Effect of calcination temperature on the structure and properties of Raney-Ni catalyst for hydrogenation of 1, 4-butenediol
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摘要: 在Ni-Al合金粉上浸渍硝酸铜溶液，经不同温度焙烧得到Cu改性Ni-Al合金粉，采用质量分数10% NaOH溶液浸渍上述改性合金粉得Cu/Raney-Ni催化剂。采用EDX、XRD、N2吸附-脱附、TEM和NH3-TPD等手段表征了Ni-Al合金粉及相应Raney-Ni催化剂的元素含量、晶体结构、孔结构特征、表面形貌和表面酸碱性，并以1，4-丁烯二醇加氢制1，4-丁二醇为探针反应，考察了焙烧温度对Raney-Ni催化剂加氢性能的影响。表征分析表明，焙烧温度500 ℃所制备的CRT500催化剂比表面积较大，为64.96 m2/g；弱酸中心比例较高，达81.2%。结果表明，焙烧温度升高，BED可实现完全转化，BDO选择性和收率均先升高后降低。其中，CRT500加氢性能较好，BED转化率为100.00%，BDO选择性为61.88%。进一步升高焙烧温度，催化剂RCT550和RCT600的BDO选择性和收率反而降低，这是由于高温下催化剂易发生团聚或烧结。结合催化剂表征可知，CRT500具有较好的加氢性能，这与该催化剂具有合适的Ni/Al物质的量比（3.84）、弱酸中心所占比例较大和活性组分Ni分散性好等因素有较大关联。
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关键词:
- 浸渍法 /
- Raney-Ni催化剂 /
- 1, 4-丁烯二醇 /
- 焙烧温度
Abstract: Ni-Al alloy powder was impregnated with copper nitrate solution, and calcined at different temperatures to obtain Cu-modified Ni-Al alloy powder. The modified alloy powder was leached with a 10% (mass ratio) NaOH solution to obtain the Cu/Raney-Ni catalyst. Elemental composition, crystal structure, pore structure, surface morphology and surface acidity of the Ni-Al alloy powder and corresponding Raney-Ni catalysts were characterized by EDX, XRD, N2 adsorption-desorption, TEM and NH3-TPD. The hydrogenation performance of the Raney-Ni catalysts were evaluated using the reaction of 1, 4-butenediol (BED) hydrogenation to 1, 4-butanediol (BDO) as the probe reaction. The characteristic results showed that the CRT500 catalyst prepared at the calcination temperature of 500 ℃ presented larger specific surface area of 64.96 m2/g, and the proportion of weak acid sites was high of 81.2%. The reaction results proposed that the reactant of BED could be completely converted, and the selectivity and yield of BDO increased firstly and then decreased as the calcination temperature increased. The CRT500 catalyst presented good hydrogenation performance, with BED conversion of 100.00%, BDO selectivity of 61.88%, while the BDO selectivity of the RCT550 and RCT600 were lower, which might be due to the agglomeration or sintering of the catalyst at higher calcination temperature. The CRT500 catalyst showed excellent hydrogenation performance, which might be attributed to the appropriate molar ratio of Ni/Al (3.84), the large proportion of weak acid sites and good dispersion of active component Ni.-
Key words:
- impregnation /
- Raney-Ni catalyst /
- 1, 4-butenediol /
- calcination temperature
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图 1 Ni-Al合金活化装置示意图
Figure 1 Equipment for the activation of Ni-Al alloys
1: heater; 2: water bath; 3: three-necked flask; 4: feeding port; 5: thermometer; 6: rotor
图 2 1, 4-丁烯二醇加氢反应评价装置示意图
Figure 2 Scheme diagram of the evaluation device for 1, 4-butenediol hydrogenation
图 3 不同焙烧温度合金粉的XRD谱图
Figure 3 XRD patterns of the alloy powder calcined at different temperatures
图 4 不同温度焙烧后试样的SEM照片
Figure 4 SEM images of the samples calcined at different temperatures
(a): CRT350; (b): CRT400; (c): CRT450; (d): CRT500; (e): CRT550; (f): CRT600
图 5 不同焙烧温度合金粉N2吸附-脱附等温线和孔径分布
Figure 5 N2 adsorption-desorption isotherm(a) and pore distributions (b) of the alloy powder calcined at different temperatures
图 6 催化剂的EDX-Mapping照片
Figure 6 EDX-Mapping diagrams of the catalysts
(a): CRT350-Al; (b): CRT350-Ni; (c): CRT350-Cu; (d): CRT400-Al; (e): CRT400-Ni; (f): CRT400-Cu; (g): CRT450-Al; (h): CRT450-Ni; (i): CRT450-Cu; (j): CRT500-Al; (k): CRT500-Ni; (l): CRT500-Cu; (m): CRT550-Al; (n): CRT550-Ni; (o): CRT550-Cu; (p): CRT600-Al; (q): CRT600-Ni; (r): CRT600-Cu
图 8 催化剂的SEM照片
Figure 8 SEM images of the catalysts
(a): CRT350; (b): CRT400; (c): CRT450; (d): CRT500; (e): CRT550; (f): CRT600
图 9 催化剂的N2吸附-脱附等温线和孔径分布
Figure 9 N2 adsorption-desorption isotherms (a) and pore distributions(b) of the catalysts
图 11 催化剂的TEM照片
Figure 11 TEM images of the catalysts
(a): CRT350; (b): CRT400; (c): CRT450; (d): CRT500; (e): CRT550; (f): CRT600
图 12 催化剂BED的转化率、BDO的选择性和收率
Figure 12 BED conversion, selectivity and yield of BDO over the catalysts calcined at different temperatures
图 14 1, 4-丁烯二醇反应机理示意图
Figure 14 Proposed mechanism for hydrogenation of 1, 4-butenedio
表 1 Ni2Al3相的晶粒粒径
Table 1 Grain size of Ni2Al3
Sample Size of Ni2Al3 d/nm RT350 1.059 RT400 1.027 RT450 0.886 RT500 0.876 RT550 0.863 RT600 0.678 
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表 2 焙烧后试样的元素含量
Table 2 Elemental contents of the catalysts calcined at different temperatures
Catalyst Content w/% O Al Ni Cu RT350 1.33 44.13 43.36 11.18 RT400 0.14 52.42 37.20 10.24 RT450 0.14 52.42 38.92 8.53 RT500 0.13 43.17 49.90 6.80 RT550 0.15 45.25 49.04 5.55 RT600 0.19 56.81 38.54 4.46
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表 3 合金粉的比表面积、孔体积和平均孔径
Table 3 Specific surface area, pore volume, average pore diameter of the alloy powder
Sample Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Average pore diameter d/nm RT350 21.1 0.025 4.92 RT400 14.37 0.019 5.36 RT450 33.44 0.019 3.68 RT500 13.49 0.020 5.59 RT550 10.44 0.016 5.61 RT600 11.06 0.018 5.88
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表 4 催化剂的元素含量
Table 4 Elemental contents of the catalyst samples
Sample Content w/% Ni/Al
(mol ratio)Al Ni Cu CRT350 12.07 75.60 12.33 2.88 CRT400 12.78 75.28 11.94 2.71 CRT450 9.91 80.48 9.61 3.76 CRT500 9.68 80.83 9.49 3.84 CRT550 8.39 81.78 9.83 4.48 CRT600 8.58 82.56 8.86 4.42
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表 5 Cu相和Ni相的晶粒粒径
Table 5 Crystal grain size of Ni and Cu
Sample Pore size d /nm Cu Ni CRT350 0.486 0.229 CRT400 0.434 0.167 CRT450 0.610 0.217 CRT500 0.461 0.179 CRT550 0.466 0.183 CRT600 0.498 0.196
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表 6 催化剂的比表面积、孔体积和平均孔径
Table 6 Specific surface area, pore volume, average pore diameter of the catalysts
Sample Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Average pore diameter d/nm CRT350 33.75 0.047 5.44 CRT400 51.54 0.063 4.82 CRT450 62.18 0.060 4.13 CRT500 64.96 0.075 4.85 CRT550 52.27 0.063 4.88 CRT600 57.83 0.065 4.73
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表 7 弱酸和中强酸峰面积所占比例
Table 7 Proportion of weak acid peak area and medium acid peak area
Sample Peak area proportion
of the weak acid /%Peak area proportion
of the medium acid /%CRT350 67.8 32.2 CRT400 72.5 27.5 CRT450 79.5 20.5 CRT500 81.2 18.8 CRT550 75.3 24.7 CRT600 75.7 24.3
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