双环戊二烯加氢NiMox/γ-Al2O3催化剂耐硫特性的研究

doi:10.11949/0438-1157.20200529

摘要/Abstract

摘要：

研究了钼元素及其添加量对镍基催化剂在双环戊二烯（DCPD）加氢反应中耐硫特性的影响规律。催化剂∶DCPD =1∶10，反应温度150℃，压力3.5 MPa，转速600 r/min，噻吩浓度为：500 mg/L时，Ni/γ-Al₂O₃催化剂的双环戊二烯8、9位双键的加氢速率显著降低，3、4位双键的加氢活性完全抑制；而NiMo_0.2/γ-Al₂O₃催化剂，在4 h内完成加氢反应，四氢双环戊二烯（endo-THDCPD）收率达到98%，抗硫特性显著提高。不同镍钼比的系列催化剂中，NiMo_0.2/γ-Al₂O₃具有最好的加氢活性与耐硫特性。0~2000 mg/L噻吩浓度内，低浓度条件下，NiMo_0.2/γ-Al₂O₃催化剂对双环戊二烯的加氢活性高，选择性好；随着噻吩浓度增加，催化性能有所下降，2000 mg/L时，加氢反应延长至6 h，endo-THDCPD收率降至95%。

关键词: 双环戊二烯, 加氢, 耐硫特性, 钼, 镍基催化剂

Abstract:

The effect of Mo and its addition amount on the sulfur tolerance of Ni catalyst in the hydrogenation of dicyclopentadiene (DCPD) was studied. A series of γ-Al₂O₃supported nickel-molybdenum bimetallic catalysts were prepared by the equal volume impregnation method. The performance test of the catalyst was carried out in an autoclave, the feed ratio was the catalyst∶DCPD∶cyclohexane = 1∶10∶100. The reaction was carried out at a temperature of 150℃ and a pressure of 3.5 MPa, with a stirring speed 600 r/min. Before the reaction starts, a certain amount of thiophene was added in cyclohexane in order to know the sulfur resistance of the catalyst. When the concentration of thiophene cyclohexane solution is 500 mg/L, the hydrogenation rate of the double bond of 8, 9 position of dicyclopentadiene is significantly reduced under the catalysis of Ni/γ-Al₂O₃, and the hydrogenation activity of double bond of 3,4 position is completely suppressed; under NiMo_0.2/γ-Al₂O₃ catalysis, however, the hydrogenation reaction is completed within 4 h, the yield of tetrahydrodicyclopentadiene (endo-THDCPD) reaches 98%, and the sulfur resistance of the catalyst is significantly improved. Among the series of catalysts with different nickel-molybdenum ratios, NiMo_0.2/γ-Al₂O₃ exhibited the best hydrogenation activity and sulfur resistance. Catalyst NiMo_0.2/γ-Al₂O₃ was tested for sulfur resistance with a thiophene concentration range of 0~2000 mg/L. When the concentration of thiophene is low, the NiMo_0.2/γ-Al₂O₃ catalyst has high hydrogenation activity and good selectivity for dicyclopentadiene; as the concentration of thiophene increases, the catalytic performance of the catalyst decreases. When the thiophene concentration is increased to 2000 mg/L, the hydrogenation reaction is extended to 6 hours, and the yield of endo-THDCPD is reduced to 95%.

Key words: dicyclopentadiene, hydrogenation, sulfur resistance, molybdenum, nickel-based catalyst

中图分类号:

TQ 517.2

史大昕, 李爱如, 方祝青, 李继娟, 矫庆泽, 吴芹, 冯彩虹, 赵芸, 黎汉生. 双环戊二烯加氢NiMo_x/γ-Al₂O₃催化剂耐硫特性的研究[J]. 化工学报, 2020, 71(9): 4177-4188.

Daxin SHI, Airu LI, Zhuqing FANG, Jijuan LI, Qingze JIAO, Qin WU, Caihong FENG, Yun ZHAO, Hansheng LI. Study on sulfur tolerance of NiMo_x/γ-Al₂O₃ catalyst for dicyclopentadiene hydrogenation[J]. CIESC Journal, 2020, 71(9): 4177-4188.

图/表 11

图1 DCPD加氢过程中的主要反应网络图

Fig.1 Reaction system of dicyclopentadiene hydrogenation

图2 双环戊二烯加氢反应装置1—氮气气瓶；2—氢气气瓶；3—温度和转速控制装置；4—压力表；5—磁力搅拌器；6—加热装置；7—取样管；8—元素瓶；9—气相色谱仪

Fig.2 Dicyclopentadiene hydrogenation reaction device

图3 前体NiO/γ-Al2O3和NiMoxO/γ-Al2O3（x=0.1,0.2,0.5）H2-TPR表征结果

Fig.3 H2-TPR characterization of NiO/γ-Al2O3和NiMoxO/γ-Al2O3（x=0.1,0.2,0.5）

图4 前体NiO/γ-Al2O3、NiMoxO/γ-Al2O3(x=0.1,0.2和0.5)以及载体γ-Al2O3的N2吸附-脱附实验结果

Fig.4 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of the precursors NiMoxO/γ-Al2O3(x=0.1,0.2 and 0.5), NiO/γ-Al2O3 and γ-Al2O3

表1 前体和载体的孔体积（Vp）、比表面积（SBET）和平均孔径（MPD）

Table 1 Symbols and several characteristics of the precursors [specific pore volume(Vp), specific surface area (SBET) and mean pore diameter (MPD)]

样品	V_p/(cm³/g)	MPD/nm	S_BET/(m²/g)
γ-Al₂O₃	0.64	10.9	236
NiO/γ-Al₂O₃	0.56	10.5	213
NiMo_0.1O/γ-Al₂O₃	0.49	9.7	201
NiMo_0.2O/γ-Al₂O₃	0.49	9.4	209
NiMo_0.5O/γ-Al₂O₃	0.46	9.2	198

图5 NiMox/γ-Al2O3 (x=0.1,0.2,0.5), Ni/γ-Al2O3及载体γ-Al2O3的XRD谱图

Fig.5 XRD patterns of fresh catalysts NiMox/γ-Al2O3 (x= 0.1, 0.2, 0.5), Ni/γ-Al2O3 and γ-Al2O3

图6 催化剂Ni/γ-Al2O3和NiMox/γ-Al2O3（x = 0.1, 0.2, 0.5）EDS表征结果

Fig.6 EDS characterization of catalysts Ni /γ-Al2O3 and NiMox /γ-Al2O3 (x = 0.1, 0.2, 0.5)

图7 Ni/γ-Al2O3和NiMo0.2 /γ-Al2O3催化DCPD加氢性能图（催化剂∶DCPD∶环己烷=1∶10∶100；150℃，3.5 MPa，600 r/min）

Fig.7 Results of DCPD hydrogenation reaction (Cata∶DCPD∶cyclohexane=1∶10∶100；150℃，3.5 MPa，600 r/min)

图8 噻吩对催化剂Ni/γ-Al2O3和NiMo0.2 /γ-Al2O3催化DCPD加氢的影响（催化剂∶DCPD∶环己烷=1∶10∶100，噻吩浓度500 mg/L，150℃，3.5 MPa，600 r/min）

Fig.8 The effect of thiophene on DCPD hydrogenation (Cata∶DCPD∶cyclohexane=1∶10∶100，thiophene 500 mg/L，150℃，3.5 MPa，600 r/min)

图9 Mo含量对NiMox/γ-Al2O3(x=0.1、0.2、0.5)催化DCPD加氢耐硫性能的影响（催化剂∶DCPD∶环己烷=1∶10∶100，噻吩浓度500 mg/L，150℃，3.5 MPa，600 r/min）

Fig.9 Effect of molybdenum content on NiMox/γ-Al2O3(x=0.1,0.2,0.5) sulfur resistance (Cata∶DCPD∶cyclohexane=1∶10∶100，thiophene 500 mg/L，150℃，3.5 MPa，600 r/min)

图10 噻吩浓度对NiMo0.2 /γ-Al2O3催化DCPD加氢性能的影响（催化剂∶DCPD∶环己烷=1∶10∶100，噻吩浓度0、500、1000、2000 mg/L，150℃，3.5 MPa，600 r/min）

Fig.10 Effect of thiophene content on NiMo0.2 /γ-Al2O3 catalytic hydrogenation characteristics (Cata∶DCPD∶cyclohexane=1∶10∶100，thiophene 0，500，1000，2000 mg/L，150℃，3.5 MPa，600 r/min)

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双环戊二烯加氢NiMo_x/γ-Al₂O₃催化剂耐硫特性的研究

Study on sulfur tolerance of NiMo_x/γ-Al₂O₃ catalyst for dicyclopentadiene hydrogenation

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