the previous work of our laboratory, a three-step process of “Adsorption desulfurization - Regeneration by elution - Biodesulfurization for recycle” was projected. In this thesis, the synthesis and regeneration of adsorbents, the thermodynamics of adsorption, the improvement and large-scale preparation of biocatalyst, the design and application of integration process for deep desulfurization were studied. Firstly, the synthesis conditions and metal modified methods were optimized, and high efficient desulfurization adsorbents, the metal loaded Mesoporous Aluminosilicate (MAS), were obtained. The effect of ion-exchange modification on desulfurization was related to not only the type of adsorbent carrier, but also the type of transition metal ions. In order to be reusable, the adsorbents were regenerated through solvent elution method. By comparing ther regeneration rate and the influence on biodesulfurization activity of different types of solvents, 3% isopropyl alcohol of aqueous solution was finally selected as the regeneration liquid. The desulfurization activity of adsorbents was totally recovered under the flow rate of regeneration liquid is 0.6 mL/min. Secondly，in order to improve the desulfurization ability of metal loaded MAS, the thermodynamics of adsorption was studied. The equilibrium adsorption data were analyzed by linear regression method, and the results showed that the adsorption of sulfur compounds by pi-complexation adsorbents was completely consistent with the Langmuir adsorption model. According to the theoretical assumptions, the effects of adsorption temperature and the transition metal on desulfurization activity were further investigated. When the adsorption temperature was raised from 30 ℃ to 110 ℃, the saturation adsorptive capacity of Ag-MAS for DBT was increased from 0.030 mmol/g to 0.071 mmol/g, and the volume of clean oil was increased from 7 mL/g to 21 mL/g. The valence state of the metal elements was adjusted by changing the hydrogen reduction conditions in the pretreatment process. When all Ni2+ ions in Ni-Y and Ni-MAS adsorbent were reduced intoNi0, the saturated adsorptive capacity increased by 14.1% and 65.2%, and the selectivity increased by 41.4% and 25.7%, respectively. Thirdly, in the biocatalyst part, R-8 cells with a good tolerance and a wide substrate range in gasoline and diesel were obtained by oriented cultivation. Through high density cultivation and improved immobilization method, the large scale preparation of biocatalyst was achieved. Under the condition of oil/water ratio is 5:1, the removal rate of T and DBT by immobilized R-8 cells were 33.3 μmol S/g DCW/ h and 20.0 μmol S/g DCW/ h respectively. The immobilized R-8 cells were used for 17 times of repeated desulfurization, and lasted 450 hours in model oil. The desulfurization rate and repeated times of R-8 cells in gasoline was 16.2 μmol S/g DCW/h and 12, respectively. While for hydro-treated diesel, those of R-8 cells were 13.1 μmol S/g DCW/h and 16 times, respectively. Finally, an integrated system for deep desulfurization was designed and built up, then the integrated process was optimized and applied in deep desulfurization of model oil and diesel. 60 mL oil (initial sulfur content is 100 ppm) was treated by 1.0 g adsorbents, the final volume of model oil was 54 mL and the sulfur content was 5.1 ppm, while those of diesel was 51 mL and 8.92 ppm, respectively. The economical efficiency of the integrated technology for deep desulfurization was analyzed, which showed a good competitiveness and prospect in application by comparing with the present hydrogenation refining.
语种	中文
公开日期	2013-09-25
内容类型	学位论文
源URL	[http://ir.ipe.ac.cn/handle/122111/1863]
专题	过程工程研究所_研究所（批量导入）
推荐引用方式 GB/T 7714	唐煌. 吸附-微生物耦合深度脱硫工艺研究[D]. 中国科学院研究生院. 2012.

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