两步催化法制备异松油烯的工艺研究
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摘要
异松油烯是一种价格昂贵的精细化学品，制备高收率的异松油烯有着重要的意义。
本论文是以松节油为原材料，采用两步催化制备异松油烯。第一步催化是松节油在13X钠型分子筛的催化下，获得较高收率的双戊烯和部分异松油烯；通过考察不同条件处理的13X钠型分子筛催化剂的活性，发现分子筛-C-d催化剂的活性最佳。第二步催化是以SO_4~(2-)/ZrO_2固体超强酸为催化剂，使第一步产物中的双戊烯向异松油烯转化，从而获得高收率的异松油烯；不同条件下制备的SO_4~(3-)/ZrO_2固体超强酸有着不同的活性，根据实验知，SO_4~(2-)/ZrO_2-Ⅱ-C-3、SO_4~(2-)/ZrO_2-Ⅱ-D-3催化剂的活性和选择性最佳。
第一步催化反应适宜的工艺条件为：催化剂为分子筛-C-d，催化剂用量为4%，催化剂粒径为30-100目，反应温度为150℃，反应时间为30-60分钟。第二步催化反应适宜的工艺条件为：催化剂为SO_4~(2-)/ZrO_2-Ⅱ-D-3，催化剂用量为4%，反应温度为80℃，反应时间8-12小时。松节油在以上工艺条件下经两步催化后，异松油烯的收率可达35.24%。
Terpinolene is a kind of fine chemicals, and its price is very expensive.lt is important to abtain the high-yield terpinolene.
This paper prepared terpinolene using turpentine as raw material by two-stage catalyze. First, turpentine was inverted to high-yied dipentene and part terpinolene using 13X molecular sieve as catalyst.lt was found that catalyst , Molecular sieve-C-d, had optimum activity by inspecting the activity of 13X molecular sieve with different handling conditions. Second,dipentene in the first-stage products was inverted to terpinolene using SO427ZrO2 solid superacid as catalyst.so as to obtain the high-yield terpinolene.The SO42YZrO2 solid superacid catalyst which was prepared in different conditions had different activity.According to experiment ,the SO42YZrO2 - n -C-3 solid superacid catalyst and the SO42YZrO2-II-D-3 solid superacid catalyst had both optimum activity and optimum selectivity.
The appropriate technology conditions in the first-stage reaction were as follows: catalyst was Molecular sieve-C-d, the ratio of catalyst and raw material was 4: 100, the diameter of catalyst was 30-100 cohorts, the reaction-temperature was 150, the reaction-time was 30-60 minutes. The appropriate technology conditions in the second-stage reaction were as follows: catalyst was SO427ZrO2-II-D-3 solid superacid catalyst, the ratio of catalyst and raw material was 4: 100, the reaction-temperature was 80, the reaction-time was 8-12 hours. Under the techonology conditions as the above, the yield of terpinolene can reach 35.24% by two-stage catalyzing turpentine.
本论文是以松节油为原材料，采用两步催化制备异松油烯。第一步催化是松节油在13X钠型分子筛的催化下，获得较高收率的双戊烯和部分异松油烯；通过考察不同条件处理的13X钠型分子筛催化剂的活性，发现分子筛-C-d催化剂的活性最佳。第二步催化是以SO_4~(2-)/ZrO_2固体超强酸为催化剂，使第一步产物中的双戊烯向异松油烯转化，从而获得高收率的异松油烯；不同条件下制备的SO_4~(3-)/ZrO_2固体超强酸有着不同的活性，根据实验知，SO_4~(2-)/ZrO_2-Ⅱ-C-3、SO_4~(2-)/ZrO_2-Ⅱ-D-3催化剂的活性和选择性最佳。
第一步催化反应适宜的工艺条件为：催化剂为分子筛-C-d，催化剂用量为4%，催化剂粒径为30-100目，反应温度为150℃，反应时间为30-60分钟。第二步催化反应适宜的工艺条件为：催化剂为SO_4~(2-)/ZrO_2-Ⅱ-D-3，催化剂用量为4%，反应温度为80℃，反应时间8-12小时。松节油在以上工艺条件下经两步催化后，异松油烯的收率可达35.24%。
Terpinolene is a kind of fine chemicals, and its price is very expensive.lt is important to abtain the high-yield terpinolene.
This paper prepared terpinolene using turpentine as raw material by two-stage catalyze. First, turpentine was inverted to high-yied dipentene and part terpinolene using 13X molecular sieve as catalyst.lt was found that catalyst , Molecular sieve-C-d, had optimum activity by inspecting the activity of 13X molecular sieve with different handling conditions. Second,dipentene in the first-stage products was inverted to terpinolene using SO427ZrO2 solid superacid as catalyst.so as to obtain the high-yield terpinolene.The SO42YZrO2 solid superacid catalyst which was prepared in different conditions had different activity.According to experiment ,the SO42YZrO2 - n -C-3 solid superacid catalyst and the SO42YZrO2-II-D-3 solid superacid catalyst had both optimum activity and optimum selectivity.
The appropriate technology conditions in the first-stage reaction were as follows: catalyst was Molecular sieve-C-d, the ratio of catalyst and raw material was 4: 100, the diameter of catalyst was 30-100 cohorts, the reaction-temperature was 150, the reaction-time was 30-60 minutes. The appropriate technology conditions in the second-stage reaction were as follows: catalyst was SO427ZrO2-II-D-3 solid superacid catalyst, the ratio of catalyst and raw material was 4: 100, the reaction-temperature was 80, the reaction-time was 8-12 hours. Under the techonology conditions as the above, the yield of terpinolene can reach 35.24% by two-stage catalyzing turpentine.
引文
[1]刘玉春．美国松节油的生产利用和市场．林产化工通讯，1992(6)：34～37
[2]刘玉春．世界松节油的生产和消费．林产化工通讯，1998(1)：14
[3]陈舒．松节油销势由旺转疲．林产化工通讯，1998(1)：46
[4]刘玉春摘译．美国松节油二次加工的趋向．林产化工通讯，1993(2)：41
[5]韩太保等．松香和松节油综合利用的发展动态．化学通讯，1986(1)：986
[6]林业部林产工业公司松香、松节油再加工产品市场调查组．松香、松节油再加工产品市场调查报告．林产化工通讯，1990，24(4)：5～11
[7]荣德美．相转移催化剂在合成松油醇中的应用．林产化工通讯，1996(2)：15
[8]黄永平．我国松节油深加工开发的里程碑．林产化学与工业，1985，5(2)：31
[9]游晴如．莰烯在合成香料中的应用．林产化工通讯，1996(3)：24
[10]Goryaev M I, Battalova Sh B.U.S.S. R, 418 460
[11]I. Battalova Sh B, Mukitanova T R. Izv. Akad. Nauk Kaz. SSR. Ser. Khim., 1975,25(4): 49-52
[12]Gorgaev M I, Artamonov A F. Vestn. Aakad. Nauk Kaz SSR, 1975, (3): 59-62
[13]Popov A A. Gidroliz. Lesokhim.Prom-st, 1979, (6): 18-20
[14]Battalova Sh B. Gidroliz Lesokhim Promst, 1984, (2): 8-9
[15]Ohnishi Ryuichiro. Z. Phys. Chem., 1982, 130 (2): 205-209
[16]Yasuhara Yushi Kogyo Co. Ltd, J.P., 58 26 826
[17]Plate A F, Milvitskaya E M. Izv. Vyssh. Ucheb. Zaved. Khim. Tekhnol., 1967,10 (12): 1340-1344
[18]SCM Corp. Neth. Appl., 74 03 89
[19]Kaiser Gregory L. U.S., 3 974 103
[20]Kaiser Gregory L.U.S., 3 974 102
[21]高南，戴金山等，涂料工业，1978，(6)：7
[22]张晋康，王文龙等，南京林业大学学报，1990，14(3)；27
[23]王文龙，张晋康．南京林业大学学报，1990，14(3)：32-36
[24]Ryuichro Ohnishi. Bull. Chem. Soc. Jap., 1974, 47 (3): 571
[25]Edward Andrew Takacs. U. S., 3 700 747
[26]Morikawa Toshiyuki Jpn. KoKai Tokkyo Koho JP 01, 319, 413
[27]Tsunehiro Tanaka Journal Of Catalysis 122, 384-388 (1990)
[28]王发石等，林产化学与工业，1996，16(3)：32
[29]曾健青等．SO_4~(2-)/MxOy型固体超强酸催化剂的研究进展．石油化工，1994，23(3)：191～195
[30]荒田一志．石油化工译从，1992(1)：9
[31]于世涛，高根云，杨锦宗．硫酸或金属氧化物负载的固体超强酸的制备及其在有机合成中的应用研究发展．化工进展，1995(9)：17～19
[32]曾健青，钟炳．用程序升温氨脱附研究SO_4~(2-)/ZrO_2超强酸催化剂的酸性质．石油化工，1998，27(3)：168
[33]黄碧纯，黄仲涛等．超强酸催化剂SO_4~2-MoO_3-ZrO_2的制备与表征．精细石油化工，1996(4)：34
[34]Matsuhashi H.Tanabe K ed. Proc intern symp acidbase catal, Sappora,1988,Tokyo: Kodansha, 1989:357
[35]Srinirasom R, Davis B H.Preprints. 1991,36 (4): 635
[36]庸新硕．固体超强酸催化剂研究进展．石油化工，1984，13(4)：284
[37]伍忠萌．固体超强酸及其在松香、松节油深加工中应用潜力．林产化工通讯，1996(4)：36～37．
[38]华伟明，陈建民等．流动指示剂法表征固体超强酸强度．石油化工，1995，24(6)：385
[39]荒田一志，日野诚．触媒，1982，24(3)：241
[40]Tanabe K, Misono M, Ono Y et al.New Solid Acids and Basws. Kodansha, Tokyo, 1989:6-7
[41]Parera J M. Catal Taday, 1992, 15:481
[42]Wen M Y, Wender I, Tierney J W. Energy and Fuels, 1990, 4:372
[43]姚胜．化学通报，1990，2；23
[2]刘玉春．世界松节油的生产和消费．林产化工通讯，1998(1)：14
[3]陈舒．松节油销势由旺转疲．林产化工通讯，1998(1)：46
[4]刘玉春摘译．美国松节油二次加工的趋向．林产化工通讯，1993(2)：41
[5]韩太保等．松香和松节油综合利用的发展动态．化学通讯，1986(1)：986
[6]林业部林产工业公司松香、松节油再加工产品市场调查组．松香、松节油再加工产品市场调查报告．林产化工通讯，1990，24(4)：5～11
[7]荣德美．相转移催化剂在合成松油醇中的应用．林产化工通讯，1996(2)：15
[8]黄永平．我国松节油深加工开发的里程碑．林产化学与工业，1985，5(2)：31
[9]游晴如．莰烯在合成香料中的应用．林产化工通讯，1996(3)：24
[10]Goryaev M I, Battalova Sh B.U.S.S. R, 418 460
[11]I. Battalova Sh B, Mukitanova T R. Izv. Akad. Nauk Kaz. SSR. Ser. Khim., 1975,25(4): 49-52
[12]Gorgaev M I, Artamonov A F. Vestn. Aakad. Nauk Kaz SSR, 1975, (3): 59-62
[13]Popov A A. Gidroliz. Lesokhim.Prom-st, 1979, (6): 18-20
[14]Battalova Sh B. Gidroliz Lesokhim Promst, 1984, (2): 8-9
[15]Ohnishi Ryuichiro. Z. Phys. Chem., 1982, 130 (2): 205-209
[16]Yasuhara Yushi Kogyo Co. Ltd, J.P., 58 26 826
[17]Plate A F, Milvitskaya E M. Izv. Vyssh. Ucheb. Zaved. Khim. Tekhnol., 1967,10 (12): 1340-1344
[18]SCM Corp. Neth. Appl., 74 03 89
[19]Kaiser Gregory L. U.S., 3 974 103
[20]Kaiser Gregory L.U.S., 3 974 102
[21]高南，戴金山等，涂料工业，1978，(6)：7
[22]张晋康，王文龙等，南京林业大学学报，1990，14(3)；27
[23]王文龙，张晋康．南京林业大学学报，1990，14(3)：32-36
[24]Ryuichro Ohnishi. Bull. Chem. Soc. Jap., 1974, 47 (3): 571
[25]Edward Andrew Takacs. U. S., 3 700 747
[26]Morikawa Toshiyuki Jpn. KoKai Tokkyo Koho JP 01, 319, 413
[27]Tsunehiro Tanaka Journal Of Catalysis 122, 384-388 (1990)
[28]王发石等，林产化学与工业，1996，16(3)：32
[29]曾健青等．SO_4~(2-)/MxOy型固体超强酸催化剂的研究进展．石油化工，1994，23(3)：191～195
[30]荒田一志．石油化工译从，1992(1)：9
[31]于世涛，高根云，杨锦宗．硫酸或金属氧化物负载的固体超强酸的制备及其在有机合成中的应用研究发展．化工进展，1995(9)：17～19
[32]曾健青，钟炳．用程序升温氨脱附研究SO_4~(2-)/ZrO_2超强酸催化剂的酸性质．石油化工，1998，27(3)：168
[33]黄碧纯，黄仲涛等．超强酸催化剂SO_4~2-MoO_3-ZrO_2的制备与表征．精细石油化工，1996(4)：34
[34]Matsuhashi H.Tanabe K ed. Proc intern symp acidbase catal, Sappora,1988,Tokyo: Kodansha, 1989:357
[35]Srinirasom R, Davis B H.Preprints. 1991,36 (4): 635
[36]庸新硕．固体超强酸催化剂研究进展．石油化工，1984，13(4)：284
[37]伍忠萌．固体超强酸及其在松香、松节油深加工中应用潜力．林产化工通讯，1996(4)：36～37．
[38]华伟明，陈建民等．流动指示剂法表征固体超强酸强度．石油化工，1995，24(6)：385
[39]荒田一志，日野诚．触媒，1982，24(3)：241
[40]Tanabe K, Misono M, Ono Y et al.New Solid Acids and Basws. Kodansha, Tokyo, 1989:6-7
[41]Parera J M. Catal Taday, 1992, 15:481
[42]Wen M Y, Wender I, Tierney J W. Energy and Fuels, 1990, 4:372
[43]姚胜．化学通报，1990，2；23