Preparation of modified β zeolite with phosphorus for catalytic alkylation of C9 aromatics with propylene
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摘要: 利用浸渍法对β沸石进行磷改性,制备了不同磷负载量的改性β沸石催化剂。采用XRD、SEM、EDX、MAS NMR、Py-FTIR、N2吸附-脱附和NH3-TPD手段对催化剂样品进行了表征,并且研究了改性β沸石在催化C9芳烃与丙烯烷基化反应中的性能。结果表明,β沸石经磷改性后,其形貌和晶体结构没有发生明显变化。然而,随着磷添加量的增加,β沸石的比表面积和表面硅铝质量比逐渐减小;磷与β沸石相互作用,改变了催化剂酸强度分布。β沸石上磷的负载量显著影响C9芳烃烷基化反应结果。与未改性的β沸石相比,β-0.5P催化剂烷基化反应活性明显提高,烷基化反应产物中C12+重芳烃的比例达到17%,m1,3,5-TMB/mC9值增加了5.3%,连续反应10 h,活性稳定;然而,当磷负载量过高,催化剂烷基化活性降低,异构化和歧化反应性能增强。Abstract: To investigate the catalytic properties of β zeolite for catalytic alkylation of C9 aromatics with propylene, β zeolites modified with phosphorus were prepared by using impregnation method. The modified β catalysts with different loading amount of phosphorus were characterized by XRD, SEM, EDX, MAS NMR, Py-IR, N2 adsorption-desorption, and NH3-TPD. The results showed that the morphology and crystal structure of the β zeolite catalysts did not change obviously after modification with phosphorus. However, the specific surface area and the surface Si/Al mass ratio of the β zeolite decreased with the increase of amount of phosphorus. It was proved that the interaction between the phosphorus and β zeolite could affect the acid strength distribution of β zeolite and the catalytic performance of alkylation of C9 aromatics. In comparison with β zeolite, the β zeolite modified with 0.5% phosphorus (β-0.5P) had good catalytic performance in alkylation reaction of C9 aromatics. The ratio of C12+ aromatics in the alkylation products was up to 17%, and the value of m1,3,5-TMB/mC9 was increased by 5.3%. The β-0.5P catalytic activity showed stable after reaction for 10 h. However, when the loading amount of phosphorus on β zeolite was too high, the alkylation activity of the catalyst decreased and the isomerization and disproportionation performance of the catalyst increased.
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Key words:
- β zeolite /
- modification /
- C9 aromatics /
- propylene /
- alkylation
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表 1 C9芳烃组成
Table 1 Composition of C9 aromatics
Component NPB m, p-MEB 1,3,5-TMB o-MEB 1,2,4-TMB 1,2,3-TMB w/% 0.05 10.66 33.41 55.14 0.72 0.02 表 2 不同磷负载量的β沸石的结构参数
Table 2 Structure properties of differnet modified β zeolite samples
Sample Surface area/(m2·g−1) Pore volume/(cm3·g−1) SBET SMicro SMeso vMicro vtota β 431.1 302.5 128.6 0.16 0.41 β-0.5P 429.2 301.8 127.4 0.16 0.42 β-1.0P 422.4 299.5 122.9 0.16 0.42 β-2.0P 395.0 283.1 111.9 0.15 0.43 表 3 磷修饰的β沸石酸强度分布
Table 3 Distribution of acidity amount of β zeolite modified with phosphorus
Sample LT-peak/℃ HT-peak/℃ Total area Weak acid area Strong acid area LT/HT* β 210 380 3770 2925 845 3.46 β-0.5P 210 367 3766 3130 636 4.92 β-1.0P 212 367 3749 3149 600 5.25 β-2.0P 200 356 2870 2453 417 5.88 * ratio of low temperature (LT) peak area to high temperature (HT) peak area 表 4 不同磷负载量的β沸石样品的吡啶红外数据
Table 4 Py-FTIR data of β zeolite samples with different phosphorus loadings
Sample 150 ℃ B/L 400 ℃ B/L B/(10−2 mmol·g−1) L/(10−2 mmol·g−1) B/(10−2 mmol·g−1) L/(10−2 mmol·g−1) β 3.75 2.15 2.32 2.50 1.55 2.14 β-0.5P 2.87 1.84 2.08 1.90 1.42 1.78 β-1.0P 2.75 1.16 3.15 1.85 1.03 2.40 β-2.0P 2.35 0.64 4.89 1.73 0.59 3.94 -
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