THFS-2硫化型重整预加氢催化剂的工业应用
收稿日期: 2023-12-08
网络出版日期: 2024-05-15
Industrial application of THFS-2 sulfurized reforming prehydrogenation catalysts
Received date: 2023-12-08
Online published: 2024-05-15
基于高氮环烷基直馏石脑油加氢生产重整原料的需求，通过自主研发的原位活化技术开发了THFS-2硫化型重整预加氢催化剂，采用N2吸附-脱附、H2-程序升温还原、X射线衍射、NH3-程序升温脱附、吡啶吸附红外光谱和高分辨率透射电镜等方法进行分析表征。结果表明，相比THFS-1加氢催化剂，有机磷助剂的引入优化了催化剂的孔道结构，增加了强酸和B酸（质子酸）量，提高了金属硫化度和原子利用率，形成了更多的“Ni—Mo—S”II类活性中心相。THFS-2催化剂应用于中海油惠州石化有限公司80万t/a重整预加氢装置，开工过程高效环保，活化时间缩短至18 h，循环氢中硫化氢最高含量小于2 000 μg/g。在反应器入口温度为289 ℃、氢分压为2.4 MPa、反应空速为5.0 h-1、氢油比（气液体积比，Nm3/m3）为130的满负荷工况下，加氢石脑油中硫、氮含量均小于0.5 μg/g，溴指数小于100 mg/100 g，砷含量小于1.0 µg/kg，氯含量小于0.5 µg/g。工业运行结果表明，THFS-2硫化型重整预加氢催化剂性能优异，可以满足高氮石脑油在高空速条件下的加氢活性，为重整装置提供合格原料。
王超 , 宋国良 , 肖寒 . THFS-2硫化型重整预加氢催化剂的工业应用[J]. 无机盐工业, 2024 , 56(5) : 94 -100 . DOI: 10.19964/j.issn.1006-4990.2023-0593
According to the demand on hydrogenation of the high nitrogen and naphthenic base of traight naphtha for reforming raw materials，THFS-2 sulfurized reforming pre-hydrogenation catalyst was developed through the independently developed in-situ activation technique.The catalysts were characterized by BET，H2-TPR，XRD，NH3-TPD，Py-FTIR and TEM techniques.The results showed that compared to the THFS-1 hydrogenation catalyst，the addition of organic phosphorus assistant optimized the pore structure of the catalyst，increased the distributions of medium strong acid and B acid，improved the metal sulfide and atomic utilization rate，and formd more active “NiMoS-Ⅱ” phases.THFS-2 catalyst achieved industrial application on 800 000 t/a reforming pre-hydrogenation unit of CNOOC Huizhou Petrochemical Co.，Ltd.The activation process was more efficient and environmentally friendly，the activation time was reduced to 18 h，and the highest hydrogen sulfide content in recycle hydrogen was less than 2 000 μg/g.Under the full load conditions of reaction inlet temperature of 289 ℃，hydrogen partial pressure of 2.4 MPa，the GHSV of 5.0 h-1，and hydrogen-oil ratio of 130 Nm3/m3，the sulfur and nitrogen contents in hydrogenated naphtha were less than 0.5 μg/g，the bromine index was less than 100 mg/100 g，the arsenic content was less than 1.0 µg/kg，and the chlorine content was less than 0.5 µg/g.The result of industrial operation showed that THFS-2 sulfurized reforming prehydrogenation catalyst had excellent performance.It could meet the hydrogenation activity of the high nitrogen straight-run naphtha under the condition of high GHSV，and provided qualified raw materials for reforming plant.
| 1 | 慕彦君，宋倩倩，付凯妹，等.芳烃生产技术进展及产业发展建议［J］.石化技术与应用，2021，39（5）：371-377. |
| MU Yanjun， SONG Qianqian， FU Kaimei，et al.Progress and industrial development suggestion of aromatics production technology［J］.Petrochemical Technology & Application，2021，39（5）：371-377. | |
| 2 | 辛靖，高杨，侯章贵，等.以生产轻芳烃为目的的催化重整装置原料拓展研究进展［J］.无机盐工业，2019，51（7）：1-7. |
| XIN Jing， GAO Yang， HOU Zhanggui，et al.Research progress on expanding feedstocks for catalytic reforming units for the production of light aromatics［J］.Inorganic Chemicals Industry，2019，51（7）：1-7. | |
| 3 | ANCHEYTA-JUáREZ J， VILLAFUERTE-MACíAS E.Kinetic modeling of naphtha catalytic reforming reactions［J］.Energy & Fuels，2000，14（5）：1032-1037. |
| 4 | 李洪亮，冯连坤，陈晓华.催化重整联合装置减油增化措施［J］.石化技术与应用，2023，41（4）：315-319. |
| LI Hongliang， FENG Liankun， CHEN Xiaohua.Measures of reducing oil and increasing chemicals in catalytic reforming complex unit［J］.Petrochemical Technology & Application，2023，41（4）：315-319. | |
| 5 | 马致远，王辉，王文辰，等.催化裂化汽油馏分切割作连续重整原料生产芳烃［J］.石化技术与应用，2023，41（6）：456-460. |
| MA Zhiyuan， WANG Hui， WANG Wenchen，et al.Catalytic cracking gasoline fraction cutting as continuous reforming feedstock for producing aromatics［J］.Petrochemical Technology & Application，2023，41（6）：456-460. | |
| 6 | ZHANG Tiezhen， JIA Yungang， SUN Famin，et al.Preparation and performance evaluation of reforming prehydrogenation catalyst used for blending inferior coking gasoline［J］.International Journal of Power and Energy Research，2020，4（3）：27-33. |
| 7 | 王健，朱俊华，叶迎春，等.载体预处理对Mo/Al2O3催化剂催化裂解汽油加氢脱氮性能的影响［J］.化学反应工程与工艺，2023，39（4）：306-312. |
| WANG Jian， ZHU Junhua， YE Yingchun，et al.Effect of support treatment on hydrodenitrogenation performance for pyrolysis gasoline over Mo/Al2O3 catalysts［J］.Chemical Reaction Engineering and Technology，2023，39（4）：306-312. | |
| 8 | 刘帅，白鸿博.柴油加氢工艺及催化剂研究进展［J］.当代化工，2023，52（9）：2237-2242. |
| LIU Shuai， BAI Hongbo.Research progress of diesel hydrogenation reaction process and hydrogenation catalysts［J］.Contemporary Chemical Industry，2023，52（9）：2237-2242. | |
| 9 | RAHIMPOUR M R， JAFARI M， IRANSHAHI D.Progress in catalytic naphtha reforming process：A review［J］.Applied Energy，2013，109：79-93. |
| 10 | 胡明涛，王德胜.浅谈芳烃联合装置原料变化对芳烃产品产率的影响［J］.化工管理，2020（9）：182-183. |
| HU Mingtao， WANG Desheng.Discussion on the influence of raw material change on aromatic hydrocarbon product yield in aromatic hydrocarbon combined plant［J］.Chemical Enterprise Management，2020（9）：182-183. | |
| 11 | 张春生.连续重整装置掺炼焦化石脑油可行性研究［J］.炼油技术与工程，2023，53（4）：5-8. |
| ZHANG Chunsheng.Feasibility study on blending coking naphtha in continuous catalytic reforming unit［J］.Petroleum Refinery Engineering，2023，53（4）：5-8. | |
| 12 | 王仲义，闫作杰，单敏，等.器外预硫化加氢裂化催化剂开工技术应用总结［J］.炼油技术与工程，2021，51（1）：10-12，32. |
| WANG Zhongyi， YAN Zuojie， SHAN Min，et al.Application summary of start-up technology of ex-situ presulfiding hydrocracking catalyst［J］.Petroleum Refinery Engineering，2021，51（1）：10-12，32. | |
| 13 | MANSUR D，AMINUDDIN.Chemical conversion of calophyllum inophyllum oil into bio-hydrocarbons fuel over presulfided NiMo/Al2O3 catalyst［J］.International Journal of Energy Research，2020，44（9）：7746-7760. |
| 14 | ZHOU Lin， LAWAL A.Evaluation of presulfided NiMo/γ-Al2O3 for hydrodeoxygenation of microalgae oil to produce green diesel［J］.Energy & Fuels，2015，29（1）：262-272. |
| 15 | 彭雪峰，于海斌，宋国良，等.器外预硫化型加氢催化剂的制备与性能研究［J］.无机盐工业，2019，51（11）：78-81. |
| PENG Xuefeng， YU Haibin， SONG Guoliang，et al.Preparation and properties of ex-situ presulfurization hydrogenation catalyst［J］.Inorganic Chemicals Industry，2019，51（11）：78-81. | |
| 16 | 李洪标，梁宇，吴显军，等.预硫化型石蜡加氢精制催化剂加氢技术研究［J］.炼油与化工，2022，33（6）：21-24. |
| LI Hongbiao， LIANG Yu， WU Xianjun，et al.Study on hydrogenation technology of prevulcanized paraffin hydrofining catalyst［J］.Refining and Chemical Industry，2022，33（6）：21-24. | |
| 17 | 罗树权，孙征，高雪.加氢催化剂器外预硫化技术现状［J］.化工技术与开发，2014，43（8）：34-37. |
| LUO Shuquan， SUN Zheng， GAO Xue.Current situation of ex-situ pre-sulfiding hydrotreatment catalyst［J］.Technology & Development of Chemical Industry，2014，43（8）：34-37. | |
| 18 | 彭雪峰，于海斌，张景成，等.THFS-I硫化型重整预加氢催化剂的首次工业应用［J］.石油炼制与化工，2017，48（2）：68- 71. |
| PENG Xuefeng， YU Haibin， ZHANG Jingcheng，et al.Industrial application of sulfide-type pre-hydrogenation catalyst THFS-I for reforming unit［J］.Petroleum Processing and Petrochemicals，2017，48（2）：68-71. | |
| 19 | 彭雪峰，于海斌，张景成，等.THFS-Ⅰ硫化型重整预加氢催化剂的开发与性能研究［J］.无机盐工业，2017，49（2）：82-86. |
| PENG Xuefeng， YU Haibin， ZHANG Jingcheng，et al.Preparation and properties of THFS-Ⅰ sulfide-type reforming pre-hydrogenation catalyst［J］.Inorganic Chemicals Industry，2017，49（2）：82-86. | |
| 20 | 彭雪峰，于海斌，孙彦民，等.THFS-I硫化型加氢催化剂在80万t·a-1重整预加氢装置上的工业运行情况［J］.当代化工，2022，51（4）：989-992. |
| PENG Xuefeng， YU Haibin， SUN Yanmin，et al.Industrial application of THFS-I sulfide-type hydrogenation catalyst in the 0.8 Mt·a-1 reforming pre-hydrogenation unit［J］.Contemporary Chemical Industry，2022，51（4）：989-992. | |
| 21 | 彭雪峰，于海斌，孙彦民，等.THFS-2硫化型加氢催化剂的工业应用［J］.化学工程师，2022，36（5）：75-78. |
| PENG Xuefeng， YU Haibin， SUN Yanmin，et al.Industrial application of THFS-2 sulfide-type hydrogenation catalyst［J］.Chemical Engineer，2022，36（5）：75-78. | |
| 22 | 王甫村，朱金玲，田然，等.用于FCC柴油加氢改质的选择性开环催化剂研究进展［J］.化工进展，2011，30（9）：1951-1955. |
| WANG Fucun， ZHU Jinling， TIAN Ran，et al.Advances in selective ring opening catalysts for FCC diesel hydro-upgrading［J］.Chemical Industry and Engineering Progress，2011，30（9）：1951-1955. | |
| 23 | 郭振雪，于海斌，张国辉，等.Si改性对NiMo/Al2O3催化剂加氢脱硫性能的影响［J］.化工进展，2022，41（S1）：210-220. |
| GUO Zhenxue， YU Haibin， ZHANG Guohui，et al.Effect of Si modification on hydrodesulfurization performance of NiMo/Al2O3 catalyst［J］.Chemical Industry and Engineering Progress，2022，41（S1）：210-220. | |
| 24 | 汪佩华，秦志峰，吴琼笑，等.磷添加方式对NiMo/Al2O3催化剂加氢脱硫性能的影响［J］.化工进展，2021，40（2）：890-900. |
| WANG Peihua， QIN Zhifeng， WU Qiongxiao，et al.Effect of phosphorus adding manners on the performance of NiMo/Al2O3 catalyst in hydrodesulfurization［J］.Chemical Industry and Engineering Progress，2021，40（2）：890-900. | |
| 25 | LIU Bin， LIU Lei， WANG Zhong，et al.Effect of hydrogen spillover in selective hydrodesulfurization of FCC gasoline over the CoMo catalyst［J］.Catalysis Today，2017，282：214-221. |
| 26 | GUTIéRREZ O Y， KLIMOVA T.Effect of the support on the high activity of the（Ni）Mo/ZrO2-SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4，6-DMDBT［J］.Journal of Catalysis，2011，281（1）：50-62. |
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