论文总字数：12382字
摘 要
本文采用气相色谱-质谱分析技术对0#柴油及被(NH4)2S2O8-HCl脱硫剂氧化后的柴油，实验结果表明(NH4)2S2O8-HCl脱硫剂氧化的柴油主要成分并未发生明显的变化。关 键 词：0＃柴油，氧化脱硫，气相色谱-质谱
Abstract：The compounds in diesel 0# and diesel 0# oxidized by S2O8-2 in HCl solution were identified by gas chromatography - mass spectrometry technique, respectively. The results showed that the component of diesel 0# oxidized by S2O8-2 in HCl solution did not change significantly.
Key words: diesel 0#, oxidative desulfurization, gas chromatography - mass spectrometry.
目 录
1 前言 3
2 实验部分 3
2.1 仪器与试剂 3
2.2 仪器分析条件 3
2.3 实验方法 3
3 结果与讨论 4
3.1 色谱图 4
3.2 0#柴油成分分析 4
3.3 氧化处理后的柴油成分分析 11
结 论 22
参 考 文 献 23
致 谢 24
1 前言
我国市售的燃料柴油中含硫量较高，柴油燃烧后生成的SOx排放到大气中形成酸雨，酸雨是困扰全球各个国家难以解决的环境问题之一，对植被及建筑物均有破坏，对人体健康也会造成极大的伤害。目前存在的脱硫方法主要有催化加氢脱硫[1,2]、氧化脱硫[3-5]、吸附脱硫[6,7]、生物催化脱硫[8-11]、萃取脱硫[12,13]等诸多方法。其中氧化脱硫技术是用氧化剂在催化剂的作用下噻吩类硫化物氧化为相应的砜或亚砜，再用精溜、溶剂萃取或吸附等方法分离出砜或亚砜，从而到脱硫的目的目前石化工业对于柴油的脱硫有加氢脱硫与非加氢脱硫两类，加氢脱硫技术在柴油脱硫工业上有着广泛的应用，相比较于其他的方法，此方法是比较成熟的，但是由于深度加氢会耗氢量增加，反应容器的要求更加苛刻，生产成本提高，所以需要开发一种更加有效的脱硫方法。氧化脱硫具有操作简单，投资少，在常温常压下便可以进行，具有良好的应用前景。氧化脱硫可以使柴油中的含有的硫以极性硫砜的形式除去，故氧化脱硫是面向21世界的绿色脱硫方法，成为目前脱硫研究热点。
本文采用(NH4)2S2O8-HCl脱硫剂氧化柴油，然后采用气相色谱-质谱方法研究了柴油氧化前后的成份变化。
2 实验部分
2.1 仪器与试剂
37％HCl；10% (NH4)2S2O8；N，N-二甲基甲酰胺，试剂均为分析纯。恒温水浴锅；磁力搅拌器； GC—MS一2010 Ultra气-质联用仪(岛津公司)。
2.2 仪器分析条件
色谱柱使用的是Rtx-1ms弹性石英毛细管柱,内径为0.25毫米，柱长为30.0米,膜厚为0.25μm。 色谱柱的开始温度为40℃开始保持8分钟， 12℃每分钟升到300℃保持5分钟， 进样口的温度为300℃， 分流的进样比为50:1 ，进样的量为0.20μL， 柱流量的每分钟为0.88ml 。
质谱的离子源温度为 200℃， 接口温度为200℃， 溶剂的切出的时间为3min， 检测器的电压为1000伏 ，扫描的范围为30-1000。
2.3 实验方法
将10.00ml37％HCl，10.00ml 10%(NH4)2S2O8，0#柴油10ml同时加入圆底烧瓶中，置于恒温水浴锅中，保持水浴的温度为35℃不变，在磁力搅拌的作用下反应2h，反应结束后，取出圆底烧瓶中的反应物在室温下静置，分出油相，用10ml水分别萃取3次，然后用N，N-二甲基甲酰胺10ml分别萃取3次，取出上层清液1ml，用三氯甲烷稀释10倍，取0.20l按2.2仪器分析条件，用气质联用仪和气相色谱仪定性分析。
3 结果与讨论
3.1 色谱图
0#柴油样品经氧化处理前后的色谱图见图1和图2，可以从图中看出，柴油被处理前后的主要成分并未发生出明显的改变。
图1 0#柴油原油谱图
图2 0#柴油氧化后谱图
3.2 0#柴油的成份分析
未经过氧化处理的0#柴油经过质谱检索得到的主要成分见下表1，从表1中可以发现，共检出99种有机物质，其中烷烃26种，烯和炔烃共5种，其它的有机物有68种，其主要成分为C2-C19烃类物质。
表1 0#柴油的主要成分分析
No. 相似度 | 保留时间(min) | 分子式 | 分子结构 |
1 75 | 3.025 | C2H6N2O | |
2 75 | 7.039 | C18H38N2 | |
3 70 | 8.735 | C2H6N4O2 | |
4 75 | 10.166 | C18H38N2 | |
5 74 | 10.395 | C18H38N2 | |
6 72 | 10.705 | C9H18 | |
7 88 | 11.304 | C9H20 | |
8 70 | 11.965 | C11H22 | |
9 77 | 12.270 | C19H40 | |
10 75 | 12.435 | C19H40 | |
11 68 | 12.530 | C11H14O2 | |
12 75 | 12.950 | C19H40 | |
13 78 | 13.015 | C19H40 | |
14 77 | 13.155 | C11H24 | |
15 72 | 13.281 | C11H14O2 | |
16 71 | 13.380 | C10H18O | |
17 67 | 13.685 | C4H6N2O | |
18 93 | 13.785 | C10H22 | |
19 66 | 13.855 | C11H14O2 | |
20 66 | 13.920 | C18H38N2 | |
21 60 | 13.990 | C18H38N2 | |
22 81 | 14.275 | C11H24 | |
23 73 | 14.330 | C12H24O | |
24 74 | 14.420 | C12H22O | |
25 69 | 14.505 | C38H32O5 | |
26 71 | 14.575 | C12H25Cl | |
27 77 | 14.690 | C15H28 | |
28 66 | 14.785 | C36H46O8 | |
29 77 | 14.915 | C11H22O | |
30 73 | 14.975 | C10H20O | |
31 78 | 15.035 | C9H19Br | |
32 77 | 15.145 | C9H19Br | |
33 75 | 15.330 | C11H22O | |
34 70 | 15.475 | C10H16O | |
35 93 | 15.640 | C11H24 | |
36 67 | 15.735 | C10H16O | |
37 69 | 16.010 | C10H18O2 | |
38 73 | 16.110 | C20H41Cl | |
39 68 | 16.160 | C13H12N2 | |
40 73 | 16.230 | C17H33Cl | |
41 70 | 16.315 | C10H13N3 | |
42 68 | 16.415 | C22H32O2 | |
43 79 | 16.530 | C10H12O | |
44 75 | 16.600 | C10H22O | |
45 82 | 16.665 | C10H22 O | |
46 76 | 16.765 | C20H41Cl | |
47 75 | 16.980 | C17H32 | |
48 91 | 17.185 | C12H26 | |
49 85 | 17.410 | C19H40 | |
50 75 | 17.525 | C14H16O2 | |
51 73 | 17.885 | C11H16O | |
52 77 | 17.945 | C14H16O2 | |
53 78 | 18.020 | C12H24O | |
54 78 | 18.080 | C10H20O | |
55 78 | 18.170 | C12H24Br2 | |
56 72 | 18.230 | C10H22 | |
57 75 | 18.420 | C17H32 | |
58 93 | 18.545 | C13H28 | |
59 70 | 18.635 | C27H46 | |
60 72 | 18.925 | C22H32O2 | |
61 75 | 19.295 | C14H16O2 | |
62 75 | 19.360 | C10H20O | |
63 74 | 19.440 | C12H24Br2 | |
64 74 | 19.545 | C15H32 | |
65 92 | 19.790 | C14H30 | |
66 70 | 19.860 | C28H44O4 | |
67 71 | 19.930 | C22H32O3 | |
68 81 | 20.370 | C17H33Cl | |
69 72 | 20.420 | C8H16O |
|
70 81 | 20.545 | C16H32O3 | |
71 76 | 20.625 | C10H20O | |
72 92 | 20.945 | C15H32 | |
73 69 | 21.105 | C13H19NO | |
74 61 | 21.145 | C12H18O2 | |
75 71 | 21.470 | C13H17NO | |
76 67 | 21.540 | C16H32Cl | |
77 71 | 21.585 | C20H41Cl | |
78 73 | 21.650 | C18H36O3 | |
79 73 | 21.725 | C11H22O | |
80 93 | 22.025 | C16H34 | |
81 84 | 22.571 | C16H34 | |
82 75 | 22.635 | C20H42O | |
83 72 | 22.687 | C13H17NO | |
84 71 | 22.770 | C20H36O4 | |
85 64 | 22.975 | C7H5N5O3 | |
86 91 | 23.050 | C16H34 | |
87 84 | 23.155 | C15H32 | |
88 74 | 23.675 | C20H36O4 | |
89 91 | 24.020 | C19H40 | |
90 84 | 24.159 | C15H35 | |
91 72 | 24.619 | C16H34O | |
92 89 | 24.940 | C16H34 | |
93 71 | 25.320 | C8H17N | |
94 70 | 25.585 | C8H15N | |
95 87 | 25.820 | C19H40 | |
96 84 | 26.660 | C24H50 | |
97 82 | 27.460 | C20H42 | |
98 74 | 28.230 | C6H17N3 | |
99 72 | 28.967 | C6H17N3 |
3.3 氧化处理后的柴油成分分析
经过氧化处理后的0#柴油经过仪器质谱检索出的主要成分下见表2，可以从表2中得出，共被检测出有130种物质，其中烷烃44种，烯烃和炔烃共有4种，其它有机物共有86种，其主要成分为C2-C19烃类物质。
表2 处理后的0#柴油的主要成分分析
No. 相似度 | 保留时间(min) | 分子式 | 分子结构 |
1 73 | 3.695 | C2H6N4O2 | |
2 76 | 3.864 | CH5N3O | |
3 73 | 4.130 | C2H6N4O2 | |
4 73 | 5.120 | C7H9N3O | |
5 77 | 5.860 | C2H6N4O2 | |
6 75 | 7.075 | C2H6N2O | |
7 72 | 8.495 | C16H34N2 | |
8 70 | 8.740 | C2H6N4O2 | |
9 74 | 9.825 | C2H6N4O2 | |
10 77 | 10.180 | C16H34N2 | |
11 74 | 10.410 | C18H38N2 | |
12 70 | 10.725 | C18H38N2 | |
13 89 | 11.319 | C9H20 | |
14 70 | 11.975 | C11H22 | |
15 76 | 12.055 | C16H34N2 | |
16 71 | 12.110 | C2H6N4O2 | |
17 75 | 12.165 | C2H6N4O2 | |
18 80 | 12.280 | C19H40 | |
19 77 | 12.445 | C19H40 | |
20 65 | 12.550 | C11H17NO |
|
21 71 | 12.630 | C2H6N4O2 | |
22 77 | 12.960 | C9H20 |
|
23 82 | 13.025 | C19H40 | |
24 80 | 13.170 | C10H22 | |
25 69 | 13.301 | C9H12O2 | |
26 72 | 13.391 | C4H6N2O | |
27 69 | 13.695 | C4H6N2O | |
28 94 | 13.790 | C10H22 | |
29 66 | 13.870 | C2H5N3O2 | |
30 68 | 13.930 | C4H6N2O | |
31 66 | 13.990 | C2H5N3O2 | |
32 73 | 14.100 | C18H38N2 | |
33 85 | 14.181 | C11H24 | |
34 75 | 14.284 | C11H22 | |
35 75 | 14.340 | C18H38N2 | |
36 75 | 14.384 | C4H6N2O | |
37 67 | 14.425 | C18H38N2 | |
38 73 | 14.580 | C19H40 | |
39 74 | 14.700 | C20H40O2 | |
40 66 | 14.809 | C4H6N2O | |
41 80 | 14.925 | C19H40 | |
42 78 | 14.980 | C12H24 | |
43 79 | 15.040 | C11H24 | |
44 78 | 15.150 | C10H22O | |
45 73 | 15.340 | C4H6N2O | |
46 69 | 15.485 | C8H15N | |
47 72 | 15.546 | C4H6N2O | |
48 94 | 15.645 | C11H24 | |
49 72 | 15.745 | C14H26O2 | |
50 69 | 16.015 | C13H24 | |
51 75 | 16.120 | C7H14O | |
52 67 | 16.166 | C14H18O2 | |
53 73 | 16.236 | C8H15N | |
54 70 | 16.325 | C10H13N3 | |
55 65 | 16.422 | C8H8N2O2 | |
56 75 | 16.541 | C16H33Cl | |
57 75 | 16.604 | C12H26 | |
58 84 | 16.670 | C10H22O | |
59 79 | 16.765 | C10H22O | |
60 66 | 16.890 | C36H46O8 | |
61 71 | 16.990 | C10H18O | |
62 76 | 17.035 | C11H22O | |
63 92 | 17.190 | C12H26 | |
64 88 | 17.414 | C19H40 | |
65 71 | 17.550 | C10H18O | |
66 72 | 17.626 | C4H6N2O | |
67 73 | 17.720 | C11H22O | |
68 74 | 17.765 | C8H15N | |
69 68 | 17.890 | C11H16O | |
70 78 | 17.955 | C10H22O |
|
71 79 | 18.021 | C10H22O | |
72 81 | 18.084 | C10H22O | |
73 82 | 18.174 | C20H42 | |
74 79 | 18.235 | C10H22 | |
75 74 | 18.350 | C8H15N | |
76 74 | 18.424 | C8H15N | |
77 94 | 18.550 | C13H28 | |
78 68 | 18.642 | C27H46 | |
79 70 | 18.720 | C26H30O | |
80 78 | 18.800 | C19H40 | |
81 68 | 18.931 | C36H46O8 | |
82 65 | 19.090 | C10H20O2 | |
83 80 | 19.201 | C19H40 | |
84 73 | 19.236 | C19H40 | |
85 77 | 19.300 | C7H14O | |
86 81 | 19.365 | C20H42 | |
87 80 | 19.445 | C19H40 |
|
88 82 | 19.550 | C15H32 | |
89 76 | 19.725 | C8H15N | |
90 93 | 19.790 | C14H30 | |
91 74 | 19.865 | C19H40 | |
92 71 | 19.932 | C28H46O | |
93 71 | 20.216 | C8H15N | |
94 83 | 20.370 | C20H42O | |
95 75 | 20.420 | C19H40 | |
96 76 | 20.485 | C19H40 | |
97 85 | 20.550 | C15H32 | |
98 78 | 20.628 | C20H36O4 | |
99 75 | 20.770 | C8H15N | |
100 93 | 20.945 | C16H34 | |
101 72 | 21.070 | C7H14O | |
102 68 | 21.150 | C4H13N3 | |
103 76 | 21.475 | C19H40 | |
104 78 | 21.530 | C11H22O | |
105 74 | 21.586 | C19H40 | |
106 78 | 21.651 | C19H40 | |
107 76 | 21.725 | C19H40 | |
剩余内容已隐藏，请支付后下载全文，论文总字数：12382字
您需要先支付 80元 才能查看全部内容！立即支付
该课题毕业论文、开题报告、外文翻译、程序设计、图纸设计等资料可联系客服协助查找; 您可能感兴趣的文章
|
