Study on the hydrogenation reaction and coking behavior in Golmud residue hydrogenation
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摘要: 选用超低沥青质含量的格尔木渣油（沥青质质量分数：0.32%）作为加氢原料，考察反应条件对加氢反应样品组分性质、胶体稳定性参数（CSP）、生焦性能的影响。结果表明，随着加氢反应温度的升高和反应时间的延长，沥青质和饱和分的含量增加，胶质和芳香分的含量减少；胶体稳定性参数降低，生焦率不断增加；胶质与沥青质的缩合度增加，芳碳率fA不断增大；金属与杂原子在加氢过程中不断得到脱除，V比Ni更容易脱除、S比N更容易脱除；催化剂表面形成了类似石墨有序结构的炭基物质，使得催化剂的孔结构参数不断减小。在所研究的反应中，当反应温度和时间分别为420℃和5 h时，催化剂的孔结构损害最为严重，出现了较大的微孔分布。Abstract: The ultra-low asphaltene content of Golmud residue (asphaltene content:0.32%) was used as the hydrogenation feedstock. The effect of reaction conditions on the composition properties, colloidal stability parameters (CSP) and coke performance of the hydrogenation reaction samples was investigated. The results show that with the increase in hydrogenation temperature and reaction time, the content of asphaltene and saturated fraction increases, the content of colloid and aromatic fraction as well as the colloid stability parameter decrease, and the coke yield increases continuously. Meanwhile, as the degree of condensation of asphaltenes increases, the aromatic carbon ratio fA increases continuously, the metals and heteroatoms are continuously removed during hydrogenation, V is easier to remove than Ni, and S is easier to remove than N. On the catalyst surface is a carbon-based substance similar to the graphite with ordered structure formed, leading to the continuous reduction in pore structure parameters of the catalyst. When the reaction temperature and time are 420 ℃ and 5 h, respectively, the pore structure damage of the catalyst is the most serious, and a dominant distribution of micropore appears.
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Key words:
- residue hydrogenation /
- colloidal stability /
- catalyst /
- coke yield
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图 1 不同温度加氢反应后组分组成的变化
Figure 1 Variation of the fraction composition after the reaction at different temperatures
图 2 不同时间加氢反应后组分组成变化
Figure 2 Variation of the fraction composition after the reaction at different times
图 3 胶体稳定性参数与生焦率关系
Figure 3 Relationship of colloidal stability parameters and coke yield
图 8 不同反应温度催化剂的XRD谱图
Figure 8 XRD patterns of the coked catalysts at different reaction temperatures
图 9 新鲜催化剂和不同反应时间催化剂的XRD谱图
Figure 9 XRD patterns of coked catalysts at different reaction times
图 10 温度对催化剂结构参数影响
Figure 10 Effect of reaction temperature on the catalyst structure parameters
图 11 时间对催化剂结构参数影响
Figure 11 Effect of reaction time on the catalyst structure parameters
图 12 不同反应温度下催化剂的孔径分布
Figure 12 Pore size distribution of catalysts at different reaction temperatures
图 13 不同反应时间下催化剂的孔径分布
Figure 13 Pore size distribution of catalysts at different reaction times
表 1 GM渣油的基本物性
Table 1 Basic properties of GM residue
Analysis item Value Analysis item Value Density(20 ℃) ρ/(g·cm-3) 0.91 SARA Kinematic viscosity(50 ℃)η/(Pa·s) 0.46 Saturate w/% 43.43 Carbon residue w/% 6.67 Aromatic w/% 28.00 CSP* /(g·g-1) 14.2 Resin w/% 28.25 Molecular weight /(g·mol-1) 1302 C7-asphaltene w/% 0.32 *: mass fraction conductivity method 
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表 2 实验试剂一览表
Table 2 List of experimental reagents
Reagent Specification Manufacturer N-heptane Analytic reagent Sinopharm chemical reagent Co. Ltd Methylbenzene Analytic reagent Sinopharm chemical reagent Co. Ltd Neutral alumina Chromatography Shanghai 54 chemical reagent factory Absolute ethyl alcohol Analytic reagent Sinopharm chemical reagent Co. Ltd Light petroleum Analytic reagent Sinopharm chemical reagent Co. Ltd
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表 3 实验仪器一览表
Table 3 List of experimental equipments
Instrument name Type Manufacturer High temperature high pressure reactor CQF0.15 Dalian lean reactor Co. LTD TGA STA408PC NETZSCH NMR Avance 500 Bruker CHSN elemental analyzer VARIOEL Ⅲ German company elementar AAS ControAA700 Jena analytical instruments ag Physical adsorption apparatus ASAP2020M Micrometrics Inc LCR measurement instrument 4263B Agilent company
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表 4 催化剂的基本性质
Table 4 Properties of catalyst
Analysis item Pre-cure number Post-cure number Surface area A/(m2·g-1) 128.08 80.58 Pore size d/nm 19.33 21.07 Pore volume v/(cm3·g-1) 0.63 0.26 Carrier γ-Al2O3 γ-Al2O3 Active component MoO3, NiO MoS2, Ni3S2
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表 5 温度对反应后沥青质平均结构的影响
Table 5 Effect of reaction temperature on the asphaltene structure
Sample fA σ HAU/CA fN fP RA RN RT CA* n BI GM-asp 0.42 0.50 0.50 0.10 0.47 20.01 5.14 25.15 25.47 2.51 0.25 360 ℃-asp 0.42 0.46 0.82 0.04 0.63 34.87 3.88 30.99 44.42 11.70 0.49 380 ℃-asp 0.48 0.16 0.44 0.01 0.52 33.16 0.38 33.53 32.39 3.19 0.46 400 ℃-asp 0.56 0.38 0.25 0.17 0.27 71.45 22.10 33.54 102.29 2.13 0.29 420 ℃-asp 0.64 0.28 0.43 0.07 0.30 35.55 3.78 39.33 34.11 3.24 0.38
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表 6 时间对反应后沥青质平均结构的影响
Table 6 Effect of reaction time on the asphaltene structure
Sample fA σ HAU/CA fN fP RA RN RT CA* n BI GM-asp 0.42 0.50 0.50 0.10 0.47 20.01 5.14 25.15 25.47 2.51 0.25 2 h-asp 0.53 0.21 0.55 0.04 0.52 30.66 2.69 27.96 20.56 4.67 0.15 3 h-asp 0.56 0.39 0.36 0.12 0.32 46.81 10.60 57.41 48.04 3.01 0.24 4 h-asp 0.56 0.38 0.25 0.17 0.27 57.59 18.33 75.93 102.29 1.73 0.29 5 h-asp 0.58 0.10 0.17 0.16 0.31 58.10 18.45 76.56 218.57 1.00 0.35
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表 7 温度对反应后胶质平均结构的影响
Table 7 Effect of reaction temperature on the resin structure
Sample fA σ HAU/CA fN fP RA RN RT CA* n BI GM-res 0.31 0.55 0.77 0.06 0.64 9.56 2.09 11.66 10.69 3.06 0.20 360 ℃-res 0.28 0.67 0.77 0.13 0.60 5.55 3.13 8.68 10.63 1.94 0.34 380 ℃-res 0.28 0.68 0.73 0.14 0.58 5.05 3.26 8.32 11.81 1.62 0.26 400 ℃-res 0.37 0.49 0.67 0.12 0.51 5.88 2.25 8.13 14.16 1.53 0.21 420 ℃-res 0.41 0.46 0.70 0.11 0.48 5.72 1.92 7.64 12.96 1.63 0.31
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表 8 时间对反应后胶质平均结构的影响
Table 8 Effect of reaction time on the resin structure
Sample fA σ HAU/CA fN fP RA RN RT CA* n BI GM-res 0.31 0.55 0.77 0.06 0.64 9.56 2.09 11.66 10.69 3.06 0.20 2 h-res 0.36 0.50 0.61 0.09 0.56 9.71 2.74 12.45 16.68 1.98 0.20 3 h-res 0.36 0.52 0.67 0.11 0.53 7.13 2.47 9.60 14.11 1.80 0.18 4 h-res 0.37 0.53 0.67 0.14 0.50 5.19 2.49 7.67 13.76 1.42 0.18 5 h-res 0.38 0.50 0.57 0.12 0.52 8.23 3.10 11.33 19.55 1.37 0.21
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