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摘要: 利用蒸发诱导法制备了HCl改性的MoO3/Al-SBA-15系列催化剂,采用XRD、BET、TEM、NH3-TPD进行了表征。结果表明,改性后的催化剂保留着SBA-15的六角结构,孔道结构保持有序状态,改性后样品的孔径8 nm左右,壁厚4 nm左右,属于典型的介孔分子筛,活性组分在载体中分布良好。以预加氢后的中低温煤焦油为原料,采用固定床加氢裂化对催化剂进行了评价,结果表明,经过预硫化之后,负载了MoO3的Al-SBA-15具有良好的加氢裂化活性,MoO3负载量14.9%的情况下,65-145℃石脑油和145-280℃航煤馏分两种较轻组分合计收率为79.21%,其中,石脑油具备很高的芳潜值,最高可达72.4,是优良的重整制取芳烃的原料,裂化后的尾油BMCI值过高,不适宜作为裂化乙烯的原料。Abstract: A series MoO3/Al-SBA-15 catalysts modified by HCl were prepared by evaporation induction method. The catalysts were characterized by XRD, BET, TEM and NH3-TPD. The results showed that the modification of the catalyst retained the hexagonal structure of SBA-15 with ordered pore structure. The pore size of the modified samples was about 8 nm with wall thickness of about 4 nm. The catalysts were typical mesoporous molecular sieves over which the active components were well distributed. The Al-SBA-15 loaded with MoO3 had good hydrocracking activity after prevulcanization. Under the condition of 14.9% MoO3 loading, the total yield of naphtha and aviation kerosene fraction was 79.21%. The naphtha had the highest aromatic potential of 72.4, which was an excellent feedstock for reforming to produce aromatics. The high BMCI value of the cracked tail oil was not suitable for ethylene production by cracking.
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Key words:
- coal tar /
- SBA-15 /
- hydrocracking /
- aromatic potential
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表 1 MoO3/Al-SBA-15样品一览表
Table 1 Elements contents of MoO3/Al-SBA-15 samples
Sample Si/Mo (mol ratio) Al/Mo (mol ratio) MoO3 w/% Mow/% 1# - - 0 0 2# 43.5 2.18 5.1 3.4 3# 22.4 1.12 9.9 6.5 4# 14.9 0.75 14.9 9.8 5# 11.0 0.55 20.1 13.3 表 2 煤焦油预加氢油性质
Table 2 Properties of the coal tar after pre-hydrogenation
Elemental analysis ρ20c/ (kg· m-3) Hydrocarbon group composition w/% Hw/% Cw/% Oaw/% Sb/(mg·kg-1) Nb/(mg·kg-1) alkane naphthene aromatics polar fraction monocyclic bicyclic tricyclic 10.73 88.32 0.86 349 557 0.9751 24.9 28.68 22.83 16.29 5.15 2.13 Fraction distribution v/% IBP 5 10 20 30 40 50 60 70 80 90 99.5 t/℃ 97.2 158.4 181.3 241.2 270.6 283.6 318.6 328.3 350.1 370.2 388.8 423.1 a: by difference; b: detected by micro sulfur and nitrogen analyzer; c: density at 20 ℃ 表 3 催化剂样品的孔结构参数
Table 3 Physico-chemical properties of the catalysts
Sample MoO3w/% SBETa/(m2·g-1) vPb/(cm3·g-1) d cBJH/nm 1# 0 854 1.17 7.7 2# 5.1 434 0.74 6.1 3# 9.9 335 0.69 5.9 4# 14.9 295 0.64 5.8 5# 20.1 99 0.28 4.7 a:specific surface area determined by Brunauer-Emmett-Teller (BET) method;b:total pore volume recorded at p/p0 = 0.99;c:pore diameter calculated by Barrett-Joyner-Halenda (BJH) method 表 4 加氢裂化物料平衡
Table 4 Mass balance of hydro-cracking processing
Sample 1# 2# 3# 4# 5# Input w/% Coal tar 100 100 100 100 100 DMDS 0.25 0.25 0.25 0.25 0.25 H2 4.14 5.07 5.63 5.92 5.31 Total 104.39 105.32 105.88 106.17 105.56 Output w/% H2S 0.20 0.22 0.22 0.22 0.22 NH3 0.05 0.06 0.07 0.07 0.06 CO 0.08 0.07 0.04 0.03 0.04 CO2 0.05 0.03 0.03 0.02 0.03 <65℃* 7.49 4.53 4.71 5.07 4.25 65-145℃ 26.23 40.12 45.28 47.42 40.33 145-280 ℃ 20.72 25.61 29.59 31.89 33.8 280-370 ℃ 30.17 20.25 15.89 12.88 14.67 >370 ℃ 18.31 13.62 9.17 7.67 11.26 H2O 0.73 0.81 0.88 0.90 0.90 Total 104.39 105.32 105.88 106.17 105.56 *:<65 ℃: C1-5 表 5 加氢裂化产物性质
Table 5 Properties of hydrocracking products
Sample 1# 2# 3# 4# 5# 65-145 ℃ ρ20c/(kg·m-3) 777.9 765.8 758.3 749.4 750.1 H/C 1.98 2.04 2.07 2.11 2.09 Aromatic potential 69.4 70.6 72.4 71.1 68.7 145-280 ℃ ρ20c/(kg·m-3) 853.2 847.1 843.3 838.5 841.1 H/C 1.94 1.96 1.97 1.98 2.02 Freezing point /℃ <-60 <-60 <-60 <-60 <-60 280-370 ℃ ρ20c/(kg·m-3) 907.6 905.5 903.2 899.6 901.1 H/C 1.71 1.77 1.79 1.83 1.82 Condensation point -33 -39 -42 -43 -46 Cetane index 41 39 38 37 39 >370 ℃ ρ20c/(kg·m-3) 972.3 968.6 965.4 963.8 964.1 H/C 1.39 1.40 1.43 1.42 1.44 BMCI 74.4 70.1 68.6 65.7 69.3 -
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