Research for structure and composition of coke on spent commercial residue hydrotreating catalysts along HDM bed
-
摘要: 针对取自中石油某装置不同床层轴向位置的工业固定床渣油加氢脱金属废催化剂，采用元素分析、热重分析、X射线光电子能谱、傅里叶变换红外光谱和核磁共振碳谱等，研究了催化剂上沉积焦炭的结构组成特征参数。结果表明，不同轴向位置废催化剂上的焦炭具有某些共同特征，如相同的碳类型和官能团等，但其结构和组成各不相同。模拟建立了基于各种表征结果的焦炭结构组成模型，并利用可计算核磁共振波谱化学位移和预测核磁共振谱图的gNMR软件对所建立焦炭模型的精确性进行了验证，表明模型与实验结果具有很好的一致性。Abstract: The spent residue hydrotreating catalysts were taken out from the different HDM bed axial position of a fixed-bed residue hydrotreating reactor of Petro-China. The coke on spent catalysts were studied by the technologies such as EA, TG, XPS, FT-IR and 13C NMR to get the structure characteristics and parameters. The results showed that the coke on spent residue hydrotreating catalysts located on different beds positions share some characteristics such as the kind of coke, the functional group, but the structure and composition were different from each other. Based on the result of each characterization technique, chemical structure models of coke were established. In order to ensure the accuracy of the structures, a software called gNMR helped to calculate the chemical shifts and predict the NMR spectra of the structure models. The model structures can be corrected to match the experimental results through comparing experimental spectra and the predicted ones.
-
Key words:
- residue hydrotreating catalysts /
- coke /
- 13C NMR /
- chemical structure model /
- gNMR
-
Figure 2 C 1s XPS and peak separation and fitting of catalysts
(a): HDM 1; (b): HDM 2; (c): HDM 3; (d): fitting of HDM 2
Table 1 Basic information of catalysts
Catalyst No. Reactor No. Catalyst species Sampling location in bed HDM 1 1 Ch-B top HDM 2 1 Ch-B middle HDM 3 1 Ch-B bottom 
下载: 导出CSV
Table 2 Elemental contents of spent catalysts
No. Catalyst species Content w/% nH/nC H C N S HDM 1 Ch-B 0.89 10.40 0.21 1.66 1.02 HDM 2 Ch-B 1.39 19.42 0.35 6.73 0.85 HDM 3 Ch-B 1.04 10.05 0.20 2.95 1.23
下载: 导出CSV
Table 3 Attribution and distribution of different carbon in catalysts
HDM 1 HDM 2 HDM 3 energy attribution AT/% energy attribution AT/% energy attribution AT/% 284.56 C-C 53.55 284.52 C-C 60.13 284.58 C-C 56.66 285.16 C-H 34.28 285.06 C-H 21.21 285.10 C-H 25.54 286.10 C-N 5.14 285.85 C-N 4.05 286.14 C-N 4.66 287.00 C-S 7.03 260.08 C-S 14.59 286.55 C-S 13.15
下载: 导出CSV
Table 4 Functional groups of coke deposit on the spent catalysts[9]
FT-IR peak wavenumber σ/cm-1 Functional group Mode of vibration HDM 1 HDM 2 HDM 3 577 590 571 C-S ν 744 766 740 -CH2- γ 816 810 816 R-Ar-H δ 974 1130 980 H-C=C-H δ 1124 1080 1120 C-N ν 1628 1600 1620 Ar ν 2940 2930 2930 C-H ν 3334 3360 3400 N-H ν
下载: 导出CSV
-
[1] SUN Y D, GU Z J, YANG C H. Influence of catalysts on product distribution of residue hydrotreating[J]. J Petrochem Univ, 2013, 26(30):9-12. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syhggdxx201303003 [2] XU C M, YANG C H. Petroleum Refining Engineering[M]. 4th ed. Beijing:Petroleum Industry Press, 2009. [3] GUO C L, FANG X C, JIA L M, LIU Q J, ZHANG X W, ZHAO X D. Investigation on coking deactivation behavior of molecular sieve catalysts[J]. Ind Catal, 2011, 19(12):15-20. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=gych201112003 [4] XUN J K, ZHOU W, WANG J H, LI Z J, MA J X. Characterization and analysis of carbon deposited during the dry reforming of methane over No/La2O3/Al2O3 catalysts[J]. Chin J Catal, 2009, 30(11):1076-1084. doi: 10.1016/S1872-2067(08)60139-4 [5] ZHANG H C, MA B, LI J B, LIU S Q, GENG J Y, WANG J F. Analysis of coke on spent catalysts used for residue hydrotreating process[J]. Contemp Chem Ind, 2008, 37(3):277-282. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=ddhg200803016 [6] WANG X. Study on structure and composition of coke on spent catalysts of commercial fixed-bed residue hydrotreating unit[D]. Qingdao: China University of Petroleum, 2014. [7] CHANG H Z, WANG C G, ZENG F G, LI J, LI W Y, XIE K C. XPS comparative analysis of coal macerals with different reducibility[J]. J Fuel Chem Technol, 2006, 34(4):389-394. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200604002 [8] MENG G, KONG D J, QI X L, XU Z Q. Carbon deposition on a toluene disproportionation and transalkylation catalyst[J]. Acta Phys-Chim Sin, 2010, 26(11):3017-3022. http://en.cnki.com.cn/Article_en/CJFDTOTAL-WLHX201011023.htm [9] ZHENG Q R, ZENG F G, ZANG S T. FT-IR study on structure evolution of middle maturate coals[J]. J China Coal Soc, 2011, 36(3):481-486. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=QK201100257156 [10] ZHU N, WANG Y, CHEN F Q, ZHAN X L. Application of In situ FT-IR to deactivation by coke deposition[J]. Prog Chem, 2008, 20(10):1447-1452. [11] YANG X, TIAN H P, WANG S H. Characterization of coke on spent catalytic cracking catalysts by integrated techniques[J]. Acta Pet Sin (Pet Proc Sect), 2011, 27(2):198-206. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syxb-syjg201102008 [12] SUN Q L, LI W, LI D T, CHEN H K, LI B Q, BAI X F, LI W H. Relationship between structure characteristics and thermal conversion property of Shenmu maceral concentrates[J]. J Fuel Chem Technol, 2003, 31(2):97-102. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200302001 [13] HE Y G, HE Y F. Characterization of coke precursor deposited on the surface of solid acid alkylation catalysts[J]. Chin J Catal, 2000, 21(2):175-178. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=cuihuaxb200002022 [14] ANDRE H, ANTHONY S, ABDULAZEM M, AWATERF A. Initial coke deposition on hydrotreating catalysts. PartⅡ. Structure elucidation of initial coke on hydrodematallation catalysts[J]. Fuel, 2005, 84(2/3):259-269. https://www.sciencedirect.com/science/article/pii/S0016236104002340 [15] MEI Y F, ZHAO X, SUN W F, TANG J, QIAO A X. Spectral analysis of coal tar from Xiaohuangshan region[J]. Chin J Magn Reson, 2011, 28(3):339-348. http://en.cnki.com.cn/Article_en/CJFDTOTAL-PPXZ201103007.htm [16] XIANG J H, ZENG F G, LI B, ZHANG L, LI M F, LIANG H Z. Construction of macromolecular structural model of anthracite from Chengzhuang coal mine and its molecular simulation[J]. J Fuel Chem Technol, 2013, 41(4):391-399. doi: 10.1016/S1872-5813(13)60022-5 [17] JIA J B, ZENG F G, SUN B L. Construction and modification of macromolecular structure model for vitrinite from Shendong 2-2 coal[J]. J Fuel Chem Technol, 2011, 39(9):652-657. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb201109003 [18] XIANG J H, ZENG F G, LIANG H Z, SUN B L, ZHANG L, LI M F, JIA J B. Model construction of the macromolecular structure of Yanzhou coal and its molecular simulation[J]. J Fuel Chem Technol, 2011, 39(7):481-488. doi: 10.1016/S1872-5813(11)60031-5 -
点击查看大图
图(7) / 表(5)
计量
- 文章访问数: 88
- HTML全文浏览量: 40
- PDF下载量: 14
- 被引次数: 0
