表面改性的活性炭在合成乙二醇反应中的应用研究
摘要
本论文首次在环氧乙烷水合反应中，引入表面改性的活性
炭作为多相催化剂，并对经磺化改性的石油焦活性炭在反应中
的催化性能进行了系统的研究。
结果表明，磺化石油焦活性炭对环氧乙烷水合反应有很高
的活性和乙二醇选择性。其活性大小依次为：25℃磺化的石油
焦活性炭≈50℃磺化的石油焦活性炭＞100℃磺化的石油焦活性
炭＞150℃磺化的石油焦活性炭＞200℃磺化的石油焦活性炭＞
230℃磺化的石油焦活性炭，因此磺化温度对石油焦活性炭的活
性有一定的影响，低温磺化比高温磺化的效果好；并且随着磺
化温度的上升，石油焦活性炭的酸中心数逐渐增多，而活性却
逐渐减弱，说明环氧乙烷水合反应只适于弱酸催化；反应温度
对石油焦活性炭的性能影响最大，随着反应温度的升高，催化
剂活性是快速增强的，但超过一定温度范围后，活性还有所减
弱；石油焦活性炭的活性还随反应压力的增大而加强，压力超
过一定值时，乙二醇的选择性会降低；空速的增加也会引起石
油焦活性炭的活性减弱。
实验中也对木质活性炭进行了考查，发现其对环氧乙烷水
合反应也有很好的活性，有待进一步的研究。
Applied Study on the Superficial Transformation of Active
Carbon in the Hydration of Ethylene Oxide to Ethylene Glycol
ABSTRACT
In this paper , the superficial transformation of active
carbon , the sulfonated petroleum coke is firstly used to synthesize
ethylene glycol (EG) by hydration of ethylene oxide (EO) , and the
catalysis of sulfonated petroleum coke (SPC) is studied.
The results indicate that SPE has high activity and good
selectivity of EG in hydration reaction of EO . And sulfonation
temperature has a certain effect on the activity of SPC , the higher
the temperature , the feebler the activity , thus when petroleum
coke is sulfonated in low temperature , its activity will be better
than in high temperature ; Moreover, alone with the sulfonation
temperature ascending , the number of acid-site of SPC gradually
increase , but the activity wears off, it also shows that weak acid
catalyst is more sutible for hydration reaction of EO ; In addition,
the effect of reactive temperature on the activity of SPC is greatest,
when reactive temperature going up , the activity of SPC is
speedily enhanced , but when temperature exceeds a certain range,
the activity of SPC will reduce ; And the activity of SPC will
become stronger alone with reactive pressure rising , but when
pressure exceeds a certain value , selectivity of EG will decrease
Also , increasing airspeed will weaken the activity of SPC.
Abstract
At the same time , through investigating the catalysis of
woodiness active carbon , the results show that it also has good
activity in the hydration reaction of EO to EG , but that awaits for
further studying.
炭作为多相催化剂，并对经磺化改性的石油焦活性炭在反应中
的催化性能进行了系统的研究。
结果表明，磺化石油焦活性炭对环氧乙烷水合反应有很高
的活性和乙二醇选择性。其活性大小依次为：25℃磺化的石油
焦活性炭≈50℃磺化的石油焦活性炭＞100℃磺化的石油焦活性
炭＞150℃磺化的石油焦活性炭＞200℃磺化的石油焦活性炭＞
230℃磺化的石油焦活性炭，因此磺化温度对石油焦活性炭的活
性有一定的影响，低温磺化比高温磺化的效果好；并且随着磺
化温度的上升，石油焦活性炭的酸中心数逐渐增多，而活性却
逐渐减弱，说明环氧乙烷水合反应只适于弱酸催化；反应温度
对石油焦活性炭的性能影响最大，随着反应温度的升高，催化
剂活性是快速增强的，但超过一定温度范围后，活性还有所减
弱；石油焦活性炭的活性还随反应压力的增大而加强，压力超
过一定值时，乙二醇的选择性会降低；空速的增加也会引起石
油焦活性炭的活性减弱。
实验中也对木质活性炭进行了考查，发现其对环氧乙烷水
合反应也有很好的活性，有待进一步的研究。
Applied Study on the Superficial Transformation of Active
Carbon in the Hydration of Ethylene Oxide to Ethylene Glycol
ABSTRACT
In this paper , the superficial transformation of active
carbon , the sulfonated petroleum coke is firstly used to synthesize
ethylene glycol (EG) by hydration of ethylene oxide (EO) , and the
catalysis of sulfonated petroleum coke (SPC) is studied.
The results indicate that SPE has high activity and good
selectivity of EG in hydration reaction of EO . And sulfonation
temperature has a certain effect on the activity of SPC , the higher
the temperature , the feebler the activity , thus when petroleum
coke is sulfonated in low temperature , its activity will be better
than in high temperature ; Moreover, alone with the sulfonation
temperature ascending , the number of acid-site of SPC gradually
increase , but the activity wears off, it also shows that weak acid
catalyst is more sutible for hydration reaction of EO ; In addition,
the effect of reactive temperature on the activity of SPC is greatest,
when reactive temperature going up , the activity of SPC is
speedily enhanced , but when temperature exceeds a certain range,
the activity of SPC will reduce ; And the activity of SPC will
become stronger alone with reactive pressure rising , but when
pressure exceeds a certain value , selectivity of EG will decrease
Also , increasing airspeed will weaken the activity of SPC.
Abstract
At the same time , through investigating the catalysis of
woodiness active carbon , the results show that it also has good
activity in the hydration reaction of EO to EG , but that awaits for
further studying.
引文
1.PCT WO 85 04 392
2.PCT WO 85 04 406
3.US 4 760 200
4.EP 156 447
5.JP 85 61 545
6.Haruo Mastuda Complete Control of Product Distribution in the Hydration of Ethylene Oxide with Organatimony Compounds as Catalyst Ind. Eng. Chem. Prod. Res. Dev.23 (3), 422-425 (1984)
7.JP 82 139 026
8.UK 2 083 026
9.JP 81 92 228
10.JP 81 90 029
11.JP 81 71 028
12.JP 81 71 029
13.JP 81 71 026
14.JP 81 45 426
15.JP 81 73 035
16.JP 81 73 036
17.Showa Denko K.K. Neth. Appl. 78 08 966
18.Ger. Offen. 2 838 030
19.UK 2 023 601
20.US 4 160 116
21.JP 79 19 905
22.Ger. Offen. 2 615 595
23.US 3 992 314
24.Ger. Offen. 2 359 497
25.Ger. Offen. 1 793 246
26.Ger. Offen. 2 141 470
27.US 287 916
28.Brit. UK 1 177 877
29.Belg. 878 902
30.US 4 014 945
31.PCT. WO 95 20 559
32.JP 87 116 530
33.JP 87 126 145
34.JP 87 116 528
35.US 4 701 571
36.J.R.Briggs,SELECTIVE ETHYLENE OXIDE HYDROLYSIS CATALYSED BY OXO-MOLYBDENUM SPECIES Polyhedron 5(1-3),281-7(Eng.1986)
37.US 4 620 044
38.EP 156 449
39.PCT. WO 85 04 393
40.EP 156 446
41.JP 84 82 325
42.US 4 393 254
43.JP 81 118 024
44.Czech. 176 699
45.US 4 165 440
46.R. Boeva, HYDRATION OF EO IN THE PRESENCE OF CATION EXCHANGERS Khim. Ind. 49(2), 78~9(Bulg. 1977)
47.Japan Kokai 7322 406
48.EP 156 448
49.JP 94 336 463
50.N. Iranpoor, Tris[tyinitrate Ce(IV)]paraperiodate,an efficent heterogeneous catalyst for alcoholysis,acetolysis and hydrolysis of epoxides Synth. Commun.,24(14), 1959-1969, (Eng. 1994)
51.N.N. Lebedev, Study of the Selectivity of α-Oxide Hydrolysis during Catalysis by Carbonate Salts Kinet Katal 1971,17(3),583-8, (Russ.)
52.N.N. Lebedev, Kinetics and Mechanicm of the Hydrolysis of α-Oxide during Catalysis by Carbonate Salts Kinet Katal 1971,17(3),576-82, (Russ.)
53.US 2 807 651
54.JP 57 139 026
55．宋冠秦，我国乙二醇的生产及需求，《现代化工》，12，39-40(1995)
56．宋丽萍，乙二醇的合成与展望，《广州化学》，3，50-55(1993)
57．沈景余，世界环氧乙烷、乙二醇生产现状及技术进展，《石油化工》，23(9)，611-617(1994)
58．陈乐怡，乙烯直接氧化工艺中乙烯碳酸酯法制备乙二醇的国外科技动态，《燕山油化》，3，221-232(1984)
59．胥勃等，杂多酸(盐)——一种多用途的催化剂，《化学通报》，4，34-39(1985)
60．郑宁来，乙二醇的发展趋势，《石油化工》，17(12)，821-827(1988)
61．张玉宝，大连理工大学硕士学位论文，1997
62．周斌，大连理工大学硕士学位论文，1998
63．王晓平，大连理工大学硕士学位论文，1998
2.PCT WO 85 04 406
3.US 4 760 200
4.EP 156 447
5.JP 85 61 545
6.Haruo Mastuda Complete Control of Product Distribution in the Hydration of Ethylene Oxide with Organatimony Compounds as Catalyst Ind. Eng. Chem. Prod. Res. Dev.23 (3), 422-425 (1984)
7.JP 82 139 026
8.UK 2 083 026
9.JP 81 92 228
10.JP 81 90 029
11.JP 81 71 028
12.JP 81 71 029
13.JP 81 71 026
14.JP 81 45 426
15.JP 81 73 035
16.JP 81 73 036
17.Showa Denko K.K. Neth. Appl. 78 08 966
18.Ger. Offen. 2 838 030
19.UK 2 023 601
20.US 4 160 116
21.JP 79 19 905
22.Ger. Offen. 2 615 595
23.US 3 992 314
24.Ger. Offen. 2 359 497
25.Ger. Offen. 1 793 246
26.Ger. Offen. 2 141 470
27.US 287 916
28.Brit. UK 1 177 877
29.Belg. 878 902
30.US 4 014 945
31.PCT. WO 95 20 559
32.JP 87 116 530
33.JP 87 126 145
34.JP 87 116 528
35.US 4 701 571
36.J.R.Briggs,SELECTIVE ETHYLENE OXIDE HYDROLYSIS CATALYSED BY OXO-MOLYBDENUM SPECIES Polyhedron 5(1-3),281-7(Eng.1986)
37.US 4 620 044
38.EP 156 449
39.PCT. WO 85 04 393
40.EP 156 446
41.JP 84 82 325
42.US 4 393 254
43.JP 81 118 024
44.Czech. 176 699
45.US 4 165 440
46.R. Boeva, HYDRATION OF EO IN THE PRESENCE OF CATION EXCHANGERS Khim. Ind. 49(2), 78~9(Bulg. 1977)
47.Japan Kokai 7322 406
48.EP 156 448
49.JP 94 336 463
50.N. Iranpoor, Tris[tyinitrate Ce(IV)]paraperiodate,an efficent heterogeneous catalyst for alcoholysis,acetolysis and hydrolysis of epoxides Synth. Commun.,24(14), 1959-1969, (Eng. 1994)
51.N.N. Lebedev, Study of the Selectivity of α-Oxide Hydrolysis during Catalysis by Carbonate Salts Kinet Katal 1971,17(3),583-8, (Russ.)
52.N.N. Lebedev, Kinetics and Mechanicm of the Hydrolysis of α-Oxide during Catalysis by Carbonate Salts Kinet Katal 1971,17(3),576-82, (Russ.)
53.US 2 807 651
54.JP 57 139 026
55．宋冠秦，我国乙二醇的生产及需求，《现代化工》，12，39-40(1995)
56．宋丽萍，乙二醇的合成与展望，《广州化学》，3，50-55(1993)
57．沈景余，世界环氧乙烷、乙二醇生产现状及技术进展，《石油化工》，23(9)，611-617(1994)
58．陈乐怡，乙烯直接氧化工艺中乙烯碳酸酯法制备乙二醇的国外科技动态，《燕山油化》，3，221-232(1984)
59．胥勃等，杂多酸(盐)——一种多用途的催化剂，《化学通报》，4，34-39(1985)
60．郑宁来，乙二醇的发展趋势，《石油化工》，17(12)，821-827(1988)
61．张玉宝，大连理工大学硕士学位论文，1997
62．周斌，大连理工大学硕士学位论文，1998
63．王晓平，大连理工大学硕士学位论文，1998