Zr改性Y分子筛中油型加氢裂化催化剂设计制备

doi:10.11949/0438-1157.20190651

摘要/Abstract

摘要：

采用等体积浸渍法对Y分子筛进行了Zr修饰改性，系统考察了不同用量Zr对改性Y分子筛的结构、催化剂的理化性质和加氢裂化反应性能的影响规律。通过XRD、NH₃-TPD、H₂-TPR和TEM等方法对改性分子筛和催化剂进行表征分析。结果表明：Zr改性降低了Y分子筛的酸量，随着改性Zr用量的增加，这种变化趋势不断增大。同时，Zr改性有效地削弱了分子筛催化剂中金属活性组分与载体间的作用，提高了W物种在催化剂表面的分散程度。加氢裂化反应结果表明：与Y分子筛催化剂相比，Zr改性Y分子筛催化剂的减压馏分油(VGO)转化率降低，中间馏分油选择性提高约20%，随着改性Zr用量的增加，VGO的转化率不断降低，中间馏分油选择性略有增加。

关键词: 催化剂, 分子筛, 载体, 加氢裂化, Zr改性, 中间馏分油

Abstract:

Y zeolite was modified with Zr by equal volume impregnation method. The effects of different amounts of Zr on the structure of modified Y zeolite, the physicochemical properties of the catalyst and the performance of hydrocracking reaction were investigated systematically. The modified Y zeolite and catalyst were characterized by X-ray diffraction (XRD), NH₃ temperature programmed desorption (NH₃-TPD), H₂ temperature programmed reduction (H₂-TPR) and transmission electron microscopy (TEM). The results show that Zr modification decreased the amount of acid sites of Y zeolite, and the trend became larger with an increase of Zr content. Moreover, Zr modification availably weakened the relation of metal species and support in the catalyst with Y zeolite, and improved the dispersion of W species on the catalyst surface. The hydrocracking reaction results suggested that VGO conversion over the catalyst with Y zeolite modified with Zr decreased compared with that with Y zeolite, and middle distillates increased about 20%(mass), as well as VGO conversion gradually decreased and the middle distillates slightly increased as the Zr content increased.

Key words: catalyst, zeolite, support, hydrocracking, Zr modification, middle distillates

中图分类号:

TQ 426.92

崔勍焱, 张浩彬, 魏强, 岳源源, 王廷海, 朱海波, 周亚松, 鲍晓军. Zr改性Y分子筛中油型加氢裂化催化剂设计制备[J]. 化工学报, 2019, 70(10): 3949-3955.

Qingyan CUI, Haobin ZHANG, Qiang WEI, Yuanyuan YUE, Tinghai WANG, Haibo ZHU, Yasong ZHOU, Xianjun BAO. Development of hydrocracking catalyst supported on Y zeolite modified with Zr[J]. CIESC Journal, 2019, 70(10): 3949-3955.

图/表 8

图1 Zr改性Y分子筛的XRD谱图

Fig.1 XRD patterns of Y zeolite modified with Zr

图2 Zr改性Y分子筛的NH3-TPD图

Fig.2 NH3-TPD profiles of Y zeolite modified with Zr

图3 Zr改性Y分子筛催化剂的H2-TPR图

Fig.3 H2-TPR profiles of catalysts with Y zeolite modified with Zr

图4 硫化态NiW催化剂的TEM图

Fig.4 TEM images of sulfide NiW catalysts

图5 催化剂WS2相长度和堆垛层数的分布

Fig.5 Distributions of WS2 slab length and number of layers for catalysts

表1 催化剂WS2相的平均长度和堆垛层数 layers for catalysts

Table 1 Average WS2 slab length and number of layers for catalysts

催化剂	平均长度/nm	平均堆垛层数
Cat-Y	3.23	2.31
Cat-2ZrY	3.00	2.69
Cat-4ZrY	2.92	2.75

图6 催化剂不同温度下的加氢裂化转化率

Fig.6 Hydrocracking conversions of catalysts at different reaction temperatures

表2 转化率为60%~70%时的产品收率和选择性

Table 2 Product yield and selectivity at conversions of 60%－70%

催化剂	转化率/%	收率/%		选择性/%
催化剂	转化率/%	石脑油	中间馏分油	石脑油	中间馏分油
Cat-Y	63.9	18.7	33.0	32.6	51.7
Cat-2ZrY	65.1	19.8	44.5	30.4	68.4
Cat-4ZrY	62.5	16.9	45.6	27.1	72.9

参考文献 32

1	Jarullah A T , Mujtaba IM , Wood A S . Improvement of the middle distillate yields during crude oil hydrotreatment in a Trickle-bed reactor [J]. Energy Fuels, 2011, 25: 773-781.
2	Lababidi H M S , Chedadeh D , Riazi M R , et al . Prediction of product quality for catalytic hydrocracking of vacuum gas oil [J]. Fuel, 2011, 90: 719-727.
3	Park H B , Lee Y K . Designing supported NiMoS₂ catalysts for hydrocracking of vacuum residue[J]. Fuel, 2019, 239: 1265-1273.
4	Ali M A , Tatsumi T , Masuda T . Development of heavy oil hydrocracking catalysts using amorphous silica-alumina and zeolites as catalyst supports [J]. Applied Catalysis A: General, 2002, 233: 77-90.
5	Looi P Y , Mohamed A R , Tye C T . Hydrocracking of residual oil using molybdenum supported over mesoporous alumina as a catalyst [J]. Chemical Engineering Journal, 2012, 181/182: 717-724.
6	Ohshio N , Enomoto T , Honna K , et al . Development of zeolite-based catalyst for resid hydrocracking [J]. Fuel, 2004, 83: 1895-1898.
7	Manrique C , Guzman A , Perez-Pariente J , et al . Effect of synthesis conditions on zeolite beta properties and its performance in vacuum gas oil hydrocracking activity [J]. Microporous and Mesoporous Materials, 2016, 234: 347-360.
8	Manrique C , Guzmán A , Pérez-Pariente J , et al . Vacuum gas-oil hydrocracking performance of beta zeolite obtained by hydrothermal synthesis using carbon nanotubes as mesoporous template [J]. Fuel, 2016, 182: 236-247.
9	Francis J , Guillona E , Bats N , et al . Design of improved hydrocracking catalysts by increasing the proximity between acid and metallic sites [J]. Applied Catalysis A: General, 2011, 409/410: 140-147.
10	Guisnet M , Alvarez F , Giannetto G , et al . Hydroisomerization and hydrocracking of n-heptane on Pt zeolites. Effect of the porosity and of the distribution of metallic and acid sites [J]. Catalysis Today, 1987, 1: 415-433.
11	Henry R , Tayakout-Fayolle M , Afanasiev P , et al . Vacuum gas oil hydrocracking performance of bifunctional Mo/Y zeolite catalysts in a semi-batch reactor [J]. Catalysis Today, 2014, 220/221/222: 159-167.
12	Eller Z , Varga Z , Hancsók J . Advanced production process of jet fuel components from technical grade coconut oil with special hydrocracking [J]. Fuel, 2016, 182: 713-720.
13	Dik P P , Klimov O V , Koryakina G I , et al . Composition of stacked bed for VGO hydrocracking with maximum diesel yield [J]. Catalysis Today, 2014, 220/221/222: 124-132.
14	Agudelo J L , Hensen E J M , Giraldo S A , et al . Effect of USY zeolite chemical treatment with ammonium nitrate on its VGO hydrocracking performance [J]. Energy Fuels, 2016, 30: 616-625.
15	Alwan B A , Sari E , Salley S O , et al . Effect of metal ratio and preparation method on nickel-tungsten carbide catalyst for hydrocracking of distillers dried grains with solubles corn oil [J]. Industrial & Engineering Chemistry Research, 2014, 53: 6923-6933.
16	Leckel D , Liwanga-Ehumbu M . Diesel-selective hydrocracking of an iron-based Fischer-Tropsch wax fraction (C₁₅—C₄₅) using a MoO₃-modified noble metal catalyst [J]. Energy Fuels, 2006, 20: 2330-2336.
17	Li D , Nishijima A , Morris D E , et al . Activity and structure of hydrotreating Ni, Mo, and Ni-Mo sulfide catalysts supported on γ-Al₂O₃-USY zeolite [J]. Journal of Catalysis, 1999, 188: 111-124.
18	Rana M S , Trejo F , Ancheyta J , et al . Heavy crude oil hydroprocessing: a zeolite-based CoMo catalyst and its spent catalyst characterization [J]. Catalysis Today, 2008, 130: 411-420.
19	Ding L , Zheng Y , Zhang Z , et al . Hydrotreating of light cycled oil using WNi/Al₂O₃ catalysts containing zeolite beta and/or chemically treated zeolite Y [J]. Journal of Catalysis, 2006, 241: 435-445.
20	Sanchez-Castillo M A , Madon R J , Dumesic J A . Role of rare earth cations in Y zeolite for hydrocarbon cracking [J]. The Journal of Physical Chemistry B, 2005, 109: 2164-2175.
21	Liu C H , Gao X H , Zhang Z D , et al . Surface modification of zeolite Y and mechanism for reducing naphtha olefin formation in catalytic cracking reaction [J]. Applied Catalysis A: General, 2004, 264: 225-228.
22	Oumia Y , Manabe T , Sasaki H , et al Preparation of Ti incorporated Y zeolites by a post-synthesis method under acidic conditions and their catalytic properties [J]. Applied Catalysis A: General, 2010, 388: 256-261.
23	Agudelo J L , Hensen E J M , Giraldo S A , et al . Influence of steam-calcination and acid leaching treatment on the VGO hydrocracking performance of faujasite zeolite [J]. Fuel Processing Technology, 2015, 133: 89-96.
24	Chang X W , He L F , Liang H N . Screening of optimum condition for combined modification of ultra-stable Y zeolites using multi-hydroxyl carboxylic acid and phosphate [J]. Catalysis Today, 2010, 158: 198-204.
25	Shimada H , Sato K , Honna K , et al . Design and development of Ti modified zeolite-based catalyst for hydrocracking heavy petroleum [J]. Catalysis Today, 2009, 141: 43-51.
26	Cui Q Y , Zhou Y S , Wei Q . Performance of Zr- and P-modified USY-based catalyst in hydrocracking of vacuum gas oil [J]. Fuel Processing Technology, 2013, 106: 439-446.
27	Vermaire D C , Berge P C . The preparation of WO₃TiO and WO₃Al₂O₃ and characterization by temperature-programmed reduction [J]. Journal of Catalysis, 1989, 116: 309-317.
28	Scheffer B , Molhoek P , Moulijn J A . Temperature-programmed reduction of NiOWO₃/Al₂O₃ hydrodesulphurization catalysts [J]. Applied Catalysis, 1989, 46:11-30.
29	Manoli J M , Da Costa P , Brun M , et al . Hydrodesulfurization of 4,6-dimethyldibenzothiophene over promoted (Ni, P) alumina-supported molybdenum carbide catalysts: activity and characterization of active sites [J]. Journal of Catalysis, 2004, 221: 365-377.
30	Zhou W W , Liu M F , Zhang Q , et al . Synthesis of NiMo catalysts supported on gallium-containing mesoporous Y zeolites with different gallium contents and their high activities in the hydrodesulfurization of 4,6- dimethyldibenzothiophene [J]. ACS Catalysis, 2017, 7: 7665-7679.
31	Rezgui Y , Guemini M . Effect of acidity and metal content on the activity and product selectivity for n-decane hydroisomerization and hydrocracking over nickel-tungsten supported on silica–alumina catalysts [J]. Applied Catalysis A: General, 2005, 282: 45-53.
32	Vissers J P R , Scheffer B , de Beer V H J . Effect of the support on the structure of Mo-based hydrodesulfurization catalysts: activated carbon versus alumina [J]. Journal of Catalysis, 1987, 105: 277-284.

[1]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[2]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[3]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[4]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[5]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[6]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[7]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[8]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[9]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[10]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[11]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[12]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.
[13]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.
[14]	王辰, 史秀锋, 武鲜凤, 魏方佳, 张昊虹, 车寅, 吴旭. 氧化还原法制备Mn₃O₄催化剂及其甲苯催化氧化性能与机理研究[J]. 化工学报, 2023, 74(6): 2447-2457.
[15]	李勇, 高佳琦, 杜超, 赵亚丽, 李伯琼, 申倩倩, 贾虎生, 薛晋波. Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢[J]. 化工学报, 2023, 74(6): 2458-2467.