由分子氧和环己烯合成己二酸的研究
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摘要
本文为河南省重点科技攻关资助项目(项目编号：523050300)。
己二酸是一种重要的二元脂肪酸，主要用于尼龙-66，聚氨酯等高分子材料的合成。己二酸传统生产工艺存在环境污染问题，而近年新开发的双氧水直接氧化环己烯合成己二酸工艺因双氧水价格高、产品生产成本高之重大缺陷，尚不具有工业应用价值。鉴于烯烃易于与臭氧发生反应之特点，本文间接利用分子氧，将氧气经臭氧发生器使其部分生成臭氧，开辟了一个以环己烯、w(H_2O_2)=30％的双氧水溶液以及氧气为主要原料，经臭氧化及氧化分解反应合成己二酸的新方法。本文开展的主要工作如下：
在臭氧化反应过程，选择以塔高径比为10：1(塔外径为30mm)，气体分布器为G4玻璃砂芯的鼓泡反应塔为臭氧化反应器。考察了溶剂种类、用量、臭氧化时间、臭氧化温度对反应的影响，确定了制备臭氧化中间体的适宜的反应条件，具体为：V(环己烯)：V(乙酸)=1：10(以2.8 mmol，约3ml环己烯计)，反应时间1.5 h，O_2流量200 mL/min，臭氧发生器效率100％，反应温度为5-10℃。
在氧化分解臭氧化中间体合成己二酸过程中，首先采用质量百分浓度w(H_2O_2)=30％的双氧水溶液为氧化剂，开展了氧化分解臭氧化中间体的研究。考察双氧水溶液氧化分解中H_2O_2与环己烯的摩尔比、氧化分解温度、氧化分解时间等因素对合成己二酸反应的影响，确定了H_2O_2氧化分解臭氧化中间体的最佳反应条件，具体为：n(H_2O_2)：n(C_6H_(10))=2.4：1(以2.8 mmol环己烯计)，氧化分解温度为75℃，氧化分解时间为3.5 h时，经三组平行试验检验，产品己二酸的平均收率约80.4％。
双氧水作为氧化剂虽是绿色氧化剂，但成本较高。鉴于此，开展了以氧气为氧源氧化分解臭氧化中间体的研究。探讨了氧化分解温度、氧化分解时间、催化剂种类、催化剂加入量、氧气气速等主要影响因素对氧化分解反应的影响。采用两次正交试验对反应条件进行优化，得出了最佳反应条件为：氧化分解温度为75℃，氧化分解时间为3.5h，钼金属用量1 mmol(折合三氧化钼质量0.144 g)，氧气气速为40 mL/min，己二酸的收率可达到79.5％，乙酸回收收率可达到70％。
本研究特点在于全部采用清洁氧源，以代替现行有重大污染的工业路线。从上述结果看：以O_2为氧源氧化分解所得的己二酸收率虽较H_2O_2略低，但从原料成本上讲O_2为氧源更具有优越性，具有较好的潜在应用前景。
This dissertation was financial supported by the Key Scientific and Technological Project Funds of Henan Province (523050300).
Adipic acid is an important dicarboxylic acid, which mainly in making some of polymers, such as 6,6-nylon, polyurethane and so on. There is pollution problem in the traditional technology of synthesis adipic acid. And in recent years, hydrogen peroxide is used to synthesize adipic acid by oxidating cyclohexene directly. for higher price of H_2O_2, this new technology can not be applied in industry. It is well-known that olefin is easy to react with ozone, so this paper uses O_2 indirectly, some of the O_2 is transformed into O_3 in a ozonizer, this is a new way to synthesize adipic acid with cyclohexene, 30 wt% H_2O_2 and oxygen as raw materials. Main results obtained on research work are as follows:
In the process of the ozonation reaction, the bubble column, whose ratio of column height to diameter was 10 : 1 and the gas distributer was G4 glass sand core, was adopted as the ozonation reaction column. Several factors which influence the ozonation reaction, such as, sorts and volumes of solvent, ozonolysis temperature had been investigated. The proper ozonolysis condition was confirmed, that is, V(C_6H_(10)) : V(C_2H_4O_2)=1:10 (based on 2.8 mmol of cyclohexene, approx 3 ml), ozonolysis time 1.5 h, flux of oxygen 200 mL/min, efficiency of zonator 100 %, ozonolysis temperature 5-10℃.
In the process of synthesis adipic acid by oxygenolysis of the ozonized intermediate, firstly, 30 wt% H_2O_2 was used as oxidant. Effects of some factors were investigated in oxygenolysis of ozonized intermediate, such as, molar ratio of hydrogen proxide to cyclohexene, oxygenolysis temperature and time. The proper oxygenolysis condition was n(H_2O_2) : n(C_6H_(10))=2.4 : 1 (based on 2.8 mmol of cyclohexene), oxygenolysis temperature 75℃, oxygenolysis time 3.5 h. Under this optimum condition, the average yield of adipic acid synthesized by three parallel tests was about 80.4 %.
Although H_2O_2 is an important "green" oxidant, its price is higher than general oxidants. And then oxygen is natural, cheap and rich oxidant, therefore, O_2 was choosed as an oxidant from some oxygen sources in oxygenolysis of the ozonized intermediate. The main factors which influence the reaction, such as, oxygenolysis temperature and time, sorts and weights of catalysts and flux of oxygen. Twice orthognol test was adopted to optimize the reaction conditions, the optimal oxygenolysis condition was as follows: oxygenolysis temperature 75℃, oxygenolysis time 3.5 h, amount of molybdenum in molybdenum trioxydatum 1 mmol, flux of oxygen 40 mL/min. Under the condition, the yield of adipic acid was 79.5 %, the recovery rate of acetic acid was 70 %.
Clean oxidant was used in this work to replace the traditional industry process, which would pollute the environment seriously. The results showed, in oxygenolysis of ozonized intermediate, the yield of adipic acid was synthesized by using O_2 as oxidant is a little lower than that of by using H_2O_2. Considering the cost of oxidants, it is sure that the former is better than the latter, and so technology of O_2 as oxidant possesses more potential foreground in application of industrial fields.
己二酸是一种重要的二元脂肪酸，主要用于尼龙-66，聚氨酯等高分子材料的合成。己二酸传统生产工艺存在环境污染问题，而近年新开发的双氧水直接氧化环己烯合成己二酸工艺因双氧水价格高、产品生产成本高之重大缺陷，尚不具有工业应用价值。鉴于烯烃易于与臭氧发生反应之特点，本文间接利用分子氧，将氧气经臭氧发生器使其部分生成臭氧，开辟了一个以环己烯、w(H_2O_2)=30％的双氧水溶液以及氧气为主要原料，经臭氧化及氧化分解反应合成己二酸的新方法。本文开展的主要工作如下：
在臭氧化反应过程，选择以塔高径比为10：1(塔外径为30mm)，气体分布器为G4玻璃砂芯的鼓泡反应塔为臭氧化反应器。考察了溶剂种类、用量、臭氧化时间、臭氧化温度对反应的影响，确定了制备臭氧化中间体的适宜的反应条件，具体为：V(环己烯)：V(乙酸)=1：10(以2.8 mmol，约3ml环己烯计)，反应时间1.5 h，O_2流量200 mL/min，臭氧发生器效率100％，反应温度为5-10℃。
在氧化分解臭氧化中间体合成己二酸过程中，首先采用质量百分浓度w(H_2O_2)=30％的双氧水溶液为氧化剂，开展了氧化分解臭氧化中间体的研究。考察双氧水溶液氧化分解中H_2O_2与环己烯的摩尔比、氧化分解温度、氧化分解时间等因素对合成己二酸反应的影响，确定了H_2O_2氧化分解臭氧化中间体的最佳反应条件，具体为：n(H_2O_2)：n(C_6H_(10))=2.4：1(以2.8 mmol环己烯计)，氧化分解温度为75℃，氧化分解时间为3.5 h时，经三组平行试验检验，产品己二酸的平均收率约80.4％。
双氧水作为氧化剂虽是绿色氧化剂，但成本较高。鉴于此，开展了以氧气为氧源氧化分解臭氧化中间体的研究。探讨了氧化分解温度、氧化分解时间、催化剂种类、催化剂加入量、氧气气速等主要影响因素对氧化分解反应的影响。采用两次正交试验对反应条件进行优化，得出了最佳反应条件为：氧化分解温度为75℃，氧化分解时间为3.5h，钼金属用量1 mmol(折合三氧化钼质量0.144 g)，氧气气速为40 mL/min，己二酸的收率可达到79.5％，乙酸回收收率可达到70％。
本研究特点在于全部采用清洁氧源，以代替现行有重大污染的工业路线。从上述结果看：以O_2为氧源氧化分解所得的己二酸收率虽较H_2O_2略低，但从原料成本上讲O_2为氧源更具有优越性，具有较好的潜在应用前景。
This dissertation was financial supported by the Key Scientific and Technological Project Funds of Henan Province (523050300).
Adipic acid is an important dicarboxylic acid, which mainly in making some of polymers, such as 6,6-nylon, polyurethane and so on. There is pollution problem in the traditional technology of synthesis adipic acid. And in recent years, hydrogen peroxide is used to synthesize adipic acid by oxidating cyclohexene directly. for higher price of H_2O_2, this new technology can not be applied in industry. It is well-known that olefin is easy to react with ozone, so this paper uses O_2 indirectly, some of the O_2 is transformed into O_3 in a ozonizer, this is a new way to synthesize adipic acid with cyclohexene, 30 wt% H_2O_2 and oxygen as raw materials. Main results obtained on research work are as follows:
In the process of the ozonation reaction, the bubble column, whose ratio of column height to diameter was 10 : 1 and the gas distributer was G4 glass sand core, was adopted as the ozonation reaction column. Several factors which influence the ozonation reaction, such as, sorts and volumes of solvent, ozonolysis temperature had been investigated. The proper ozonolysis condition was confirmed, that is, V(C_6H_(10)) : V(C_2H_4O_2)=1:10 (based on 2.8 mmol of cyclohexene, approx 3 ml), ozonolysis time 1.5 h, flux of oxygen 200 mL/min, efficiency of zonator 100 %, ozonolysis temperature 5-10℃.
In the process of synthesis adipic acid by oxygenolysis of the ozonized intermediate, firstly, 30 wt% H_2O_2 was used as oxidant. Effects of some factors were investigated in oxygenolysis of ozonized intermediate, such as, molar ratio of hydrogen proxide to cyclohexene, oxygenolysis temperature and time. The proper oxygenolysis condition was n(H_2O_2) : n(C_6H_(10))=2.4 : 1 (based on 2.8 mmol of cyclohexene), oxygenolysis temperature 75℃, oxygenolysis time 3.5 h. Under this optimum condition, the average yield of adipic acid synthesized by three parallel tests was about 80.4 %.
Although H_2O_2 is an important "green" oxidant, its price is higher than general oxidants. And then oxygen is natural, cheap and rich oxidant, therefore, O_2 was choosed as an oxidant from some oxygen sources in oxygenolysis of the ozonized intermediate. The main factors which influence the reaction, such as, oxygenolysis temperature and time, sorts and weights of catalysts and flux of oxygen. Twice orthognol test was adopted to optimize the reaction conditions, the optimal oxygenolysis condition was as follows: oxygenolysis temperature 75℃, oxygenolysis time 3.5 h, amount of molybdenum in molybdenum trioxydatum 1 mmol, flux of oxygen 40 mL/min. Under the condition, the yield of adipic acid was 79.5 %, the recovery rate of acetic acid was 70 %.
Clean oxidant was used in this work to replace the traditional industry process, which would pollute the environment seriously. The results showed, in oxygenolysis of ozonized intermediate, the yield of adipic acid was synthesized by using O_2 as oxidant is a little lower than that of by using H_2O_2. Considering the cost of oxidants, it is sure that the former is better than the latter, and so technology of O_2 as oxidant possesses more potential foreground in application of industrial fields.
引文
[1] 何秉忠，朱圣东．己二酸生产技术与市场[J]．化工时刊，2001，(4)：50-51
[2] 翌晨．己二酸市场需求前景看好[J]．化工管理，2003，(4)：26
[3] 田文平，贾飞，张华．己二酸的国内外生产消费现状及发展[J]．2005，3：1-4
[4] 周亚明．己二酸的市场、生产和发展前景[J]．增塑剂，2004，(3)：9-16
[5] 杨学萍．己二酸生产技术现状及发展方向[J]．精细石油化工进展，2004，5(9)：15-18
[6] Castellan A,Bart J C J,Cavallaro S.Industrial production and use of adipic acid[J].Catalysis Today,1991,9(3):237-254
[7] 化工百科全书编写组．化工百科全书[M]．北京：科学出版社，2001，853-874
[8] 陈银生，周亚明，王霞．己二酸的各种生产工艺及污染物处理[J]．皮革化工2005，22(3)：30-34
[9] 潘强，盛琳，曹莉，等．己二酸生产工艺比较[J]．河南化工，2004，21(5)：10-11
[10] 戴新民．己二酸生产工艺技术路线评述[J]．河南化工，1996，13(12)：2-5
[11] Khan L, Khan S. Catalytic conversion of cyclohexane to adipic acid using oxygen under mild conditions[J]. Journal of Scientific and Industrial Research, 1999, 42(6): 336-338
[12] Alessandro N, Liberatore L, Tonucci L, Morvillo A, Bressan M. Direct synthesis of adipic acid by monopersulfate oxidation of cyclohexane, cyclohexanone or cyclohexanol catalyzed by water-soluble transition-metal complexes[J]. New Journal of Chemistry, 2001, 25(10): 1319-1324
[13] Belkhir I, Germain A, Fajula F, etal. Liquid-phase oxidation of cyclohexane to adipic acid catalyzed by cobalt-containing zeolites[J]. Studies in Surface Science and Catalysis, 1997, 110:577-584
[14] Belkhir I, Germain A, Fajula F, etal. Role of cobalt molecular sieves in the liquid-phase oxidation of cyclohexane to adipic acid[J]. Journal of the Chemical Society, 1998, 94(12), 1761-1764
[15] Belkhir I, Germain A, Fajula F, etal. Liquid-phase oxidation of cyclohexane to adipic acid catalyzed by manganese-containing zeolites[J]. Special Publication-Royal Society of Chemistry, 1998, 216:48-53
[16] Iwahama T, Syojyo K, Sakaguchi S, etal. Direct conversion of cyclohexane into adipic acid with molecular oxygen catalyzed by n-hydroxyphthalimide combined with Mn(acac)_2 and Co(OAc)_2[J]. Organic Process Research & Development, 1998, 2(4): 255-260
[17] Dugal M, Sankar G, Raja R, etal. Designing a heterogeneous catalyst for the production of adipic acid by aerial oxidation of cyclohexane[J]. Angewandte Chemie, International Edition, 2000, 39(13): 2310-2313
[18] Castellan A, Bart J C J, Cavallaro S. Industrial production and use of adipic acid[J]. Catalysis Today, 1991, 9(3): 237-254.
[19] 饶兴鹤．世界己二酸生产现状和生产技术进展[J]．世界观察，2005，7：70-73
[20] Steinmetz G R, Lafferty N L, Sumner C E. The cobalt/zirconium-catalyzed oxidation of cyclohexane to adipic acid[J]. Journal of Molecular Catalysis, 1988, 49(1): 39-42
[21] Kulsrestha G N, Shankar U, Sharma J S, etal. One-step oxidation of cyclohexane to adipic acid[J]. Journal of Chemical Technology and Biotechnology, 1991, 50(1):57-65
[22] Rao D G. A semiempirical model for the oxidation of cyclohexane[J]. Industrial & Engineering Chemistry Research, 1990, 29(4): 696-699
[23] Rao D G, Tirukkoyilur R S. Liquid-phase oxidation of cyclohexane to adipic acid in a single stage[J]. Industrial & Engineering Chemistry Process Design and Development, 1986, 25(1): 299-304
[24] 杨杏生．己二酸生产工艺的新进展[J]．合成纤维工业，1995，18(2)：39-45．
[25] 冯美平．丁二烯法制己二酸[J]．合成纤维工业，1999，22(2)：22-25
[26] 饶兴鹤．世界己二酸产需现状和生产技术进展[J]．中国石油和化工，2005，(7)：70-73
[27] European Chemical News, 1999,7,1
[28] Rapoport.M. Hydrocyanation of ButadiEne[P], US4714744, 1987
[29] Benzie R J, Waddan Dhafir Y. Organic Nitriles[P].US4230634, 1980
[30] Raja R, Lee S O, Sanchez M,etal. Towards an environmentally acceptable heterogeneous catalytic method of producing adipic acid by the oxidation of hydrocartions in air[J]. Topics in Catalysis, 2002, 20(4): 85-88
[31] Niu Wei,Drths.K.M,Frost.J.W, etal. Benzene-free synthesis of adipic acid[J]. Biotechnology Progress, 2002, 18:201-211
[32] 吴毓林，龙亚秋．合成化学—新世纪再创辉煌[J]．大学化学，2001，16(3)：1-6．
[33] Anastas P T, Williamson T C. Green Chemistry-Designing for the Environment[Z]. ACS Symposium Seres, Amerrican Chemical Society Washington D C, 1996
[34] Mooney W, Chauveau F, Folcher, Gerard, etal. Catalytic photooxidation of cyclohexene by aqueous uranyl/polymolybdate(Ⅵ) systems[J]. Journal of Chemical Society, 1988,(8): 1479-1484
[35] 梁诚．己二酸合成技术进展与市场分析[J]．石油化工技术经济，2006，3：45-50
[36] 陈银生，周亚明，王霞．己二酸市场状况及发展趋势[J]．江苏化工，33(3)：69-71
[37] Venturello C, Ricci M. Carboxylic acids from vicinal water-soluble diols[P]. European Patent 123495, 1984
[38] Ishii Y, Yamawaki K, Ura T, etal. Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpy-ridinium chloride. Epoxidation of olefins and allylic alcohols, ketoniza-tion of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins[J]. Journal of Organic Chemistry, 1988, 53(15): 3587-3593
[39] Fujitani Tsuratake, Nakazawa Mikiro. Process for the catalytic preparation of carboxylic acids from(cyclo)olefins[P]. JP63093746, 1988
[40] Sato K, Aoki M, Noyori R. A"Green"route to adipic acid: direct oxidation of cyclohexenes with 30 percent hydrogen peroxide[J]. Science, 1998, 281(5383): 1646-1647
[41] Reed S M, Hutchison J E. Green chemistry in the organic teaching laboratory: an environmentally benign synthesis of adipic acid[J]. Journal Chemical Education, 2000, 77(12): 1627-1629
[42] Lapisardi G, Cjoler F, Launay F, etal. Preparation, chatacterisation and catalytic activity of new bifunctional Ti-A1SBA15 materials.Application to a"one-pot" green synthesis of adipic acid from cyslohexene and organic hydroperoxides[J]. Microporaus and Mesoporous Materials. 2005,78(2-3): 289-295
[43] 马祖福，邓友全，王坤，等．清洁催化氧化合成己二酸[J]．2001，2：116-119
[44] 宫红，姜恒，吕振波．己二酸绿色合成新途径[J]．高等学校化学学报，2000，21(7)：1121-1123
[45] 曹发斌，姜恒，宫红，等．Na_2WO_4/1，2，3，4-丁烷四羧酸催化氧化环己烯合成己二酸[J]．化工科技，2004，12(5)：1-4
[46] 阎松，姜恒，宫红，等．三氧化钨催化氧化环己烯合成己二酸[J]．2005，2(20)：33-35
[47] 杜建舟，刘丹，丛晓辉，等．酸性离子液体中环己烯催化氧化合成己二酸[J]．石油化工高等学校学报，2006，19(1)：6-9
[48] Mall Sanjib, Kumar, Sreeramagiri Siva. Process and activated catalyst for the preparation of adipic acid from cyclohexane and oxygen[P]. US 6235932.2001
[49] Reddy M M, Punniyamurthy T, Igbal J. Cobalt catalyzed oxidation of cyclic alkenes with molecular oxygen:Allylic oxidation versus double band attack[J]. Tretrahedron Letters, 1995, 36(1): 159
[50] Keillani A, Schreiner A F, Hilal H S, etal. The catalytic activity ofpoly(siloxane)-supported metlloporphyrins in olefin oxidation reactions: The effect support on the catalytic activity and selectivity[J]. J Mol Catal A:Chemical, 1996, 113(1/2):151-157
[51] Chavan S. A., Srinivas D., Ratnasamy P. Oxidation of Cyclohexane, Cyclohexanone, and Cyclohexanol to Adipic Acid by a Non-HNO_3 Route over Co/Mn Cluster Complexes[J]. Journal of Catalysis. 2002, 212(1), 39-45
[52] Ziqiang Lei. Selective oxidation of cyclohexene catalyzed by polymer-bound ruthenium-2,2-bipyridine complexes[J]. Reactive&Functional Polymers.2000, 43(1): 139-143
[53] David G., Gao Ruomei, Celaje Jeff, etal. Phosphadioxirane:A Peroxide from an Ortho-Substituted Arylphosphine and Singlet Dioxygen[J]. Science. 2003, 302(5643): 259-261
[54] 白希尧，张芝涛，白敏菂等．臭氧产生方法及其应用[J]．自然杂志，2000，22 (6)：347-353
[55] 张芝涛，沈丽，扈群，等．高浓度臭氧水溶液研究[J]．中国环境科学，2000，20(4)：309-312
[56] Rounsaville J. Rice R.G. Evolution of ozone for the bleaching of paper pulps[J]. Ozone: Science engineering, 1997, 18(6): 549-566
[57] 沙耀武，王欣．臭氧化物的生成机理研究综述[J]．有机化学，1999，19：224-235
[58] Liu Xiongmin, Yi Fengping, Li Weiguang, etal. The salty Mwasures of Ozonede in Ozoneze Reaction[C]. CJSEMSE. Nanjing, China, oct7-11, 1996, 213-216
[59] Roger Atkinson, William P L Carter. Kinetics and Mechanisms of the Gas-Phase Reactions of Ozone with Organic Compounds under Atmospheric conditions[J]. Chem.Rev. 1984,84(5): 437-470
[60] Odinokov V N, Zhemaiduk L P, Tolstikov G A. Alkene ozonolysis and study of reactions of polyfunctional compounds. Ⅻ. New ozonolytic synthesis of carboxylic acids.[J]. Zhurnal Organicheskoi Khimii 1978, 14(1), 54-59
[61] Habib R M, Chin-Yun Chiang, Philip S. Dicarboxylic acids from ozonolysis of cycloalkenes[J]. Journal Organic Chemistry, 1984, 49(15): 2780-2784
[62] Hatakeyama Shiro, Sivanesan Subramanian, Urabe Taichiro. Formation Mechanism of Peroxides in Reactions of Cyclic Olefins with Ozone in Air[J]. Chemistry Letters, 2001, 12:1248-1249
[63] Thayer Ⅱ, Chester Arthur. One-step oxidation and ozonolysis process for producing aliphatic dicarboxylic acids from cycloalkenes[P]. U.S 6426432, 2002
[64] Moran, Edward F. Process for making a C6-12 dicarboxylic acid or azelaic acid using pure ozone generated by electric corona-discharge treatment of pure carbon dioxide and ozonolysis of a C6-12 cycloalkene or oleic acid followed by treatment of the ozonide with oxygen[P]. U.S.2003010622, 2003
[65] Razumovskii S D, Zaikov G E, Mushenko D V, etal. Dicarboxylic acids[P]. U.S. 3911000, 1975
[66] 陈甘棠，王樟茂著．多相反应工程[M]．杭州：浙江大学出版社，1996，第一版
[67] 梁红军．烯烃臭氧化反应及其传质过程的研究[D]．南宁，广西大学，2001
[68] 杨颖．臭氧综述[J]．攀枝花大学学报，2002，19(2)：84-86
[69] 李英春，宋湛谦．油酸臭氧化制备壬二酸[J]．精细石油化工．2003，6：37-39
[70] 刘光启，马连湘，刘杰．化学化工物性数据手册[M]．北京：化学工业出版社，2002
[71] 王书谦，李英春．臭氧化法制备十三烷二酸的研究[J]．上海化工．2005，30(4)：21-22
[72] 黄越球．臭氧氧化法合成洋茉莉醛[D]．杭州，浙江大学：2003
[73] Louis R. Process for making carboxylic acids[P]. US Patent:5420316,1995
[74] Frost, John, Draths, etal. Synthesis of adipic acid from biomass-derived carbon sources[J].Biotechnology Advances, 1997, 15(1): 294
[2] 翌晨．己二酸市场需求前景看好[J]．化工管理，2003，(4)：26
[3] 田文平，贾飞，张华．己二酸的国内外生产消费现状及发展[J]．2005，3：1-4
[4] 周亚明．己二酸的市场、生产和发展前景[J]．增塑剂，2004，(3)：9-16
[5] 杨学萍．己二酸生产技术现状及发展方向[J]．精细石油化工进展，2004，5(9)：15-18
[6] Castellan A,Bart J C J,Cavallaro S.Industrial production and use of adipic acid[J].Catalysis Today,1991,9(3):237-254
[7] 化工百科全书编写组．化工百科全书[M]．北京：科学出版社，2001，853-874
[8] 陈银生，周亚明，王霞．己二酸的各种生产工艺及污染物处理[J]．皮革化工2005，22(3)：30-34
[9] 潘强，盛琳，曹莉，等．己二酸生产工艺比较[J]．河南化工，2004，21(5)：10-11
[10] 戴新民．己二酸生产工艺技术路线评述[J]．河南化工，1996，13(12)：2-5
[11] Khan L, Khan S. Catalytic conversion of cyclohexane to adipic acid using oxygen under mild conditions[J]. Journal of Scientific and Industrial Research, 1999, 42(6): 336-338
[12] Alessandro N, Liberatore L, Tonucci L, Morvillo A, Bressan M. Direct synthesis of adipic acid by monopersulfate oxidation of cyclohexane, cyclohexanone or cyclohexanol catalyzed by water-soluble transition-metal complexes[J]. New Journal of Chemistry, 2001, 25(10): 1319-1324
[13] Belkhir I, Germain A, Fajula F, etal. Liquid-phase oxidation of cyclohexane to adipic acid catalyzed by cobalt-containing zeolites[J]. Studies in Surface Science and Catalysis, 1997, 110:577-584
[14] Belkhir I, Germain A, Fajula F, etal. Role of cobalt molecular sieves in the liquid-phase oxidation of cyclohexane to adipic acid[J]. Journal of the Chemical Society, 1998, 94(12), 1761-1764
[15] Belkhir I, Germain A, Fajula F, etal. Liquid-phase oxidation of cyclohexane to adipic acid catalyzed by manganese-containing zeolites[J]. Special Publication-Royal Society of Chemistry, 1998, 216:48-53
[16] Iwahama T, Syojyo K, Sakaguchi S, etal. Direct conversion of cyclohexane into adipic acid with molecular oxygen catalyzed by n-hydroxyphthalimide combined with Mn(acac)_2 and Co(OAc)_2[J]. Organic Process Research & Development, 1998, 2(4): 255-260
[17] Dugal M, Sankar G, Raja R, etal. Designing a heterogeneous catalyst for the production of adipic acid by aerial oxidation of cyclohexane[J]. Angewandte Chemie, International Edition, 2000, 39(13): 2310-2313
[18] Castellan A, Bart J C J, Cavallaro S. Industrial production and use of adipic acid[J]. Catalysis Today, 1991, 9(3): 237-254.
[19] 饶兴鹤．世界己二酸生产现状和生产技术进展[J]．世界观察，2005，7：70-73
[20] Steinmetz G R, Lafferty N L, Sumner C E. The cobalt/zirconium-catalyzed oxidation of cyclohexane to adipic acid[J]. Journal of Molecular Catalysis, 1988, 49(1): 39-42
[21] Kulsrestha G N, Shankar U, Sharma J S, etal. One-step oxidation of cyclohexane to adipic acid[J]. Journal of Chemical Technology and Biotechnology, 1991, 50(1):57-65
[22] Rao D G. A semiempirical model for the oxidation of cyclohexane[J]. Industrial & Engineering Chemistry Research, 1990, 29(4): 696-699
[23] Rao D G, Tirukkoyilur R S. Liquid-phase oxidation of cyclohexane to adipic acid in a single stage[J]. Industrial & Engineering Chemistry Process Design and Development, 1986, 25(1): 299-304
[24] 杨杏生．己二酸生产工艺的新进展[J]．合成纤维工业，1995，18(2)：39-45．
[25] 冯美平．丁二烯法制己二酸[J]．合成纤维工业，1999，22(2)：22-25
[26] 饶兴鹤．世界己二酸产需现状和生产技术进展[J]．中国石油和化工，2005，(7)：70-73
[27] European Chemical News, 1999,7,1
[28] Rapoport.M. Hydrocyanation of ButadiEne[P], US4714744, 1987
[29] Benzie R J, Waddan Dhafir Y. Organic Nitriles[P].US4230634, 1980
[30] Raja R, Lee S O, Sanchez M,etal. Towards an environmentally acceptable heterogeneous catalytic method of producing adipic acid by the oxidation of hydrocartions in air[J]. Topics in Catalysis, 2002, 20(4): 85-88
[31] Niu Wei,Drths.K.M,Frost.J.W, etal. Benzene-free synthesis of adipic acid[J]. Biotechnology Progress, 2002, 18:201-211
[32] 吴毓林，龙亚秋．合成化学—新世纪再创辉煌[J]．大学化学，2001，16(3)：1-6．
[33] Anastas P T, Williamson T C. Green Chemistry-Designing for the Environment[Z]. ACS Symposium Seres, Amerrican Chemical Society Washington D C, 1996
[34] Mooney W, Chauveau F, Folcher, Gerard, etal. Catalytic photooxidation of cyclohexene by aqueous uranyl/polymolybdate(Ⅵ) systems[J]. Journal of Chemical Society, 1988,(8): 1479-1484
[35] 梁诚．己二酸合成技术进展与市场分析[J]．石油化工技术经济，2006，3：45-50
[36] 陈银生，周亚明，王霞．己二酸市场状况及发展趋势[J]．江苏化工，33(3)：69-71
[37] Venturello C, Ricci M. Carboxylic acids from vicinal water-soluble diols[P]. European Patent 123495, 1984
[38] Ishii Y, Yamawaki K, Ura T, etal. Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpy-ridinium chloride. Epoxidation of olefins and allylic alcohols, ketoniza-tion of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins[J]. Journal of Organic Chemistry, 1988, 53(15): 3587-3593
[39] Fujitani Tsuratake, Nakazawa Mikiro. Process for the catalytic preparation of carboxylic acids from(cyclo)olefins[P]. JP63093746, 1988
[40] Sato K, Aoki M, Noyori R. A"Green"route to adipic acid: direct oxidation of cyclohexenes with 30 percent hydrogen peroxide[J]. Science, 1998, 281(5383): 1646-1647
[41] Reed S M, Hutchison J E. Green chemistry in the organic teaching laboratory: an environmentally benign synthesis of adipic acid[J]. Journal Chemical Education, 2000, 77(12): 1627-1629
[42] Lapisardi G, Cjoler F, Launay F, etal. Preparation, chatacterisation and catalytic activity of new bifunctional Ti-A1SBA15 materials.Application to a"one-pot" green synthesis of adipic acid from cyslohexene and organic hydroperoxides[J]. Microporaus and Mesoporous Materials. 2005,78(2-3): 289-295
[43] 马祖福，邓友全，王坤，等．清洁催化氧化合成己二酸[J]．2001，2：116-119
[44] 宫红，姜恒，吕振波．己二酸绿色合成新途径[J]．高等学校化学学报，2000，21(7)：1121-1123
[45] 曹发斌，姜恒，宫红，等．Na_2WO_4/1，2，3，4-丁烷四羧酸催化氧化环己烯合成己二酸[J]．化工科技，2004，12(5)：1-4
[46] 阎松，姜恒，宫红，等．三氧化钨催化氧化环己烯合成己二酸[J]．2005，2(20)：33-35
[47] 杜建舟，刘丹，丛晓辉，等．酸性离子液体中环己烯催化氧化合成己二酸[J]．石油化工高等学校学报，2006，19(1)：6-9
[48] Mall Sanjib, Kumar, Sreeramagiri Siva. Process and activated catalyst for the preparation of adipic acid from cyclohexane and oxygen[P]. US 6235932.2001
[49] Reddy M M, Punniyamurthy T, Igbal J. Cobalt catalyzed oxidation of cyclic alkenes with molecular oxygen:Allylic oxidation versus double band attack[J]. Tretrahedron Letters, 1995, 36(1): 159
[50] Keillani A, Schreiner A F, Hilal H S, etal. The catalytic activity ofpoly(siloxane)-supported metlloporphyrins in olefin oxidation reactions: The effect support on the catalytic activity and selectivity[J]. J Mol Catal A:Chemical, 1996, 113(1/2):151-157
[51] Chavan S. A., Srinivas D., Ratnasamy P. Oxidation of Cyclohexane, Cyclohexanone, and Cyclohexanol to Adipic Acid by a Non-HNO_3 Route over Co/Mn Cluster Complexes[J]. Journal of Catalysis. 2002, 212(1), 39-45
[52] Ziqiang Lei. Selective oxidation of cyclohexene catalyzed by polymer-bound ruthenium-2,2-bipyridine complexes[J]. Reactive&Functional Polymers.2000, 43(1): 139-143
[53] David G., Gao Ruomei, Celaje Jeff, etal. Phosphadioxirane:A Peroxide from an Ortho-Substituted Arylphosphine and Singlet Dioxygen[J]. Science. 2003, 302(5643): 259-261
[54] 白希尧，张芝涛，白敏菂等．臭氧产生方法及其应用[J]．自然杂志，2000，22 (6)：347-353
[55] 张芝涛，沈丽，扈群，等．高浓度臭氧水溶液研究[J]．中国环境科学，2000，20(4)：309-312
[56] Rounsaville J. Rice R.G. Evolution of ozone for the bleaching of paper pulps[J]. Ozone: Science engineering, 1997, 18(6): 549-566
[57] 沙耀武，王欣．臭氧化物的生成机理研究综述[J]．有机化学，1999，19：224-235
[58] Liu Xiongmin, Yi Fengping, Li Weiguang, etal. The salty Mwasures of Ozonede in Ozoneze Reaction[C]. CJSEMSE. Nanjing, China, oct7-11, 1996, 213-216
[59] Roger Atkinson, William P L Carter. Kinetics and Mechanisms of the Gas-Phase Reactions of Ozone with Organic Compounds under Atmospheric conditions[J]. Chem.Rev. 1984,84(5): 437-470
[60] Odinokov V N, Zhemaiduk L P, Tolstikov G A. Alkene ozonolysis and study of reactions of polyfunctional compounds. Ⅻ. New ozonolytic synthesis of carboxylic acids.[J]. Zhurnal Organicheskoi Khimii 1978, 14(1), 54-59
[61] Habib R M, Chin-Yun Chiang, Philip S. Dicarboxylic acids from ozonolysis of cycloalkenes[J]. Journal Organic Chemistry, 1984, 49(15): 2780-2784
[62] Hatakeyama Shiro, Sivanesan Subramanian, Urabe Taichiro. Formation Mechanism of Peroxides in Reactions of Cyclic Olefins with Ozone in Air[J]. Chemistry Letters, 2001, 12:1248-1249
[63] Thayer Ⅱ, Chester Arthur. One-step oxidation and ozonolysis process for producing aliphatic dicarboxylic acids from cycloalkenes[P]. U.S 6426432, 2002
[64] Moran, Edward F. Process for making a C6-12 dicarboxylic acid or azelaic acid using pure ozone generated by electric corona-discharge treatment of pure carbon dioxide and ozonolysis of a C6-12 cycloalkene or oleic acid followed by treatment of the ozonide with oxygen[P]. U.S.2003010622, 2003
[65] Razumovskii S D, Zaikov G E, Mushenko D V, etal. Dicarboxylic acids[P]. U.S. 3911000, 1975
[66] 陈甘棠，王樟茂著．多相反应工程[M]．杭州：浙江大学出版社，1996，第一版
[67] 梁红军．烯烃臭氧化反应及其传质过程的研究[D]．南宁，广西大学，2001
[68] 杨颖．臭氧综述[J]．攀枝花大学学报，2002，19(2)：84-86
[69] 李英春，宋湛谦．油酸臭氧化制备壬二酸[J]．精细石油化工．2003，6：37-39
[70] 刘光启，马连湘，刘杰．化学化工物性数据手册[M]．北京：化学工业出版社，2002
[71] 王书谦，李英春．臭氧化法制备十三烷二酸的研究[J]．上海化工．2005，30(4)：21-22
[72] 黄越球．臭氧氧化法合成洋茉莉醛[D]．杭州，浙江大学：2003
[73] Louis R. Process for making carboxylic acids[P]. US Patent:5420316,1995
[74] Frost, John, Draths, etal. Synthesis of adipic acid from biomass-derived carbon sources[J].Biotechnology Advances, 1997, 15(1): 294