Preparation and deep adsorption denitrification from diesel oil of heteroatoms mesoporous molecular sieve Co-MCM-41
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摘要: 以硝酸钴为钴源, 采用水热法合成了MCM-41和不同Co含量的Co-MCM-41分子筛, 并利用XRD、FT-IR和低温N2吸附-脱附等方法对合成的分子筛进行表征。当加入的Co/Si物质的量比达到0.1时, 依然能够成功合成具有规整有序的介孔结构的Co-MCM-41。MCM-41和Co-MCM-41静态吸附脱除0#柴油中碱氮的实验结果表明, Co/Si物质的量比为0.06的Co-MCM-41(2) 分子筛的吸附容量最大, 达到5.324 mg (N)/g分子筛, 明显高于MCM-41分子筛的吸附容量2.532 mg (N)/g, 说明Co进入MCM-41分子筛骨架后显著提高了分子筛的吸附脱除碱氮能力。当加入的Co/Si物质的量比大于0.06时, 分子筛吸附脱除柴油中碱氮的能力反而下降, 这是由于加入过多Co会使其以Co3O4形式高度分散在分子筛孔道中, 堵塞了吸附活性位, 使其无法与碱性氮化物接触造成吸附脱氮能力下降。动态吸附脱除0#柴油中碱性氮化物的结果表明, 每克Co-MCM-41(2) 分子筛可将35 mL柴油的碱氮从147.54 μg/g吸附脱除到10 μg/g以下, 吸附容量为4.2 mg (N)/g (吸附剂), 由于动态吸附的接触时间较短使MCM-41失去了吸附脱氮能力, 说明Co-MCM-41(2) 对柴油中的碱氮具有较好的选择性。Abstract: The mesoporous molecular sieves MCM-41 and Co-MCM-41 containing different cobalt contents were prepared by hydrothermal synthesis method with cobalt nitrate as cobalt source and characterized using X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR) and nitrogen adsorption. The characterization results indicate that the well-ordered mesostructure was obtained even when the Co/Si mol ratio was 0.1 and Co has been introduced into the framework of MCM-41. Adsorption removal of basic nitrogen compounds from 0# diesel oil was studied by static stirring method using MCM-41 and Co-MCM-41. One gram of Co-MCM-41(2) could adsorb 5.324 mg nitrogen from diesel oil while MCM-41 could adsorb 2.532 mg, indicating that the adsorptive denitrification of Co-MCM-41(2) has been enhanced pronouncedly. But the adsorptive denitrification capacity of Co-MCM-41(2) decreased when the Co/Si exceeded 0.06, which could be ascribed to the addition of exceeded Co into the frameworks of MCM-41. The Co was well dispersed in the channel of Co-MCM-41 as Co3O4 and blocked the adsorption active sites which hindered the adsorption between the nitrogen compounds and active sites and depressed the adsorptive denitrification capacity. The results of adsorptive denitrification from diesel oil using dynamic adsorption method showed that for a breakthrough point of 10 μg/g, the breakthrough volume and breakthrough capacity of Co-MCM-41(2) at ambient conditions are 35 mL/g-adsorbent and 4.2 mg-nitrogen/g adsorbent, respectively. For MCM-41, both of the two data were almost zero, indicating that MCM-41 almost lost all the adsorptive denitrification capacity due to the shorter contact time and implying that Co-MCM-41(2) had better selectivity on basic nitrogen compounds in 0# diesel oil.
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Key words:
- Co-MCM-41 /
- synthesis /
- chatacterization /
- diesel oil /
- denitrification
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图 1 MCM-41及不同Co加入量Co-MCM-41的小角XRD谱图
Figure 1 Small angle XRD patterns of MCM-41 and Co-MCM-41
图 4 MCM-41及Co-MCM-41的吸附等温线和BJH孔径分布图
Figure 4 Adsorption isotherms and pore size distribution of MCM-41 and Co-MCM-41
a: MCM-41; b: Co-MCM-41(1)[Co/Si=0.04]; c: Co-MCM-41(2)[Co/Si=0.06]; d: Co-MCM-41(3)[Co/Si=0.08]; e: Co-MCM-41(4)[Co/Si=0.1]
图 5 MCM-41和Co-MCM-41吸附脱除柴油中碱氮的剩余含量、碱氮脱除率及氮吸附容量
Figure 5 Absorption capacity, basic nitrogen removal rate and remained basic nitrogen content of 0# diesel oil treated by MCM-41 or Co-MCM-41 (static stirring method; ambient conditions; 25 mL 0# diesel oil was treated with 0.5 g molecular sieve)
: remained basic nitrogen content; : adsorption capacity; : removal rate
图 6 MCM-41及Co-MCM-41(2) 吸附脱除0#柴油中碱性氮化物的穿透曲线
Figure 6 Breakthrough curves of the basic nitrogen of 0# diesel oil treated by MCM-41 or Co-MCM-41(2)
(ambient conditions; liquid hourly space velocity: 3.0 h-1)
表 1 MCM-41和Co-MCM-41的孔结构参数
Table 1 Pore structure parameters of MCM-41 and Co-MCM-41 samples
Initiator Value MCM-41 Co-MCM-41(1) Co-MCM-41(2) Co-MCM-41(3) Co-MCM-41(4) 2θ/(°)(100) 2.308 2 2.305 0 2.180 4 2.164 8 2.220 3 d100/nm 3.823 0 3.828 3 4.047 0 4.076 2 3.974 3 a0/nm 4.414 5 4.420 6 4.673 2 4.706 9 4.589 2 Total pore volume v/(cm3·g-1) 0.887 5 0.785 3 0.787 2 0.838 9 0.745 2 As, BET/(m2·g-1) 983.04 836.44 868.20 889.53 812.55 Average pore diameter d/nm 3.11 3.21 3.22 3.27 3.16 note：$2{d_{100}}\sin \theta = n\lambda ,{\alpha _0} = \frac{{2{d_{100}}}}{{\sqrt 3 }}$ 
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