菲醌合成的绿色工艺研究
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摘要
我省拥有丰富的煤炭资源,每年生产大量的煤焦油,而菲是煤焦油中含量较多的组分之一,菲的开发利用历来是人们重视的研究课题。到目前为止,已经提出多条菲的可利用途径,其中从菲制取菲醌是重要途径之一。菲醌是用途很广的重要中间体,由菲合成菲醌具有可观的经济效益。合成菲醌的方法虽然很多,但这些方法中不是由于技术问题,就是由于成本太高或是由于存在着严重的污染问题,致使难以实现大规模工业化生产。鉴于菲醌合成中的诸多问题,因此把开发低成本、无污染的菲醌合成新工艺作为本论文的研究课题。
本文采用液相催化氧化法,以工业菲为原料,重铬酸盐为氧化剂,水为介质,季铵盐为相转移催化剂,在酸性条件下研究了菲醌的合成。主要从以下四个方面进行了研究:第一,氧化剂和催化剂的选择;第二,通过均匀实验,研究了氧化剂用量、催化剂用量、溶液酸度、反应时间和反应温度等因素对菲醌收率的影响,确定菲醌合成的最佳条件;第三,研究并建立了测定母液主要成分的分析方法,即用氧化还原滴定法测定其中铬(Ⅲ,Ⅵ)的含量;用电位滴定法测定酸的含量,其中加入六偏磷酸钠来消除其Cr~(3+)对测定结果的干扰;第四,在最佳条件下,进行了母液的多次循环利用和回收副产物的实验。实验发现,随着循环利用的次数的增多,母液粘稠度越来越高;在分析导致母液粘稠因素的基础上,提出了萃取一结晶法,解决母液的粘稠问题。
结果表明:采用重铬酸钾作氧化剂,可以使母液与三价铬副产物容易分离,实现母液的循环利用;在实验所用的三种季铵盐中,十二烷基三甲基氯化铵的相转移催化效果最好;在影响产物收率的各个因素中,反应体系的酸度和氧化剂的用量这两个因素对菲醌收率影响较大;母液粘稠是制约母液多次循环利用的关键,萃取一结晶法可以降低母液粘稠度和促进三价铬副产物析出,使母液循环利用不断进行下去;在最佳条件下,母液每次循环的产物收率可达80%以上;三价铬副产物,经XRD测定为十二水合硫酸铬钾;在含大量Cr~(3+)的反应母液中用电位滴定法测定酸的含量是相当困难的,通过在待测液中加入一定的六偏磷酸钠,可以消除Cr~(3+)的干扰,较准确地测定母液的酸度。
综上所述:这种母液循环利用的菲醌合成的绿色工艺具有反应条件温和、成本低、母液可循环利用、无污染和三价铬的副产物易回收等优点,有着广阔的工业化前景。
Our province is rich in coal resources and largely produces coke and coal tar every year, and phenanthrene is one of the main components in the coal tar, the development and utilization of the phenanthrene have always being researched in coal chemical engineering field. So far, many ways of phenanthrene utilization have already been proposed, in which the making of phenanthrenequinone oxidated by phenanthrene is one of important directions. Phenanthrenequinone is the important intermediate with extensive applications, the synthesizing phenanthrenequinone from phenanthrene has considerable ceconomical value. Although there are many methods of synthesizing phenanthrenequinone, at present, the industry massive production have not come true because of the technic, cost, pollution and so on. In view of many problems of phenanthrenequinone synthesis, a new phenanthrenequinone synthesis technology with low cost and no pollution is determined as the research topic of this thesis.
In this paper, industrial phenanthrene was used as raw material, dichromate as oxidant, water as medium, quaternary ammonium salt as phase transfer catalyst, phenanthrenequinone synthesis was researched by liquidphase catalysis oxidation in the acid medium. The four aspects studied in the paper are as follows: first, the optimal oxidant and the optimal catalyst were selected. Second, through homogeneous design, how the factors influence on phenanthrenequinone yield was got known, such as the amount of oxidant, the amount of catalyst, the solution acidity, reaction time and temperature, the best condition of phenanthrenequinone synthesis was found. Third, the analysis methods of the mother liquor major components were established: redox titration of determining the content of chromium; potentiometric titration of the acidity, because trivalence chromium ions have serious interference, the sodium hexametaphosphate was added to eliminate the interference. Fourth, under the best conditions, the experiments of many times mother liquor recycling utilization and trivalence chromium by-product reclaim were undergone. The experiment showed: mother liquor became slabbier and slabbier with its recycling utilization times increasing; basing on analyzing the factors leading to mother liquor slabbier, the solution of mother liquor extraction-crystallization was proposed.
The results show: when potassium dichromate is used as oxidant, the by-product is easily separated from the mother liquor, and the circulation and utilization of mother liquor can go along; dodecyl tyimethyl ammonium chloride is the best phase transfer catalyst among the catalysts used in experiments; there are major effect of the liquor acidity and the oxidant amount on phenanthrenequinone yield; the mother liquor viscosity is the key which limits times of mother liquor circulation utilization, the viscosity can be reduced by extraction- crystallization and the trivalent chromium by-product can be crystaled out, and mother liquor circulation utilization can go along; Under the optimum conditions, the yield of phenanthrenequinone is high to 80 percent or more each recycle; the by-product is determined as dodecahydrated potassium chromium sulfate by the XRD; it is very difficult to make certain acidity in mother liquor with lots of Cr~(2+) by potentiometric titration, Cr~(3+) interfere can be eliminated by adding sodium hexametaphosphates into mother liquor, and acidity of mother liquor can be determined accurately.
In a word, the green technology of phenanthrenequinone synthesis has many advantages, such as the mild reaction conditions, low cost, feasible circulation utilization of mother liquor, no pollution, and easy recovery of the by-product and so on. So it has broad industrialization prospects.
本文采用液相催化氧化法,以工业菲为原料,重铬酸盐为氧化剂,水为介质,季铵盐为相转移催化剂,在酸性条件下研究了菲醌的合成。主要从以下四个方面进行了研究:第一,氧化剂和催化剂的选择;第二,通过均匀实验,研究了氧化剂用量、催化剂用量、溶液酸度、反应时间和反应温度等因素对菲醌收率的影响,确定菲醌合成的最佳条件;第三,研究并建立了测定母液主要成分的分析方法,即用氧化还原滴定法测定其中铬(Ⅲ,Ⅵ)的含量;用电位滴定法测定酸的含量,其中加入六偏磷酸钠来消除其Cr~(3+)对测定结果的干扰;第四,在最佳条件下,进行了母液的多次循环利用和回收副产物的实验。实验发现,随着循环利用的次数的增多,母液粘稠度越来越高;在分析导致母液粘稠因素的基础上,提出了萃取一结晶法,解决母液的粘稠问题。
结果表明:采用重铬酸钾作氧化剂,可以使母液与三价铬副产物容易分离,实现母液的循环利用;在实验所用的三种季铵盐中,十二烷基三甲基氯化铵的相转移催化效果最好;在影响产物收率的各个因素中,反应体系的酸度和氧化剂的用量这两个因素对菲醌收率影响较大;母液粘稠是制约母液多次循环利用的关键,萃取一结晶法可以降低母液粘稠度和促进三价铬副产物析出,使母液循环利用不断进行下去;在最佳条件下,母液每次循环的产物收率可达80%以上;三价铬副产物,经XRD测定为十二水合硫酸铬钾;在含大量Cr~(3+)的反应母液中用电位滴定法测定酸的含量是相当困难的,通过在待测液中加入一定的六偏磷酸钠,可以消除Cr~(3+)的干扰,较准确地测定母液的酸度。
综上所述:这种母液循环利用的菲醌合成的绿色工艺具有反应条件温和、成本低、母液可循环利用、无污染和三价铬的副产物易回收等优点,有着广阔的工业化前景。
Our province is rich in coal resources and largely produces coke and coal tar every year, and phenanthrene is one of the main components in the coal tar, the development and utilization of the phenanthrene have always being researched in coal chemical engineering field. So far, many ways of phenanthrene utilization have already been proposed, in which the making of phenanthrenequinone oxidated by phenanthrene is one of important directions. Phenanthrenequinone is the important intermediate with extensive applications, the synthesizing phenanthrenequinone from phenanthrene has considerable ceconomical value. Although there are many methods of synthesizing phenanthrenequinone, at present, the industry massive production have not come true because of the technic, cost, pollution and so on. In view of many problems of phenanthrenequinone synthesis, a new phenanthrenequinone synthesis technology with low cost and no pollution is determined as the research topic of this thesis.
In this paper, industrial phenanthrene was used as raw material, dichromate as oxidant, water as medium, quaternary ammonium salt as phase transfer catalyst, phenanthrenequinone synthesis was researched by liquidphase catalysis oxidation in the acid medium. The four aspects studied in the paper are as follows: first, the optimal oxidant and the optimal catalyst were selected. Second, through homogeneous design, how the factors influence on phenanthrenequinone yield was got known, such as the amount of oxidant, the amount of catalyst, the solution acidity, reaction time and temperature, the best condition of phenanthrenequinone synthesis was found. Third, the analysis methods of the mother liquor major components were established: redox titration of determining the content of chromium; potentiometric titration of the acidity, because trivalence chromium ions have serious interference, the sodium hexametaphosphate was added to eliminate the interference. Fourth, under the best conditions, the experiments of many times mother liquor recycling utilization and trivalence chromium by-product reclaim were undergone. The experiment showed: mother liquor became slabbier and slabbier with its recycling utilization times increasing; basing on analyzing the factors leading to mother liquor slabbier, the solution of mother liquor extraction-crystallization was proposed.
The results show: when potassium dichromate is used as oxidant, the by-product is easily separated from the mother liquor, and the circulation and utilization of mother liquor can go along; dodecyl tyimethyl ammonium chloride is the best phase transfer catalyst among the catalysts used in experiments; there are major effect of the liquor acidity and the oxidant amount on phenanthrenequinone yield; the mother liquor viscosity is the key which limits times of mother liquor circulation utilization, the viscosity can be reduced by extraction- crystallization and the trivalent chromium by-product can be crystaled out, and mother liquor circulation utilization can go along; Under the optimum conditions, the yield of phenanthrenequinone is high to 80 percent or more each recycle; the by-product is determined as dodecahydrated potassium chromium sulfate by the XRD; it is very difficult to make certain acidity in mother liquor with lots of Cr~(2+) by potentiometric titration, Cr~(3+) interfere can be eliminated by adding sodium hexametaphosphates into mother liquor, and acidity of mother liquor can be determined accurately.
In a word, the green technology of phenanthrenequinone synthesis has many advantages, such as the mild reaction conditions, low cost, feasible circulation utilization of mother liquor, no pollution, and easy recovery of the by-product and so on. So it has broad industrialization prospects.
引文
[1]张永华,杨锦宗.菲的提纯[J].化工时刊,1999(12):20-22.
[2]姚蒙正,曲勇.菲的综合利用[J].染料工业,1987(3):31-35.
[3]王明.9,10-菲醌[J].炼焦化学,1975(11):3.
[4]唐培堃.中间体化学元素及工艺学[M].北京:化学工业出版社,1984,62.
[5]林治穆.煤焦油中菲的利用.化学世界[J],1983,(5):151-153.
[6]顾可权.重要有机化学反应[M].上海:上海科学出版社,第二版,1988,167.
[7]姚蒙正,王晓岚.菲醌的合成[J].化学试剂,1992,14(6):367-368.
[8]程潜,李长荣,张彦文等.取代芴 292 羧酸酯衍生物的合成[J].合成化学,1997,5(1),97-101.
[9]郭建忠,薛永强.菲醌合成及利用[J].太原理工大学学报,2001,32(2):140-143.
[10]Erfinder.Verfahren zur herstllung von phenanthrenchinon[P].DE,3305528,1984-08-23.
[11]Tonnius,dietrich,Weiss et al.Method for the production of phenanthrenequinone[P].US,4510090,1985-04-09.
[12]Baneerjee A,dutt S,Sengrpta D et al.Use of potassium bromate:oxidation of various organic compounds[J].J Indis Chem,Soc,1983,60(3):275-277.
[13]Petiasamy M,Bhatt M V,Facile oxidation of aromatic rings by Mn-2(SO_4)3[J],Tetrahedron Lett,1987,46:4561-4562.
[14]Ho T L,Hall T W,Wong C M.Ceric ammonium nitrate oxidation of polynuclear aromatic hydrocarbons to quinines[J].Synthesis,1973(4):206.
[15]Jacek S.Cerium catalyzed persulfate oxidation of polycyclic aromatic hydrocarbons to quinines[J].Tetrahedron,1984,40(23):4997-5000.
[16]Mihir K C,Shiv K C,Synjukta Let al.Quinoliniu fluorochromate(QFC),C_9H_7NH[CrO_3F]:An improved Cr-oxidant for organic substrates[J].Bull Chem Soc Jpn,1994,67(7):1894-1898.
[17]Firouzabade H,Sardarian A R,Moosavipour H etal.Chrionium(based oxidants;Zinc dichromate trihydrate):A versatile and mild reagent for the oxidant of organic compound[J].Synthesis,1986(4):285-288.
[18]Nippon S K K C.9,10-phenanthrenequinone[P].JP,56012335,1981-02-06.
[19]Saito Y,Kanemura H,ArakiS et al.High-purity phenanthrenequinone[P].JP,60255747,1985-12-17.
[20]Yoshida H,MorikawaM,Iwamura T.Highly pure 9,10-phenanthrenequinone[P].JP,60238432,1985-11-27.
[21]陈文祥.菲醌的合成[P].中国专利,86109444,1988-06-29.
[22]姚蒙正,王晓岚.菲的氧化反应研究[J].染料工业,1992,29(5):17-24.
[23]Magoichi S,Seiji O,Kosaku et al.A novel of thermal oxygenation of aromatic hydrocarbons with a heterocyclic N-oxide:Unusual reactivity of pyrimido[5,4-g]pteridinetrone 10-oxide[J].Chem Pharm Bull,1991,39(1):195-198.
[24]Moshe K,Shlomo R.Functionalization of aromatic molecules using HOF-CH_3CN and CH_3OF[J].J Org Chem,1993,58:1593-1595.
[25]Bahman T,Hamid Y.Pyrazine-based polymeric complex of oxodiperoxochromium(Ⅵ)compound as a new stable,mild,efficient and versatile oxidant in organic synthesis[J].Tetrahedron,1997,53(23):7889-7896.
[26]Nicolai S H,Lars H.Syntheses of 9,10-phenanthrenequinone and 9-methoxyphenanthrene by oxidation of phenanthrene with dihydroxy phenylselenonium benzenesulfonate[J].Syn.Comm.,1997,27(1):89-94.
[27]Maeda I,Mitsui H,Nakamura T.9,10-phenanthrenequinone[P].JP,60233029,1985-11-19.
[28]Liu L B,Yang B W,Katz T J et al.Improved methodology for photocyclization reactions[J].J Org Chem,1991,56(12):3769-3775.
[29]Mallory F B,Mallory C W.Photocyclization of stilbebes.Ⅶ.unusual fluorine atom rearragement in the photocyclization of 1-fluorohelicenes[J].J Org Chem,1983,48(4):526-532.
[30]Johannes G DV,Sally A H.Conversion of benzoin into 9,10-phenanthrenequinone by photocyclisation[J].Chem Comm,1988,17:1172-1173.
[31]Denisio M T,David E N.Synthesis of 9,10-phenanthrenequinone by photocyclisation of derivatives of benzoins:Scope and limitation of the methodology[J].Syn Comm,1998,28(6):1051-1063.
[32]Gabor Spei.The reaction of 9,10-phenanthrenequinonato-bis(triphenylposphine)copper(Ⅰ)with organic peroxides[J].Inorg Chim,1988,143:149-150.
[33]王娟娟,马晓燕,刘海林等.废铬治理技术研究进展[J].西部皮革,2003(10):43-45.
[34]王娟娟,马晓燕,刘海林等.废铬治理技术研究进展续[J].西部皮革,2003(12):35-37.
[35]李树成.菲醒生产中含铬废氧化液的综合利用[J].辽宁城乡环境科技,1999(4):73-74.
[36]仇振琢.用6210净水剂直接去除电镀废水中Cr6+[J].水处理技术,2000,16(6):451.
[37]刘存海,李仲谨,卢卫军.电镀废格液的化学絮凝与铬的回收利用研究[J].西北农林科技大学学报(自然科学版),2001,29(1):66.
[38]李天铎.制革废水的资源化处理技术[J].山东化工,2001(30).
[39]王碧,马春辉,张铭让.制革废水与污泥中铬资源的回收及综合利用[J].中国皮革,2002,3(2):39.
[40]卫亚菲.制革工业污水综合治理和资源化利用[J].中国皮革,1999,26(12):25.
[41]刘明华,张新申,蒋小萍.吸附法处理制革工业中含硫、含铬废水的研究[J].中国皮革,2000,29(11):9.
[42]李硕文,陈扬,万伟.液膜法去除水中Cr(Ⅵ)的研究[J].环境科学与技术,2000(1):26-29.
[43]王靖芳,冯彦琳,孙双红等.乳状液膜法迁移及分离铬(Ⅵ)的研究[J].环境化学,1998,17(1):85-89.
[44]邵刚.膜法水处理技术[M].冶金工业出版社,1992.
[45]卫亚菲.制革工业污水综合治理和资源利用[J].中国皮革,1999,26(12):25.
[46]张建民,宋庆文,朱宝瑜等.生物法处理电镀铬废水的研究[J].西北纺织工学院学报,2001,13(4):420-424.
[47]张建民,宗刚,朱宝瑜等.生物处理电镀废水的研究[J].工业水处理,2001,19(5):21-22.
[48]李建德,冯承嬏,李瑞义等.处理六价铬溶液的一种新方法[J].工业水处理,1995,15(4):35.
[49]杨通在、刘义农,杨君等.阳离子型改性高分子絮凝剂对轻工废水的处理[J].工业水处理,1998,18(3):18.
[50]汤克勇,张铭让.循环利用铬鞣废夜的问题研究[J].皮革化学,2001,16(4):28-30.
[51]Bolbat F F,Lesh E U.New Method Nickel and Cobalt Metallurgy[M].Beijing: Metallurgy Industry Press,1981,303.
[52]LE song-guang(乐颂光).Cobalt Metallury(钴冶金)[M].Beijing:Metallurgy Industry Press,1981,303.
[53]Flynn D R,Twidwell L G.Selective recovery of nickel and cobalt from electromachining solution[A].EPD Congress91[C].Warrendale:The Mineral,Metal&Material Society,1991,353.
[54]Jiang Li(江丽).溶剂萃取法分离镍板极中镍、铬、钴的研究[J].Hydrometallurgy(湿法冶金),2000(19):46.
[55]汪小兰.有机化学[M].高等教育出版社,1987.
[56]曾毓华,陆雪芳,杜文英.相转移催化反应中界面性能的研究[J].化学学报,2000,58(1):34-38.
[57]文海,赵卫东,晨辉.提取菲醌方法研究[J].内蒙古林学院学报(自然科学版),1998,20(3):95-96.
[58]上海化工学院.工业菲气相催化氧化制取9,10-菲醌[J].炼焦化学,1975(5):13-18.
[59]#12.
[60]商振华,王淑芳,王俊德.菲氧化反应产物的高效液相色谱分析[J].分析化学,1990,18(5):461-462.
[61]汤桂娜,贺仕军,王保宁.多元校正-紫外可见分光光度法同时测定Cr(Ⅵ)与Cr(Ⅲ[J]).分析化学,1995,23(4):383.
[62]威安邦.无机化学教程[M].北京:人民教育出版社,1962,532-541.
[63]张春霞,杨放怀,孙富强.用百里酚蓝-亚甲蓝混合指示剂测定季胺盐型阳离子表面活性剂[J].郑州轻工业学院学报,1998:13(4),10-14.
[64]谢亚杰,王伟,刘深.表面活性剂制备技术与分析技术[M].北京:北京工业出版社,2006:392-393.
[65]施云海,陈斌,童思等.双烷链阳离子表面活性剂的合成与定量分析[J].分析化学研究简报,2003:31(3),322-325.
[66]刘增勋.相转移催化剂在有机化学和农药中的应用[M].北京:科学出版社,1987,1.
[2]姚蒙正,曲勇.菲的综合利用[J].染料工业,1987(3):31-35.
[3]王明.9,10-菲醌[J].炼焦化学,1975(11):3.
[4]唐培堃.中间体化学元素及工艺学[M].北京:化学工业出版社,1984,62.
[5]林治穆.煤焦油中菲的利用.化学世界[J],1983,(5):151-153.
[6]顾可权.重要有机化学反应[M].上海:上海科学出版社,第二版,1988,167.
[7]姚蒙正,王晓岚.菲醌的合成[J].化学试剂,1992,14(6):367-368.
[8]程潜,李长荣,张彦文等.取代芴 292 羧酸酯衍生物的合成[J].合成化学,1997,5(1),97-101.
[9]郭建忠,薛永强.菲醌合成及利用[J].太原理工大学学报,2001,32(2):140-143.
[10]Erfinder.Verfahren zur herstllung von phenanthrenchinon[P].DE,3305528,1984-08-23.
[11]Tonnius,dietrich,Weiss et al.Method for the production of phenanthrenequinone[P].US,4510090,1985-04-09.
[12]Baneerjee A,dutt S,Sengrpta D et al.Use of potassium bromate:oxidation of various organic compounds[J].J Indis Chem,Soc,1983,60(3):275-277.
[13]Petiasamy M,Bhatt M V,Facile oxidation of aromatic rings by Mn-2(SO_4)3[J],Tetrahedron Lett,1987,46:4561-4562.
[14]Ho T L,Hall T W,Wong C M.Ceric ammonium nitrate oxidation of polynuclear aromatic hydrocarbons to quinines[J].Synthesis,1973(4):206.
[15]Jacek S.Cerium catalyzed persulfate oxidation of polycyclic aromatic hydrocarbons to quinines[J].Tetrahedron,1984,40(23):4997-5000.
[16]Mihir K C,Shiv K C,Synjukta Let al.Quinoliniu fluorochromate(QFC),C_9H_7NH[CrO_3F]:An improved Cr-oxidant for organic substrates[J].Bull Chem Soc Jpn,1994,67(7):1894-1898.
[17]Firouzabade H,Sardarian A R,Moosavipour H etal.Chrionium(based oxidants;Zinc dichromate trihydrate):A versatile and mild reagent for the oxidant of organic compound[J].Synthesis,1986(4):285-288.
[18]Nippon S K K C.9,10-phenanthrenequinone[P].JP,56012335,1981-02-06.
[19]Saito Y,Kanemura H,ArakiS et al.High-purity phenanthrenequinone[P].JP,60255747,1985-12-17.
[20]Yoshida H,MorikawaM,Iwamura T.Highly pure 9,10-phenanthrenequinone[P].JP,60238432,1985-11-27.
[21]陈文祥.菲醌的合成[P].中国专利,86109444,1988-06-29.
[22]姚蒙正,王晓岚.菲的氧化反应研究[J].染料工业,1992,29(5):17-24.
[23]Magoichi S,Seiji O,Kosaku et al.A novel of thermal oxygenation of aromatic hydrocarbons with a heterocyclic N-oxide:Unusual reactivity of pyrimido[5,4-g]pteridinetrone 10-oxide[J].Chem Pharm Bull,1991,39(1):195-198.
[24]Moshe K,Shlomo R.Functionalization of aromatic molecules using HOF-CH_3CN and CH_3OF[J].J Org Chem,1993,58:1593-1595.
[25]Bahman T,Hamid Y.Pyrazine-based polymeric complex of oxodiperoxochromium(Ⅵ)compound as a new stable,mild,efficient and versatile oxidant in organic synthesis[J].Tetrahedron,1997,53(23):7889-7896.
[26]Nicolai S H,Lars H.Syntheses of 9,10-phenanthrenequinone and 9-methoxyphenanthrene by oxidation of phenanthrene with dihydroxy phenylselenonium benzenesulfonate[J].Syn.Comm.,1997,27(1):89-94.
[27]Maeda I,Mitsui H,Nakamura T.9,10-phenanthrenequinone[P].JP,60233029,1985-11-19.
[28]Liu L B,Yang B W,Katz T J et al.Improved methodology for photocyclization reactions[J].J Org Chem,1991,56(12):3769-3775.
[29]Mallory F B,Mallory C W.Photocyclization of stilbebes.Ⅶ.unusual fluorine atom rearragement in the photocyclization of 1-fluorohelicenes[J].J Org Chem,1983,48(4):526-532.
[30]Johannes G DV,Sally A H.Conversion of benzoin into 9,10-phenanthrenequinone by photocyclisation[J].Chem Comm,1988,17:1172-1173.
[31]Denisio M T,David E N.Synthesis of 9,10-phenanthrenequinone by photocyclisation of derivatives of benzoins:Scope and limitation of the methodology[J].Syn Comm,1998,28(6):1051-1063.
[32]Gabor Spei.The reaction of 9,10-phenanthrenequinonato-bis(triphenylposphine)copper(Ⅰ)with organic peroxides[J].Inorg Chim,1988,143:149-150.
[33]王娟娟,马晓燕,刘海林等.废铬治理技术研究进展[J].西部皮革,2003(10):43-45.
[34]王娟娟,马晓燕,刘海林等.废铬治理技术研究进展续[J].西部皮革,2003(12):35-37.
[35]李树成.菲醒生产中含铬废氧化液的综合利用[J].辽宁城乡环境科技,1999(4):73-74.
[36]仇振琢.用6210净水剂直接去除电镀废水中Cr6+[J].水处理技术,2000,16(6):451.
[37]刘存海,李仲谨,卢卫军.电镀废格液的化学絮凝与铬的回收利用研究[J].西北农林科技大学学报(自然科学版),2001,29(1):66.
[38]李天铎.制革废水的资源化处理技术[J].山东化工,2001(30).
[39]王碧,马春辉,张铭让.制革废水与污泥中铬资源的回收及综合利用[J].中国皮革,2002,3(2):39.
[40]卫亚菲.制革工业污水综合治理和资源化利用[J].中国皮革,1999,26(12):25.
[41]刘明华,张新申,蒋小萍.吸附法处理制革工业中含硫、含铬废水的研究[J].中国皮革,2000,29(11):9.
[42]李硕文,陈扬,万伟.液膜法去除水中Cr(Ⅵ)的研究[J].环境科学与技术,2000(1):26-29.
[43]王靖芳,冯彦琳,孙双红等.乳状液膜法迁移及分离铬(Ⅵ)的研究[J].环境化学,1998,17(1):85-89.
[44]邵刚.膜法水处理技术[M].冶金工业出版社,1992.
[45]卫亚菲.制革工业污水综合治理和资源利用[J].中国皮革,1999,26(12):25.
[46]张建民,宋庆文,朱宝瑜等.生物法处理电镀铬废水的研究[J].西北纺织工学院学报,2001,13(4):420-424.
[47]张建民,宗刚,朱宝瑜等.生物处理电镀废水的研究[J].工业水处理,2001,19(5):21-22.
[48]李建德,冯承嬏,李瑞义等.处理六价铬溶液的一种新方法[J].工业水处理,1995,15(4):35.
[49]杨通在、刘义农,杨君等.阳离子型改性高分子絮凝剂对轻工废水的处理[J].工业水处理,1998,18(3):18.
[50]汤克勇,张铭让.循环利用铬鞣废夜的问题研究[J].皮革化学,2001,16(4):28-30.
[51]Bolbat F F,Lesh E U.New Method Nickel and Cobalt Metallurgy[M].Beijing: Metallurgy Industry Press,1981,303.
[52]LE song-guang(乐颂光).Cobalt Metallury(钴冶金)[M].Beijing:Metallurgy Industry Press,1981,303.
[53]Flynn D R,Twidwell L G.Selective recovery of nickel and cobalt from electromachining solution[A].EPD Congress91[C].Warrendale:The Mineral,Metal&Material Society,1991,353.
[54]Jiang Li(江丽).溶剂萃取法分离镍板极中镍、铬、钴的研究[J].Hydrometallurgy(湿法冶金),2000(19):46.
[55]汪小兰.有机化学[M].高等教育出版社,1987.
[56]曾毓华,陆雪芳,杜文英.相转移催化反应中界面性能的研究[J].化学学报,2000,58(1):34-38.
[57]文海,赵卫东,晨辉.提取菲醌方法研究[J].内蒙古林学院学报(自然科学版),1998,20(3):95-96.
[58]上海化工学院.工业菲气相催化氧化制取9,10-菲醌[J].炼焦化学,1975(5):13-18.
[59]#12.
[60]商振华,王淑芳,王俊德.菲氧化反应产物的高效液相色谱分析[J].分析化学,1990,18(5):461-462.
[61]汤桂娜,贺仕军,王保宁.多元校正-紫外可见分光光度法同时测定Cr(Ⅵ)与Cr(Ⅲ[J]).分析化学,1995,23(4):383.
[62]威安邦.无机化学教程[M].北京:人民教育出版社,1962,532-541.
[63]张春霞,杨放怀,孙富强.用百里酚蓝-亚甲蓝混合指示剂测定季胺盐型阳离子表面活性剂[J].郑州轻工业学院学报,1998:13(4),10-14.
[64]谢亚杰,王伟,刘深.表面活性剂制备技术与分析技术[M].北京:北京工业出版社,2006:392-393.
[65]施云海,陈斌,童思等.双烷链阳离子表面活性剂的合成与定量分析[J].分析化学研究简报,2003:31(3),322-325.
[66]刘增勋.相转移催化剂在有机化学和农药中的应用[M].北京:科学出版社,1987,1.