过氧化氢脱毛方法及原理的研究
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摘要
本论文以牛皮为原料皮，研究了过氧化氢用量、脱毛液pH值、脱毛液温度、液比及过氧化氢加入速度等因素的变化对过氧化氢脱毛效果的影响规律。分析了脱毛废液中羟脯氨酸和氮含量与过氧化氢用量间的关系。通过检测废液中各种指标、铬鞣效果和坯革性能将过氧化氢脱毛方法和传统的硫化钠脱毛方法进行了比较，并观察了生皮和革的结构在使用不同脱毛方法时的区别，从组织学角度找到了过氧化氢脱毛的原理。
利用红外光谱技术分析了生皮中几种典型氨基酸在其与过氧化氢的碱性溶液作用后所发生的结构变化；分析了过氧化氢碱性溶液的作用对生皮的等电点、收缩温度及生皮胶原模拟物明胶的玻璃化温度的影响趋势。研究结果表明：
脱毛液pH值、过氧化氢用量的变化对过氧化氢脱毛效果影响最大，当脱毛液pH值高于12.5并且过氧化氢用量大于皮重的7.0％时，脱毛效果明显增强；脱毛液温度控制在25℃较宜，偏高或偏低均会使脱毛效果下降。较小的液比和较快的过氧化氢加入速度均对脱毛有着促进作用。但从废液中羟脯氨酸含量来看，过氧化氢用量不宜大于皮重的9.5％。
与传统硫化物脱毛方法相比，过氧化氢脱毛法不仅能降低脱毛废液的COD、硫化物、氨氮、悬浮固体含量，提高铬鞣革中Cr_2O_3含量和增大坯革的抗张强度，而且使真皮内毛根去除干净，胶原纤维分散快，革的粒面层与网状层间联结紧密。过氧化氢脱毛时毛由根部开始溶解。
过氧化氢脱毛时，毛中胱氨酸、皮板内丝氨酸、苏氨酸等发生结构变化，
四川大学博士学位论文
从而使毛的碱溶解性增大，生皮等电点被降低，生皮收缩温度及明胶玻璃化温
度被提高。
In this paper, the factors influencing hydrogen peroxide unhairing of cattle hide and the mechanism of the process were studied. The effects of hydrogen peroxide offer, pH value, temperature, float and added rate of hydrogen peroxide on efficiency of unhairing were investigated. Contents of hydroxy-proline and nitrogen in waste water were determined by colorimetry and Kjeldahl procedures so that the relationship between hydrolytic degree of hide protein and unhairing condition could be observed. The comparison of hydrogen peroxide unhairing and conventional sodium sulfide unhairing was made based component analysis of waste water, effectiveness of chrome tanning and physical properties of resultant leather. Meanwhile the influence of two unhairing techniques on microstructure of hide or leather in processing was researched by histological observation and the histological mechanism of hydrogen peroxide unhairing was elucidated.
To obtain further information of chemical mechanism, a series of typical ammo acids existing in hide collagen were treated with alkali hydrogen peroxide solution in the condition similar to unhairing process, and the change of their structure was determined by IR. Furthermore, the influences of alkali hydrogen peroxide solution on isoelectric point (IP) and shrinkage temperature (Ts) of hide and glass transition temperature (Tg) of gelatine were studied.
The trials above indicated that the offer of hydrogen peroxide and the pH value of float were the main factors affecting unhairing result. When pH value was 12.5-13.0 and hydrogen peroxide offer was more than 7.5% based on hide weight, hair could be easily removed. But when hydrogen peroxide offer was more than 9.5%, hide collagen would be damaged evidently. Suitable temperature of float was 25C; incomplete unhairing would be observed when lower temperature was used. A short float and a faster added rate of hydrogen peroxide were favourable to unhairing.
Compared with sodium sulfide unhairing, the unhairing with hydrogen peroxide could produce decreased contents of COD, S2", NH3-N2 and suspended solid in waste water; the content of S2- was particularly elimitated. It was also found that unhairing with hydrogen peroxide could increase content of Cr2O3 in leather after chrome tanning and improve tensile strength of crust. During unhairing, hair root was dissolved at the first, then hair was completely removed. At the same time, collagen fibers of hide were effectively dispersed. A distinct advantage of using hydrogen peroxide was that the connection of grain and reticular layers could be enhanced which could reduce loose grain of resultant leather.
Reacted with hydrogen peroxide, some of cystines in hiar were derived into sulfide or sulfonate, leading to hair removing. Alcoholic hydroxyl of serine in hide collagen was oxidized into carboxyl group, and that of threouine was oxidized into acetaldehyde which could link with free amino group of protein. The linkage between protein fibers was verified by increased Ts of hide and raised Tg of gelatine. Both the derivation of alcoholic hydroxyl into carboxyl group and the linkage interaction of free amino group led to lower IP of hide, as observed.
利用红外光谱技术分析了生皮中几种典型氨基酸在其与过氧化氢的碱性溶液作用后所发生的结构变化；分析了过氧化氢碱性溶液的作用对生皮的等电点、收缩温度及生皮胶原模拟物明胶的玻璃化温度的影响趋势。研究结果表明：
脱毛液pH值、过氧化氢用量的变化对过氧化氢脱毛效果影响最大，当脱毛液pH值高于12.5并且过氧化氢用量大于皮重的7.0％时，脱毛效果明显增强；脱毛液温度控制在25℃较宜，偏高或偏低均会使脱毛效果下降。较小的液比和较快的过氧化氢加入速度均对脱毛有着促进作用。但从废液中羟脯氨酸含量来看，过氧化氢用量不宜大于皮重的9.5％。
与传统硫化物脱毛方法相比，过氧化氢脱毛法不仅能降低脱毛废液的COD、硫化物、氨氮、悬浮固体含量，提高铬鞣革中Cr_2O_3含量和增大坯革的抗张强度，而且使真皮内毛根去除干净，胶原纤维分散快，革的粒面层与网状层间联结紧密。过氧化氢脱毛时毛由根部开始溶解。
过氧化氢脱毛时，毛中胱氨酸、皮板内丝氨酸、苏氨酸等发生结构变化，
四川大学博士学位论文
从而使毛的碱溶解性增大，生皮等电点被降低，生皮收缩温度及明胶玻璃化温
度被提高。
In this paper, the factors influencing hydrogen peroxide unhairing of cattle hide and the mechanism of the process were studied. The effects of hydrogen peroxide offer, pH value, temperature, float and added rate of hydrogen peroxide on efficiency of unhairing were investigated. Contents of hydroxy-proline and nitrogen in waste water were determined by colorimetry and Kjeldahl procedures so that the relationship between hydrolytic degree of hide protein and unhairing condition could be observed. The comparison of hydrogen peroxide unhairing and conventional sodium sulfide unhairing was made based component analysis of waste water, effectiveness of chrome tanning and physical properties of resultant leather. Meanwhile the influence of two unhairing techniques on microstructure of hide or leather in processing was researched by histological observation and the histological mechanism of hydrogen peroxide unhairing was elucidated.
To obtain further information of chemical mechanism, a series of typical ammo acids existing in hide collagen were treated with alkali hydrogen peroxide solution in the condition similar to unhairing process, and the change of their structure was determined by IR. Furthermore, the influences of alkali hydrogen peroxide solution on isoelectric point (IP) and shrinkage temperature (Ts) of hide and glass transition temperature (Tg) of gelatine were studied.
The trials above indicated that the offer of hydrogen peroxide and the pH value of float were the main factors affecting unhairing result. When pH value was 12.5-13.0 and hydrogen peroxide offer was more than 7.5% based on hide weight, hair could be easily removed. But when hydrogen peroxide offer was more than 9.5%, hide collagen would be damaged evidently. Suitable temperature of float was 25C; incomplete unhairing would be observed when lower temperature was used. A short float and a faster added rate of hydrogen peroxide were favourable to unhairing.
Compared with sodium sulfide unhairing, the unhairing with hydrogen peroxide could produce decreased contents of COD, S2", NH3-N2 and suspended solid in waste water; the content of S2- was particularly elimitated. It was also found that unhairing with hydrogen peroxide could increase content of Cr2O3 in leather after chrome tanning and improve tensile strength of crust. During unhairing, hair root was dissolved at the first, then hair was completely removed. At the same time, collagen fibers of hide were effectively dispersed. A distinct advantage of using hydrogen peroxide was that the connection of grain and reticular layers could be enhanced which could reduce loose grain of resultant leather.
Reacted with hydrogen peroxide, some of cystines in hiar were derived into sulfide or sulfonate, leading to hair removing. Alcoholic hydroxyl of serine in hide collagen was oxidized into carboxyl group, and that of threouine was oxidized into acetaldehyde which could link with free amino group of protein. The linkage between protein fibers was verified by increased Ts of hide and raised Tg of gelatine. Both the derivation of alcoholic hydroxyl into carboxyl group and the linkage interaction of free amino group led to lower IP of hide, as observed.
引文
[1]Shuhua zhang. Asia Pacific Leather Fair, Fashion and Finished Produts-Spring show, Hongkong. Indian Leather, 2000, 34(6): 37-44
[2]张淑华．二十年岁月流金，未来任重而道远—谈皮革工业的二次创业．中国皮革，1999，28(3)：3～6
[3]中国皮革信息编辑部．新世纪裘皮工业的机遇与挑战．中国皮革，2000，29(5)：3～7
[4]李方舟．WTO与中国皮革工业．中国皮革，2000，29(7)：17～18
[5]Editorial Office of Journal of Leather. Environmental Concerns. Leather, June, 1994: 17-18
[6]Editorial Office of Joumal of Leatherware. Keeping in Tune with Environmental Management Compulsion. Leatherware, 2000, 15(8/9): 5
[7]Editorial Office of Journal of Leatherware. Eu Sets the Trend in Environmental Concerns. Leatherware, 2000,15(2/3): 23～24
[8]A. Sahasranaman. Tanneries and Environment. Indian Leather, 1998, 31(12): 53～64
[9]J.P. Dix. Chemical Developments Leading to Cleaner Production. World Leather,2000, 13(3): 42～47
[10]A.Sahasranaman. Dustry-Dealing with Unresolved Technical Issues-Unido Initiatives-Anoverview. Indian Leather, 2000, 33(10): 15～22
[11]Editorial Office of Journal of The Leather Manufacture. Pullution Control. The Leather Manufacture, Sep., 1982:19～23
[12]汤克勇，王芳，苏智健，宋丽英，张铭让．皮革工业必须走可持续发展之路．中国皮革，2000，29(7)：19～22
[13]宋秀奇．适合中小型制革厂的污水处理技术．中国皮革．1996，25(2)：22
[14]N.K.Chandra Babu. Process Innovations for Pullution Reduction. The leather Manufacture., 2000, 118(1): 13～15
[15]BLC资料汇编
[16]张晓镭．制革清洁工艺技术及其理论．西北轻工业学院内部教材．999：31
[17]王树声．制革污水的处理与利用．轻工业出版社．1976
[18]陈学群，李文龙．制革废水处理技术的研究．中国皮革，2000，29(3)：18～21
[19]徐新鉴．对黄牛鞋面革准备工段清洁工艺的思考．中国皮革，1999，28(21)：15～19
[20]陈武勇，张洋，戚建国，田金平，姜永化，颜晓丹．二氧化氯水溶液氧化脱毛的研究与实践．中国皮革，1999，28(19)：4～5
[21]李建华．日本国的皮革清洁工艺和污水治理及综合利用．中国皮革，1996，25(10)：37
[22]丁绍兰，章川波，高孝忠，任宗奇．治理浸灰脱毛工序污染的技术综述．中国皮革，1996，25(9)：21～26
[23]温祖谋．制革水场的氨氮污染及其防治对策．中国皮革，1999，28(17)：6～7
[24]宋福荣．制革废水治理工艺技术．中国皮革，1998，27(1)：28～29
[25]常明．皮革二次创业与环境保护．中国皮革，2000，29(7)：34～37
[26]李楚华，张小林．应用奥贝尔氧化沟处理制革综合污水．中国皮革，1995，24(6)：38～39
[27]张炜，潘建国，张屹平．聚合硫酸铁在制革污水处理中的应用．中国皮革，1992，21(2)：35～36
[28]Willy Frendrup. Developments in Environmental Legislation relevant to the Leather Iudustry. World Leather, 2000, 13(7): 49～50
[29]朱荣基，罗真贵．制革废液中硫化物处理的实验研究．皮革科技动态，1979，86(6)：1～6
[30]严志弦．无机化学(上)．人民教育出版社，1972：303
[31][苏]A．A列塔维特．职业病学．人民卫生出版社，1976：205
[32]钱家骧．国内外制革厂废弃物处理概况．皮革科技动态，1978，75(7)：21～27
[33]BASF资料
[34]王吉成，乘荣声．酸化法治理含硫脱毛废水及回收毛蛋白的研究．四川皮革，1986，1：20～22
[35]胡桂英．论我国制革工业废水的防治．中国皮革，1990，19(1)：4～7
[36]Editorial Office of Journal of Leather. Pullution Control—Chinese style. Leather, 2000, 202(2): 31～33
[37]Stephen Feaivheller. ALCA Meeting Report. The Leather Manufacture, 1987(7): 6～8
[38]Editorial Office of Journal of Leather. Environmental concerns. Leather, 1994(6):17～18
[39]M.M. Taylor, D.G.Bailey and S.H.Feairheller. A Review of the Uses of Enzymes in the
Tannery. JALCA, 1987, 82:153-163
[40]汤金才，毛小平．制革厂硫化钠废水治理．皮革科技，1981，78(7)：1～4
[41]T. Feigl. Use of Enzymes in Beamhouse. JSLTC, 1999, 83(1): 57
[42]于义，潘鸿．猪皮酶法脱毛新工艺技术开发试制．皮革科学与工程．2000(1)：26
[43]Rom Ro 108,805,1994
[44]汪建根，孙献军，彭文利．黄牛皮鞋面革酶法脱毛新工艺的研究．中国皮革，2000，29(3)：25～29
[45]C.S. Cantem. Hair-Saving Unhairing Process: Patr 1. Epidermis and the characteristics of Bovine Hear. JS LTC, 2001, 85(1): 1～5
[46]C.A.Money. Unhairing and Dewooling-Reguirements for Quality and the Environment JSLTC, 1996,80:175～186
[47]R.G.Paul,I.Mohamed, D.Davighi,A.D.Covington and V.L.Addy. The Use of Neutral Protease in Enzymatic Unhairing. JALCA, 2001, 96(5): 180～185
[48]E. Befia Thangam,T nagarajan, G. Suseela Rajkumar and N.K.Chandrababu. Application of Alkaline Protease Isolated from Aicaligenes Faecalis for Enzymatic Unhairing in Tanneries. JALCA, 2001, 96(4): 127～132
[49]E. Heidermann and V.J.Smidek. Entwicklung von sulfidfreien und suIfidarmen Enthaarungen. Das Leder, 1987, 38: 48～57.
[50]D.Ivanova, M.koleva, M.Alexieva. Die Einsparung des Beizprozesses zur Herstellung von schafbekleidungsleder bei Anwendung einer Enzymatischen Weiche und Enthaamng. Leder, 1993, 44(9): 191～193
[51]Adewoye,K.O.and Lollar, R.M.. Use of Pulped Fruit of Adenopus Breviflorus (TAGIRI)As an Unhairing Agent and Characterization of the Enzymes Extracted from the fruit. JALCA, 1984, 79(12): 446～461
[52]Raju,A.A.;Chandrababu,N.K.;Samivelu,N.;Rose,C.and Rao,N.M.. Eco—Friendly Enzymatic Dehairing Using Extracellular Proteases From a Bacillus SPECIES Isolate. JALCA, 1996,91(5): 115—119
[53]R.W. Cranston,M.H.Davis and J.G.Scroggie. Development of the "Sirolime"Unhairing Process. JALCA, 1986, 81:347～355
[54]Kohkichi Uehara, Ayako Matsunaga, Katsuhiko Arai,Hamkazu Toyoda and Yasumasa Chonan. Solubilization of Steer and KipHair Recovered by the Sirolime Process. JALCA, 1987.82(4): 77～85
[55]L.J.Stephens,D.E.Peters and A.C.Trujstman. The Physical Properties of Leather From KangaRoo skin. JALCA, 1989, 84:296～305
[56]丁绍兰，章川波，高孝忠，任宗奇．常规毁毛浸灰脱毛废液循环使用的研究．中国皮革，1997，26(4)：14～19
[57]丁绍兰，章川波，高孝忠，任宗奇．碱免疫护毛法及废液的循环使用研究．中国皮革，1997，26(9)：7～9
[58]丁绍兰，章川波，高孝忠，任宗奇．小液比保毛法及其废液循环使用的研究．中国皮革，1997，26(10)：25～29
[59]Editorial Office of Journal of Leather. Ecological production. Leather, March, 1995: 86-92
[60]Max S.Maire. Chrome and Sulfide Conservation. Leather Manufacture, 1981, 99(10):22～27
[61]苏小春．大卫·温特斯介绍制革污水处理．皮革科技，1985，5：35～37
[62]屈惠东．制革浸灰废液循环使用的工艺研究．中国皮革，1994，11：40～44
[63]丁绍兰．制革浸灰脱毛废液循环使用的研究．西北轻工业学院硕士论文：16
[64]谢海宝．国外制革三废治理动向．皮革科技，1987，5：41
[65]刘镇华，魏世林，潘健，沈谡民．水牛服装革的脱毛、剖层、复灰工序的研究，中国皮革，1995，24(8)：9～12
[66]T. Ramasami, J.Raghava Rao, N.K.Chandrao Babu, K.Parthasarathi, P.G.Rao, P. Saravanay, R.Gayathri and K.J.Sreeram. Beamhouse and Tanning Operations. The Leather Mannfacture, 1998, Dec.: 10～18
[67]陈珍林．硫氢化钠在制革中的应用．中国皮革，1992，21(3)：34～35
[68]H.A.M.EL Baba, A.D.Covington and D.Davighi. The Effect of Hair Shaving on Unhairing Reactions: Part 1 JSLTC, 1999, 83:200～203
[69]H.A.M.EL Baba, A.D.Covington and D.Davighi. The Effect of Hair Shaving on Unhairing Reaction:Part 2. JSLTC, 2000, 84:48～53
[70] 天津皮革制品工业公司．制革准备．北京轻工业出版社，1977：72~99
[71] E.Heidemann.Fundamentals of Leather Manufacturing.Eduard Roether/KG.1993: 192-193
[72] J.M.Morera,E.Bartoli,M.D.Borras,D.Munoz,J.Jimenez,A.marsal.Liming Process Using Hydrogen Peroxide.JSLTC,1997,81:70-73
[73] J.M.Morera,E.Bartoli,M.D.Borras,J.Chico,A.Marsal."Study on an oxidative unhairing process free from sulphide",paper given at the XLVI AQEIC Congress.Estoril (Portugal),May,1997
[74] J.M.Morera,E.Bartoli,M.D.Borras,D.Munoz,A.Marsal."Study on an unhairing process with hydrogen peroxide".Paper given at the XLIV AQEIC Congress.Puerto Lumbreras(Spain),May,1995
[75] DE 10,008,770,2000
[76] EP 519,399,1992
[77] Kochetova,S.P.; Studenikin,S.I.; Markova,J.A.;Pogozheva,T.I..Structure of Hairless Hide Processed by a Sulfide-free Technology.CA,1996,124(20) : 263942v
[78] Kosheleva,O.E.; Steshow,G.I.;Kutsidi,D.A..Elastoplastic properties of Leather prepared by peroxy-alkaline Unhairing.CA,1989,111: 99301u
[79] Shpak,N.V.; Steshov,G.I.; Kosheleva,O.E.; Steshva,L.R.Tanning of Semifinished ProductsUnhaired by the Peroxide-alkali Procedure.CA,1989,111: 156297y.
[80] Kosheleva,O.E.; Steshov,G.I.; Kutsidi,D.A..Changes in Skin Porosity During the Oxidative Unhairing-Liming Process.CA,1989,109:75629q
[81] Morera,J.M.; Bartoli,E.; Borras,M.D.; Jimenez,F.J.; Marsal,A.; Costo Lopez,J..Liming with Hydrogen Peroxide.CA,1996,124:235424J
[82] 孙玉珍.山羊打光鞋面革重点工艺探讨．中国皮革，2000，29(3) ：30~32
[83] 卢行芳，李景梅．绵羊皮正面服装革生产技术．北京皮革，1999，2：53～56
[84] A.D.Covington.The Effects of Processing Conditions on the Hydrothermal Stability of Chrome Leather: Parti.JALCA,1991,86:376-405
[85] J.Raghava Rao,B.Chandrasekaran,V.Subramanian.Physico-Chemical and Structural Studies on Leathers Tanned Using High Exhaust Basic Chromium Sulphate Salt.JALSA,
1998, 93:139～155
[86]Paul L.Kronick and Susan landola. Persistence of Miority Macromolecules of Hide Through the Beamhouse. JALCA, 1997, 92:172-178
[87]Victoria Addy. Unravelling the Unhairing Process. World Leather. 2000, 13(6): 59～60
[88]吕希伦．无机过氧化合物化学．科学出版社，1987：65～112
[89]E.R.Trotman. Dyeing and Chemical Technology of Textile Fibres(3rd edition). London. 1964:226～233
[90][德]福瑞兹，石他特．蒲敏功译．制革化学及制革工艺学．轻工业出版社，1958：887～890
[91][苏]恰茨基．陈兰芬译．毛皮染整工艺．轻工业出版社，1986：887～890
[92]CN85102770
[93]成都科技大学，西北轻工业学院．制革化学及工艺学．轻工业出版社，1994：150～187
[94]俞从正．含胶原物质的羟基脯氨酸的测定．皮革科技，1981，9：43～44
[95]蒋莹．氨基酸的应用．世界图书出版公司，1996：12
[96]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：486～491
[97]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：468～469
[98]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：472～475
[99]O. Menderes, A. D. Covington, E. R. Waite and M.J.Colling. The Mechanism and Effects of Collagen Amide Group Hydrolysis During Liming. JSLTC, 1999, 83:107～110
[100]Heidemann,E.and Smidek, V.J.. Entwicklung von sulfidfreien und Sulfidarmen Enth Aarungen. Das Leder, 1987, 38:48～57
[101]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：959～960
[102]骆鸣汉．毛皮工艺学．轻工业出版社，2000：110
[103]郑超斌．毛皮褪色漂白：工艺．轻工业出版社，1997：59～61
[104]L.Wolfram. The Mechanisum of Hair Bleaching. J.Soc. Cosmet. Chem., 1970, 21:875
[105]赵良仲．用电子能谱研究头发角蛋白氧化机理．生物化学与生物物理学报，1981(5)：504～508
[106]赵良仲．人体头发黑色素的电子能谱研究．生物化学与生物理学报．1983(3)：21～26
[107]王学琳，孙淑萍．波谱分析．辽宁大学出版社．1990
[108]张淑良，易大年，吴天明．红外光谱分析与新技术．中国医药科技出版社，1993
[109]卢涌泉，邓振华．实用红外光谱解析．电子工业出版社．1989
[110]成都科技大学，西北轻工业学院．制革化学及工艺学(上)．轻工业出版社，1994：39
[111]成都科技大学《高分子物理》编写组．高分子物理．成都科技大学出版社，1990：145～154
[112]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：745～747
[2]张淑华．二十年岁月流金，未来任重而道远—谈皮革工业的二次创业．中国皮革，1999，28(3)：3～6
[3]中国皮革信息编辑部．新世纪裘皮工业的机遇与挑战．中国皮革，2000，29(5)：3～7
[4]李方舟．WTO与中国皮革工业．中国皮革，2000，29(7)：17～18
[5]Editorial Office of Journal of Leather. Environmental Concerns. Leather, June, 1994: 17-18
[6]Editorial Office of Joumal of Leatherware. Keeping in Tune with Environmental Management Compulsion. Leatherware, 2000, 15(8/9): 5
[7]Editorial Office of Journal of Leatherware. Eu Sets the Trend in Environmental Concerns. Leatherware, 2000,15(2/3): 23～24
[8]A. Sahasranaman. Tanneries and Environment. Indian Leather, 1998, 31(12): 53～64
[9]J.P. Dix. Chemical Developments Leading to Cleaner Production. World Leather,2000, 13(3): 42～47
[10]A.Sahasranaman. Dustry-Dealing with Unresolved Technical Issues-Unido Initiatives-Anoverview. Indian Leather, 2000, 33(10): 15～22
[11]Editorial Office of Journal of The Leather Manufacture. Pullution Control. The Leather Manufacture, Sep., 1982:19～23
[12]汤克勇，王芳，苏智健，宋丽英，张铭让．皮革工业必须走可持续发展之路．中国皮革，2000，29(7)：19～22
[13]宋秀奇．适合中小型制革厂的污水处理技术．中国皮革．1996，25(2)：22
[14]N.K.Chandra Babu. Process Innovations for Pullution Reduction. The leather Manufacture., 2000, 118(1): 13～15
[15]BLC资料汇编
[16]张晓镭．制革清洁工艺技术及其理论．西北轻工业学院内部教材．999：31
[17]王树声．制革污水的处理与利用．轻工业出版社．1976
[18]陈学群，李文龙．制革废水处理技术的研究．中国皮革，2000，29(3)：18～21
[19]徐新鉴．对黄牛鞋面革准备工段清洁工艺的思考．中国皮革，1999，28(21)：15～19
[20]陈武勇，张洋，戚建国，田金平，姜永化，颜晓丹．二氧化氯水溶液氧化脱毛的研究与实践．中国皮革，1999，28(19)：4～5
[21]李建华．日本国的皮革清洁工艺和污水治理及综合利用．中国皮革，1996，25(10)：37
[22]丁绍兰，章川波，高孝忠，任宗奇．治理浸灰脱毛工序污染的技术综述．中国皮革，1996，25(9)：21～26
[23]温祖谋．制革水场的氨氮污染及其防治对策．中国皮革，1999，28(17)：6～7
[24]宋福荣．制革废水治理工艺技术．中国皮革，1998，27(1)：28～29
[25]常明．皮革二次创业与环境保护．中国皮革，2000，29(7)：34～37
[26]李楚华，张小林．应用奥贝尔氧化沟处理制革综合污水．中国皮革，1995，24(6)：38～39
[27]张炜，潘建国，张屹平．聚合硫酸铁在制革污水处理中的应用．中国皮革，1992，21(2)：35～36
[28]Willy Frendrup. Developments in Environmental Legislation relevant to the Leather Iudustry. World Leather, 2000, 13(7): 49～50
[29]朱荣基，罗真贵．制革废液中硫化物处理的实验研究．皮革科技动态，1979，86(6)：1～6
[30]严志弦．无机化学(上)．人民教育出版社，1972：303
[31][苏]A．A列塔维特．职业病学．人民卫生出版社，1976：205
[32]钱家骧．国内外制革厂废弃物处理概况．皮革科技动态，1978，75(7)：21～27
[33]BASF资料
[34]王吉成，乘荣声．酸化法治理含硫脱毛废水及回收毛蛋白的研究．四川皮革，1986，1：20～22
[35]胡桂英．论我国制革工业废水的防治．中国皮革，1990，19(1)：4～7
[36]Editorial Office of Journal of Leather. Pullution Control—Chinese style. Leather, 2000, 202(2): 31～33
[37]Stephen Feaivheller. ALCA Meeting Report. The Leather Manufacture, 1987(7): 6～8
[38]Editorial Office of Journal of Leather. Environmental concerns. Leather, 1994(6):17～18
[39]M.M. Taylor, D.G.Bailey and S.H.Feairheller. A Review of the Uses of Enzymes in the
Tannery. JALCA, 1987, 82:153-163
[40]汤金才，毛小平．制革厂硫化钠废水治理．皮革科技，1981，78(7)：1～4
[41]T. Feigl. Use of Enzymes in Beamhouse. JSLTC, 1999, 83(1): 57
[42]于义，潘鸿．猪皮酶法脱毛新工艺技术开发试制．皮革科学与工程．2000(1)：26
[43]Rom Ro 108,805,1994
[44]汪建根，孙献军，彭文利．黄牛皮鞋面革酶法脱毛新工艺的研究．中国皮革，2000，29(3)：25～29
[45]C.S. Cantem. Hair-Saving Unhairing Process: Patr 1. Epidermis and the characteristics of Bovine Hear. JS LTC, 2001, 85(1): 1～5
[46]C.A.Money. Unhairing and Dewooling-Reguirements for Quality and the Environment JSLTC, 1996,80:175～186
[47]R.G.Paul,I.Mohamed, D.Davighi,A.D.Covington and V.L.Addy. The Use of Neutral Protease in Enzymatic Unhairing. JALCA, 2001, 96(5): 180～185
[48]E. Befia Thangam,T nagarajan, G. Suseela Rajkumar and N.K.Chandrababu. Application of Alkaline Protease Isolated from Aicaligenes Faecalis for Enzymatic Unhairing in Tanneries. JALCA, 2001, 96(4): 127～132
[49]E. Heidermann and V.J.Smidek. Entwicklung von sulfidfreien und suIfidarmen Enthaarungen. Das Leder, 1987, 38: 48～57.
[50]D.Ivanova, M.koleva, M.Alexieva. Die Einsparung des Beizprozesses zur Herstellung von schafbekleidungsleder bei Anwendung einer Enzymatischen Weiche und Enthaamng. Leder, 1993, 44(9): 191～193
[51]Adewoye,K.O.and Lollar, R.M.. Use of Pulped Fruit of Adenopus Breviflorus (TAGIRI)As an Unhairing Agent and Characterization of the Enzymes Extracted from the fruit. JALCA, 1984, 79(12): 446～461
[52]Raju,A.A.;Chandrababu,N.K.;Samivelu,N.;Rose,C.and Rao,N.M.. Eco—Friendly Enzymatic Dehairing Using Extracellular Proteases From a Bacillus SPECIES Isolate. JALCA, 1996,91(5): 115—119
[53]R.W. Cranston,M.H.Davis and J.G.Scroggie. Development of the "Sirolime"Unhairing Process. JALCA, 1986, 81:347～355
[54]Kohkichi Uehara, Ayako Matsunaga, Katsuhiko Arai,Hamkazu Toyoda and Yasumasa Chonan. Solubilization of Steer and KipHair Recovered by the Sirolime Process. JALCA, 1987.82(4): 77～85
[55]L.J.Stephens,D.E.Peters and A.C.Trujstman. The Physical Properties of Leather From KangaRoo skin. JALCA, 1989, 84:296～305
[56]丁绍兰，章川波，高孝忠，任宗奇．常规毁毛浸灰脱毛废液循环使用的研究．中国皮革，1997，26(4)：14～19
[57]丁绍兰，章川波，高孝忠，任宗奇．碱免疫护毛法及废液的循环使用研究．中国皮革，1997，26(9)：7～9
[58]丁绍兰，章川波，高孝忠，任宗奇．小液比保毛法及其废液循环使用的研究．中国皮革，1997，26(10)：25～29
[59]Editorial Office of Journal of Leather. Ecological production. Leather, March, 1995: 86-92
[60]Max S.Maire. Chrome and Sulfide Conservation. Leather Manufacture, 1981, 99(10):22～27
[61]苏小春．大卫·温特斯介绍制革污水处理．皮革科技，1985，5：35～37
[62]屈惠东．制革浸灰废液循环使用的工艺研究．中国皮革，1994，11：40～44
[63]丁绍兰．制革浸灰脱毛废液循环使用的研究．西北轻工业学院硕士论文：16
[64]谢海宝．国外制革三废治理动向．皮革科技，1987，5：41
[65]刘镇华，魏世林，潘健，沈谡民．水牛服装革的脱毛、剖层、复灰工序的研究，中国皮革，1995，24(8)：9～12
[66]T. Ramasami, J.Raghava Rao, N.K.Chandrao Babu, K.Parthasarathi, P.G.Rao, P. Saravanay, R.Gayathri and K.J.Sreeram. Beamhouse and Tanning Operations. The Leather Mannfacture, 1998, Dec.: 10～18
[67]陈珍林．硫氢化钠在制革中的应用．中国皮革，1992，21(3)：34～35
[68]H.A.M.EL Baba, A.D.Covington and D.Davighi. The Effect of Hair Shaving on Unhairing Reactions: Part 1 JSLTC, 1999, 83:200～203
[69]H.A.M.EL Baba, A.D.Covington and D.Davighi. The Effect of Hair Shaving on Unhairing Reaction:Part 2. JSLTC, 2000, 84:48～53
[70] 天津皮革制品工业公司．制革准备．北京轻工业出版社，1977：72~99
[71] E.Heidemann.Fundamentals of Leather Manufacturing.Eduard Roether/KG.1993: 192-193
[72] J.M.Morera,E.Bartoli,M.D.Borras,D.Munoz,J.Jimenez,A.marsal.Liming Process Using Hydrogen Peroxide.JSLTC,1997,81:70-73
[73] J.M.Morera,E.Bartoli,M.D.Borras,J.Chico,A.Marsal."Study on an oxidative unhairing process free from sulphide",paper given at the XLVI AQEIC Congress.Estoril (Portugal),May,1997
[74] J.M.Morera,E.Bartoli,M.D.Borras,D.Munoz,A.Marsal."Study on an unhairing process with hydrogen peroxide".Paper given at the XLIV AQEIC Congress.Puerto Lumbreras(Spain),May,1995
[75] DE 10,008,770,2000
[76] EP 519,399,1992
[77] Kochetova,S.P.; Studenikin,S.I.; Markova,J.A.;Pogozheva,T.I..Structure of Hairless Hide Processed by a Sulfide-free Technology.CA,1996,124(20) : 263942v
[78] Kosheleva,O.E.; Steshow,G.I.;Kutsidi,D.A..Elastoplastic properties of Leather prepared by peroxy-alkaline Unhairing.CA,1989,111: 99301u
[79] Shpak,N.V.; Steshov,G.I.; Kosheleva,O.E.; Steshva,L.R.Tanning of Semifinished ProductsUnhaired by the Peroxide-alkali Procedure.CA,1989,111: 156297y.
[80] Kosheleva,O.E.; Steshov,G.I.; Kutsidi,D.A..Changes in Skin Porosity During the Oxidative Unhairing-Liming Process.CA,1989,109:75629q
[81] Morera,J.M.; Bartoli,E.; Borras,M.D.; Jimenez,F.J.; Marsal,A.; Costo Lopez,J..Liming with Hydrogen Peroxide.CA,1996,124:235424J
[82] 孙玉珍.山羊打光鞋面革重点工艺探讨．中国皮革，2000，29(3) ：30~32
[83] 卢行芳，李景梅．绵羊皮正面服装革生产技术．北京皮革，1999，2：53～56
[84] A.D.Covington.The Effects of Processing Conditions on the Hydrothermal Stability of Chrome Leather: Parti.JALCA,1991,86:376-405
[85] J.Raghava Rao,B.Chandrasekaran,V.Subramanian.Physico-Chemical and Structural Studies on Leathers Tanned Using High Exhaust Basic Chromium Sulphate Salt.JALSA,
1998, 93:139～155
[86]Paul L.Kronick and Susan landola. Persistence of Miority Macromolecules of Hide Through the Beamhouse. JALCA, 1997, 92:172-178
[87]Victoria Addy. Unravelling the Unhairing Process. World Leather. 2000, 13(6): 59～60
[88]吕希伦．无机过氧化合物化学．科学出版社，1987：65～112
[89]E.R.Trotman. Dyeing and Chemical Technology of Textile Fibres(3rd edition). London. 1964:226～233
[90][德]福瑞兹，石他特．蒲敏功译．制革化学及制革工艺学．轻工业出版社，1958：887～890
[91][苏]恰茨基．陈兰芬译．毛皮染整工艺．轻工业出版社，1986：887～890
[92]CN85102770
[93]成都科技大学，西北轻工业学院．制革化学及工艺学．轻工业出版社，1994：150～187
[94]俞从正．含胶原物质的羟基脯氨酸的测定．皮革科技，1981，9：43～44
[95]蒋莹．氨基酸的应用．世界图书出版公司，1996：12
[96]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：486～491
[97]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：468～469
[98]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：472～475
[99]O. Menderes, A. D. Covington, E. R. Waite and M.J.Colling. The Mechanism and Effects of Collagen Amide Group Hydrolysis During Liming. JSLTC, 1999, 83:107～110
[100]Heidemann,E.and Smidek, V.J.. Entwicklung von sulfidfreien und Sulfidarmen Enth Aarungen. Das Leder, 1987, 38:48～57
[101]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：959～960
[102]骆鸣汉．毛皮工艺学．轻工业出版社，2000：110
[103]郑超斌．毛皮褪色漂白：工艺．轻工业出版社，1997：59～61
[104]L.Wolfram. The Mechanisum of Hair Bleaching. J.Soc. Cosmet. Chem., 1970, 21:875
[105]赵良仲．用电子能谱研究头发角蛋白氧化机理．生物化学与生物物理学报，1981(5)：504～508
[106]赵良仲．人体头发黑色素的电子能谱研究．生物化学与生物理学报．1983(3)：21～26
[107]王学琳，孙淑萍．波谱分析．辽宁大学出版社．1990
[108]张淑良，易大年，吴天明．红外光谱分析与新技术．中国医药科技出版社，1993
[109]卢涌泉，邓振华．实用红外光谱解析．电子工业出版社．1989
[110]成都科技大学，西北轻工业学院．制革化学及工艺学(上)．轻工业出版社，1994：39
[111]成都科技大学《高分子物理》编写组．高分子物理．成都科技大学出版社，1990：145～154
[112]西北轻工业学院皮革教研室．皮革分析检验．轻工业出版社，1993：745～747
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