摘要
草浆是中国大多数造纸厂的主要浆种,草浆碱法蒸煮黑液是造纸厂废水主要污染源。由于存在硅含量低、热值低和规模小的特点,现阶段最成熟的黑液治理方法——碱回收法并不适应草浆碱法蒸煮黑液的治理。虽然现阶段很多大型造纸厂均采用碱回收的方式进行黑液治理,但由于投资大、运行费用高,造成厂家不使用碱回收装置,偷排黑液;而中小造纸厂没有实力建设碱回收装置,黑液成为污染环境和制约造纸行业发展的严重问题。
本论文旨在从资源化和生物处理的角度着手,为草浆碱法蒸煮黑液治理提供新的处理模式和工艺。
通过对30株具有木质素降解能力的白腐菌株处理不同黑液体系特性研究及不同菌系处理效应分析,结果表明:不同种属菌株具有不同的处理特性:云芝属的菌株S1B具有较强的降低体系pH的能力,可以有效将体系pH由pH7降低到pH2以下,酸析出体系中大多数木质素,去除COD负荷60%以上;多孔菌属的菌株CD4可以将体系pH由pH3调节到中性,COD去除率达到50%左右;平菇属的菌株BP2可以分泌漆酶,去除体系酸溶木质素,降低幅度达到80%左右;香菇属的菌株AX2具有一定的酸溶木质素降解效果;融合株处理特性显示在木质素降解和COD去除上不同菌株之间可能具有协同效应。纯粹光解预处理对于白腐菌处理黑液没有显著的促进作用。
对产酸菌株S1B的特性研究表明,体系pH、黑液负荷和碳源对于菌株S1B产酸有显著的影响,其处理黑液可以选择如下条件:起始体系pH6-7之间,COD负荷控制在13000mg/L以下,添加0.5%的淀粉类碳源,温度选择在25℃-40℃之间,不添加相关的营养盐。
菌株S1B、AX2、BP2、CD4及其混合培养处理黑液特性表明,菌株S1B可以有效降低体系pH,是处理黑液体系的主效菌株。混合培养并不能有效提高菌株S1B耐受高碱性和高负荷的能力,反而一定程度上抑制了菌株S1B的产酸特性,菌株S1B适合单株培养处理黑液。
菌株CD4可以有效降低菌株S1B处理黑液出水的体系COD和调高体系pH。不
同菌株与菌株CD4混合培养表明,菌株组合BP2+CD4混合培养可以有效去除出水中酸溶木质素含量。
确定白腐菌处理黑液模式为:菌株S1B单株培养处理,菌株组合BP2+CD4混合培养后续处理,产生COD负荷在3000-4000mg/L、pH中性、酸溶木质素含量在0.2g/L左右的出水。
研究UV-Fenton、超声、菌糠过滤、耐碱菌微酸化、厌氧-好氧、内电解辅助工艺对白腐菌处理的影响,发现菌糠过滤+耐碱菌微酸化前处理模式效果明显,50%左右的黑液被吸收,体系pH12-13降低到pH6左右,出水pH适应于后续菌株;厌氧-好氧+内电解为较好的后处理工艺,可以将体系COD负荷降低到200mg/L以下。
进行不同单元操作的放大研究,确定菌糠过滤—耐碱菌微酸化—产酸菌酸析—降解菌群调节—厌氧水解—接触氧化—内电解处理的黑液处理工艺,经20天的连续处理证明可以实现黑液的有效处理。
本论文首次将白腐菌调节pH特性应用到污水处理体系中,通过产酸代谢调节黑液体系体系pH,实现体系木质素的析出和碱性的消除。同时利用白腐菌对小分子木质素的降解,实现白腐菌调节pH和木质素降解能力的协同。
本论文首次将菌糠应用于难降解污水的预处理中,利用菌糠吸附和白腐菌固体体系中对污染物的强降解特性,产生可以有效处理高碱性芳香化合物污染体系的单元操作。
该论文的研究,为黑液白腐菌治理提供了理论与技术实践途径。
Most paper making industry in China takes the herbaceous material as the pulp and thus the alkaline wheat straw pulping black liquor is the main wastewater produced by paper mills. For the moment, the best process method of black liquor-chemical recovery is unsuitable for the treatment of alkaline wheat straw pulping black liquor for the characteristics of little silicon content, low caloric value and small scale. Because the investment and run expense are too high for many paper mills, the black liquor is still the main source of environmental pollution and the main difficulty in development of papermaking industry.
The thesis focused on bioprocess of alkaline wheat straw pulping black liquor and provided a new technology in its treatment.
It was showed in the study of characteristics of 30 strains of white rot fungi in black liquor treatment that photodissociation did not have obvious promoting effect on black liquor treatment by white rot fungi. Different species of the strains presented distinct characteristics. Strain S1B had strong ability of pH decline and it could reduce the system pH effectively from pH 7 below pH 2. Most of the lignin in the system was acidulated and the COD removal ratio reached over 60%. Strain CD4 could adjust system pH from pH3 to neutral, and the COD removal ratio reached about 50%. Strain BP2 could secrete laccase and remove almost about 80% acid-soluble lignin from the system. Strain AX2 had certain ability of acid-soluble lignin degradation. The study of fusants showed possibly synergistic effect of different strains on lignin degradation and COD removal.
The study of the characteristics of strain S1B showed that the system pH, the load of black liquor and carbon resource had prominent effect on acid generation by strain S1B.The possible conditions in black liquor treatment was as follows: original system pH between pH6-7, COD under 13000mg/L, with supplementation of 0.5% carbon resource, temperature between 25℃ to 40℃ , without any salts.
The study of black liquor process by strain S1B, AX2, BP2, CD4 and their mixed culture indicated that strain S1B was the major strain in the process which declined system pH effectively. Mixed culture did not improve the ability of strain S1B in resistance of high alkali and high load, and on the contrary restrain the acid generation of strain S1B. Therefore, single culture was more suitable for strain S1B in black liquor process.
Strain CD4 could reduce the system COD of the filtrate of strain S1B and increase the system pH effectively. The study of different strains cultured with strain CD4 showed that the mixed culture of strain BP2 and strain CD4 removed the acid-soluble lignin of the filtrate effectively.
The final process mode of black liquor by white rot fungi was decided that strain S1B was singly cultured first, then strain BP2 and strain CD4 were mixed cultured. Finally the filtrate was with the characteristics of COD between 3000-4000mg/L, pH neutral, the content of acid-soluble lignin about 0.2g/L.
After the study on the effect of different aided methods, such as UV-Fenton, ultrasonic, filtration through fungal culture, acidification by alkali-proof strain, A/O process and interior electrolytic method on black liquor treatment by white rot fungi, it showed that the combination of filtration through fungal culture and acidification by alkali-proof strain was the better pre-processing. And consequently 50% black liquor was absorbed and the system pH was declined from pH12-13 to pH6. The combination of A/O process and interior electrolytic method was the better post-processing which declined the system COD under 200mg/L.
After the study of scale up of different unit operations, the process technology of black liquor was achieved: filtration through fungal culture- acidification by alkali-proof strain-acidulation by acid generation by white rot fungi-pH adjustment with - A/O process-interior electrolytic method. And after 20-day continuous process the black liquor was treated effectively.
The characteristic of pH adjustment
引文
鲍国强.合理利用草类.纸和造纸,1999,(5):11-12
隆言泉.制浆造纸工艺学.北京:轻工业出版社,1980:423~425
武汉钢铁公司.工业污染及其防治技术经济分析.北京:冶金出版社,1991
张珂.造纸工业污染技术与环境管理.北京:轻工业出版社,1988
联合国环境署.制浆造纸工业环境管理[M].联合国环境署工业环境管理网(NIEM)中国专家组译.北京:中国轻工业出版社,1998
环保总局公布黑名单,环境违法十大案件 http://news.sina.com.cn/c/2003-09-25/1649819694s.shtmL
滑县县长立下治污“军令状” http://news.sina.com.cn/o/2003-10-23/1024973346s.shtmL
环保总局:十起严重污毁环境案被查处 http://finance.sina.com.cn/g/20010908/105076.htmL
省环保局曝光环境违法案件 http://news.sina.com.cn/o/2003-08-21/0459604201s.shtmL
俞正千.中国造纸碱回收五十年技术进步实录.国际造纸,1999,18(1):1~13
汪苹,邹培昌,张珂,等.在碱法制浆过程中同步除硅-中型实验.中国环境科学,1995,15(6):443~446
潘锡五.中国造纸工业的发展与碱回收和环境保护.中国造纸,1996,04:46~50
Macek,A..Research on Combustion of Black-Liquor Drops.Progress in Energy and Combustion Science,1999,25(3):275~304
周长玲,姜子忠,许易真.草浆黑液硫酸酸析木素的工艺条件.东北林业大学学报,2000,28(1):45~47
杨卫明,石颐.酸析木素法处理造纸黑液的改进与应用.环境工程,1997,15(2):3~6
张小勇,张建安,韩润林,等.碱法造纸黑液木质素生物酸析法.应用与环境生物学
报,1999,5(6):618~622
王三反,张国俊,薛向东,等.木质素及造纸黑液的碱析法处理机理.中国给水排水,2002,18(6):51~53
周建红,罗文谦.絮凝法处理造纸废水现状与发展趋势.安康师专学报,2002,14(1):65~67
贾增发,李耀阳.絮凝沉淀处理造纸黑液.环境保护,1997(5):13~14
王泽民,董德明,马小凡,等.利用硅藻土复合净水剂处理造纸废水的研究.非金属矿,1997(3):33~35
胡跃华,方学平,郭国瑞,等.PFS-H2O2处理碱法造纸黑液的研究.轻工环保,1993,15(2):13~15
Golike,G.P;Pu,Q.;Holman,KL,et.al.A New Method for Calculating Equilibrium Solubility of Burkeite and Sodium Carbonate in Black Liquor.Tappi Journal,2000,l83(7):68
汪绍儒.草浆黑液回收和资源再利用.纸和造纸,1997,(1):9~10
孙连超,穆环珍,杨醒华,等.造纸黑液资源化清洁生产工程技术.环境科学,1995,16(4):1~2
王长颊.利用造纸黑液生产酒精的实验研究.环境保护,1989,(1):22~23
张学恭. 一种造纸黑液的处理方法[P]. CNll56l26A[专], 19970806(19960131)IPCC02F1/52
杜仰民.造纸工业废水治理进展与评述.工业水处理,1997,17(3):1~5
Wallberg,O.,Joensson,A-S.;Wimmerstedt,R..Ultrafiltration of Kraft Black Liquor with A Ceramic Membrane.Desalination,2003,156(1-3):145~153
韩怀芬,金漫彤.膜生物反应技术处理造纸废水实验.水处理技术,2001,27(2):96~98
Wallberg,O.;Joensson,A-S.;Wimmerstedt,R..Fractionation and Concentration of Kraft Black Liquor Lignin with Ultrafiltration.Desalination,2003,154(2):187~199
潘碌亭,朱亦仁.乳状液膜法处理造纸黑液的研究.环境保护,1998(1):20~22
Helmy,SM.;El Rafie,S.;Ghaly,MY..Bioremediation Post-photo-oxidation and Coagulation for Black Liquor Effleunt Treatment.Desalination,2003,158(1):331~339
Sricharoenchaikul,V.;Hicks,A.L.;Frederick,W.J..Carbon and Char Residue Yields from Rapid Pyrolysis of Kraft Black Liquor.Bioresource Techonology, 2001,77(2):131~138
李洪仁,王敬涛,胡晓静.湿式氧化法处理工业污水的应用与展望.工业水处理,1999,19(3):10~11
王永仪,杨志华,蒋展鹏,等.废水湿式催化氧化处理研究进展.环境科学进展,1995,3(2):35~40
李锋,汪海峰,朱丹.超临界水氧化技术的研究与应用进展.上海电力学院学报,2002,18(1):17~22
Perezm.Metal Photocatalytic Treatment of Paper Pulp Bleach Effluents. Quim.Anal.,1997,16(3):211
Vinje,M.G.;Kuntz,G.P..Testing of Naturally Occurring Materials to Aid Pulp Mill Environmental Control.Pulp & Paper Canada,2000,101(6):33~36
Lara,MA.;Rodriguez-Malaver,AJ.;Rojas,OJ.,et.al.Black Liquor Lignin Biodegradation by Trametes Elegans.International Biodeterioration & Biodegradation, 2003,52(3):167~173
Buzzini,AP.;Pires,EC..Cellulose Pulp Mill Effluent Treatment in an Upflow Anaerobic Sludge Blanket Reactor.Process Biochemistry,2002,38(5):707~713
Olsson,J.;Wessman,D.;Zacchi,G..Vapour-liquid Partition of Volatile Organic Compounds in Kraft Black Liquors.NORD PULP PAP RES J,2000,15(4):266~274
Silvestre,A.J.D.;Pereira,C.C.L.;Neto,C.P..Easy Assessment of The Composition of Low-molecular-weight Organic Components of Industrial Eucalyptus Globulus Kraft Black Liquor.J PULP PAP SCI.,2000,26(12):421~427
Sumathi,S.;Phatak,V..Fungal Treatment of Bagasse Based Pulp and Paper Mill Wastes.Environmental Technology,1999,20(1):93~98
许忠扬,吴金义.毛发载体生物膜技术处理草浆黑液的工艺研究.污染防治技
术,1999,12(2):63~66
Villar,J.C.;Caperos,A.;Garcia-Ochoa,F..Treatment for Residual Sulfate Black Liquors: The Effect of Operational Variables on Effluent Pollutant Load.Appita Journal,2000,53(2):6
张一丁,王宏韬,郑丽娜.浅谈污水活性污泥处理法的革新和替代技术.国土与自然资源研究,2002,2:54~55
柳荣展,王广建.白腐菌在制浆造纸工业中的应用进展.青岛大学学报:工程技术版,2001,16(3):46~50,59.
赵立军,滕登用,刘金玲,等.废水厌氧生物处理技术综述与研究进展.环境污染治理技术与设备.2001,2(5):58-66.
Grobicki A,Stuckey D C.Performance of the anaerobic baffled reactor understeady-state and shock loading conditions.Biotech and Bioeng.,1991:344-355
陈叶福,郭雪娜,王正祥,等.木质素生物降解与纸浆工业废水脱色.工业微生物,2001,31(4):49~53
管运涛,蒋展鹏,祝万鹏,等.两相厌氧膜-生物系统处理造纸废水.环境科学,2000,4:51~56
Ross,W,Retal.Practical Application of the ADUF Process to the Full-scale Treatment of a Maizeprocession Effluent.Wat.Sci.Tech.,1992,25(10):27~39
李剑超,褚君达,丰华丽,等.我国稳定塘处理的研究与实践.工业用水与废水,2002,33(1):1~3
骆艳娥,李华,刘树文.固定化细胞生物反应器的应用及研究进展.微生物学杂志,2002,22(2):36~39
罗建中,张新霞,乔庆霞,等.固定化细胞技术用于废水深度处理.环境污染治理技术与设备,2002,3(6):69~73
Travieso L.,Benitez,F.,Weiland,P.,et al.Experiments on Immobilization of Microalgae for Nutrient Removal in Wasterwater Treatment.Biosource Technol., 1996,55(3):
181~186
黎刚.固定化技术进展.中国生物工程杂志,2002,22(5):45~49
李慧蓉.白腐真菌的研究进展.环境科学进展,1996,4(6):69~77
李慧蓉.白腐真菌在碳素循环中的地位和作用.微生物学通报,1996,23(2):105~109
李望,韩文质.对污染物有独特降解作用的白腐真菌.生物学通报, 1997,32(12): 10~12
Oviedo,C.;Contreras,D.;Freer,J..A Screening Method for Detecting Iron Reducing Wood-rot fungi.Biotechnology Letters,2003,25(11):891~893
Kim,H-Y.;Song,H-G.,Transformation and Mineralization of 2,4,6-trinitrotoluene by the White rot fungus Irpex lacteus.Applied Microbiology and Biotechnology, 2003,61(2): 150~156
Maximo,C.;Amorim,MTP.;Costa-Ferreira,M..Biotransformation of Industrial Reactive Azo Dyes by Geotrichum sp. CCMI 1019.Enzyme and Microbial Technology, 2003,32(1):145~151
Gonzlez,C.,Alvarez,R.,Coca,J..Effects of the Use of H2SO4 in Producing Humic Materials from Kraft Black Liquors.Biores Technol.,1992,40:81~83
毕鑫,路福平,杜连祥.白腐菌木素过氧化物酶发酵条件及其酶液对稻草降解的研究.纤维素科学与技术,2002,10(4):41~48
侯红漫,蒋姣姣.白腐菌Pleurotus ostreatus漆酶的生产及其最佳诱导条件.大连轻工业学院学报,2003,22(1):28~31
胡道伟,朱雄伟,梅运军,等.白腐菌产漆酶培养条件的研究.华中科技大学学报(自然科学版),2003,31(4):111~113
Belinky,PA.;Goldberg,D.;Krinfeld,B.;et al..Manganese-containing Superoxide Dismutase from the White-rot Fungus Phanerochaete chrysosporium: Its Function,Expression and Gene Structure. Enzyme and Microbial Technology,2002,31(6):754~764
Rothschild,N.;Novotny,D.;Sasek,V..Ligninolytic Enzymes of the Fungus Irpex lacteus
(Polyporus tulipiferae):Isolation and Characterization of Lignin Peroxidase. Enzyme and Microbial Technology,2002,31(5):627~633
Zheng,Z.;Obbard,JP..Removal of Surfactant Solubilized Polycyclic Aromatic Hydrocarbons by Phanerochaete chrysosporium in a Rotating Biological Contractor Reactor.Journal of Biotechnology,2002,96(3):241~249
Nuske,J.;Scheibner,K.;Dornberger,U..Large Scale Production of Manganese- peroxidase Using Agaric White-rot Fungi.Enzyme and Microbial Technology, 2002,30(4): 556~561
Koroleva,OV.;Gavrilova,VP.;Stepanova,EV..Production of Lignin Modifying Enzymes by Co-cultivated White-rot Fungi Cerrena maxima and Coriolus hirsutus and Characterization of Laccase from Cerrena maxima.Enzyme and Microbial Technology,2002,30(4):573~580
Robinson, T; Chandran, B; Nigam, P,Studies on the production of enzymes by white-rot fungi for the decolourisation of textile dyes,2001,Enzyme and Microbial Technology. Vol 29(8-9):575-579.
Pointing, SB , Feasibility of bioremediation by white-rot fungi,2001,Applied Microbiology and Biotechnology. Vol 57( 1-2): 20-33.
Merewether,JWT..The Precipitation of Lignin from Eucalyptus Kraft Black Liquors.Tappi.1962,45(2):159~163
Mohamed,K.,Sarra,B.,Semia,C..et al..Photodegradation of Lignin from Black Liquor Using a UV/TiO2 System.Journal of Photochemistry and Photobiology A: Chemistry, 2003,154:211~218
Perezm.Metal Photocatalytic Treatment of Paper Pulp Bleach Effluents. Quim.Anal.,1997,16(3):211
周贤涛,吴娟,林鹿.白腐菌对芳香族化合物的降解途径.环境污染治理技术与设备,2002,3(12):1~8
余惠生.白腐菌对稻草的生物降解规律及在生物制浆上的潜在应用.中国造纸,1989,8(1):16~20
闫松林,周从直.白腐菌处理废水的影响因素及发展趋势.水处理技术,2002,28(5):306~307
徐成勇,郭波,周莲,等.白腐菌对染料脱色和降解作用的研究进展.生物工程进展,2002,22(1):57~60
Zhang FM., Knapp JS., Tapley KN. Development of Bioreactor Systems for Decolorization of Orange 2 Using White Rot Fungus.Enzyme & Microbial Technology, 1999,24(1-2):48~53
范伟平,曹惠君,张俊,等.稻草末固定白腐菌处理染料废水的研究.化工环保,2002,22(1):7~11
黄俊,周申范.白腐真菌生物降解TNT装药废水的研究.环境科学与技术,1999,3:17~19
张景来,常冠钦,陆爱军.白腐工程菌处理TNT炸药废水的研究.中国矿业大学学报(自然科学版),2001,30(2):161~164
Eaton,D.,Hou min chang..Method Obtains Fungal Reduction of the Color Ofexaction Slage Kraft Bleach Effluents.Tappi J.,1983,65(6):89~92
林鹿,王双飞,陈嘉翔.白腐菌对蔗渣浆CEH漂白废水的脱色.工业水处理,1996, 16(3):25~26
Marwaha,SS.,Grover,R.,Prakash,C.,et al ..Continuous Biobleaching of Black Liquor from the Pulp and Paper Industry Using an Immobilized Cell System. Journal of Chemical Technology and Biotechnology,1998,73(3):292~296
Mittar,D., Khanna,PK., Marwaha,SS.,et al. .Biobleaching of Pulp and Paper Mill Effluents by Phanerochaete chrysosporium. Journal of Chemical Technology and Biotechnology,1992,53,(1):81~92
Woodard,FE.,Sproul,OJ.,Atkins,PF..The Biological Degradation of Lignin from Pulp Mill Black Liquor.Waste Conf. Purdue Univ. Engng Extn Ser.1963,115:550~561
吴涓,肖亚中,王怡平.白腐真菌处理灰法造纸黑液废水的研究.生物学杂志, 2002,19(5):17~19
何柱生.造纸黑液酸化及木质素沉降研究.宝鸡文理学院学报(自然科学版) 1996,16(4):24-29.
John,A.B.,Jinn,C..Effect of Nutrient Nitrogen and Manganese on Manganese Peroxidase and Laccase Production by Lentinus edodes. FEMS-microbiology Letters,1995,128:81~88
Glenn,J.K.,Gold,M.H..Purification and Characterization of an Extracellular Mn(Ⅱ)-dependent Peroxidase from the Lignin Degrading Basidiomycete.Archives of Biochemistry and Biophysics,1985,242(2):329~341
Tien,M.,Kirl,TK..Lignin Degradation Enzyme from Phanerochate chrysosporium. Proc Natl Sci.,1984,81:2280~2284.