CN1266056C - 涂料废水的处理方法 - Google Patents
涂料废水的处理方法 Download PDFInfo
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- CN1266056C CN1266056C CNB031487653A CN03148765A CN1266056C CN 1266056 C CN1266056 C CN 1266056C CN B031487653 A CNB031487653 A CN B031487653A CN 03148765 A CN03148765 A CN 03148765A CN 1266056 C CN1266056 C CN 1266056C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/14—Paint wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/286—Anaerobic digestion processes including two or more steps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
提供通过将涂料废水中所含的难分解性物质转化成易分解性物质,从而与废水中的污染物质浓度的变动和处理量的变动对应的高效率的涂料废水的处理方法。向喷漆废水照射微波,分解该废水中所含的有机物质。进而根据需要,也可以对微波照射前的涂料废水进行采用凝聚剂或电解处理的凝聚处理。另外,照射微波将废水中所含的难分解性物质分解直到成为易分解性物质后,将得到的处理水供给到生物反应槽,在需氧或厌氧下进行生物处理是所希望的。
Description
发明领域
本发明涉及涂料废水的处理方法。
背景技术
过去,从喷漆工厂、涂料制造工厂等排出的涂料废水,为了迅速且效率好地分离除去其中的涂料,一般是向涂料废水中添加凝聚剂(floccu1ant),首先使涂料凝聚分离而除去,接着将该凝聚分离处理水在需氧(有氧)下进行生物处理。可是,在生物处理中,微生物分解的能力有限。因此,为了将废水中所含的污染物质转变成微生物容易分解的物质,开发了臭氧分解法、フエントン(Fenton Method)、UV照射法等各种的方法。例如,日本专利公开第1996-155308号公报公开了在光氧化催化剂的存在下,照射紫外线和/或可见光线,从而氧化分解含有有机物的废水的处理方法;日本专利公开第2001-259620号公报公开了在光催化剂的存在下,同时照射紫外线和微波,氧化分解水中的有机物的方法。另外,日本专利公开第2000-263056号公报(=WO 00/56663、EP113865)公开了在外加高电压的同时,发送高频的电磁波以分离除去有机物的方法;日本专利公开第2002-336850号公报公开了在特定的固体催化剂的存在下照射微波,以除去水中的硝酸性氮的方法。
可是,这些方法,充分分解污染物质是困难的,在污染物质浓度为高浓度,或者处理量增大的情况下,存在紫外线被有机物吸收,不能分解的物质残留在最终处理水中的危险。
本发明的目的在于,提供将涂料废水中所含的难分解性物质转换成易分解性物质的、高效率的处理涂料废水的方法。
发明内容
本发明人为解决上述课题而锐意研究的结果,发现:通过向涂料废水照射微波,分解该涂料废水中所含的有机物质,能够将难分解性物质转换成易分解性物质,进而通过将得到的处理水进行生物处理,能够容易且可靠地处理涂料废水,以至于完成本发明。
即,本发明涉及以下处理方法:涂料废水的处理方法,其特征是,向涂料废水照射微波,以分解该废水中所含的有机物质;以及,涂料废水的处理方法,其中,向涂料废水照射微波,将废水中所含的难分解性物质分解直到成为易分解性物质后,将得到的处理水供给到生物反应槽,在需氧(有氧)或厌氧(无氧)下进行生物处理。
附图的简单说明
图1是说明本发明优选实施方案的废水处理的流程图。
发明的实施方案
以下更详细地说明本发明的废水处理方法。
所谓本发明的涂料废水,例如可列举出汽车等喷漆线和修理工厂中的喷漆车间水(coating booth water)和从涂料制造工厂等产生的工业废水等。
这些废水中主要含有来自涂料的各种颜料、有机树脂、交联剂、有机溶剂等,但对于其组成和含量,根据工厂不同、根据时间不同而变动,不是一定的。例如,举出汽车的喷漆线的废水的一例,为沉淀物1-100g/升、CODMn 1000-10000mg/升、TOC 1000-15000mg/升、BOD1000-5000mg/升及有机溶剂1-10000mg/升左右。在此,CODMn意味化学氧供给量,TOC意味总有机体碳量,BOD意味生化氧要求量。作为有机溶剂,例如可列举出水溶性的醚系或醇系的溶剂。
上述涂料废水,在照射微波的前后工序的某处根据需要通过添加凝聚剂和电解处理等来凝聚分离处理是所希望的。除了污染物质的浓度非常低,或几乎不含有难分解性的物质等这些特别的情况以外,特别是在照射微波之前,首先进行凝聚分离处理,制成从该涂料废水分离除去浮游或沉淀分离的污泥(sludge)的处理水是所希望的。
作为凝聚剂,例如可列举出硫酸铝、聚合氯化铝(polyaluminumchloride)、氯化亚铁等所代表的无机系凝聚剂、表面活性剂等低分子凝聚剂、阴离子性、弱阴离子性、非离子性或阳离子性的高分子凝聚剂等。根据废水的种类可以单独使用它们、或者将多种组合来使用。
另外,电解处理是将电极放到废水中,流过电流,使用通过水的电解而产生的氧和氢的微细的气泡,吸附废水中的颜料和树脂等,由气泡的浮力将那些物质凝聚在废水表面的方法,与采用凝聚剂进行的处理组合也有效果。电解处理,通常是向所供给的废水投入·溶解电解质,在其水槽内将多个电极配置成适当的间隔,在电极间通电进行电解的。作为电极使用铝电极,作为电解质使用硝酸钠、氯化钠等为好。
在本发明中,通过按照上面所述将凝聚物沉淀和过滤等从而消除之后,对在该凝聚分离处理中不能消除的、例如亲水性的有机溶剂、水溶性的有机树脂等通过照射微波来分解。作为后面工序,在进行生物处理的场合,是通过微波的照射预备性地将难分解性物质分解处理直到成为易分解性物质,再进行采用生物处理的分解处理的。
微波是波长约0.1-1000mm的电磁波,包括UHF(分米波=decimeter wave)、SHF(厘米波=centimeter wave)、EHF(毫米波=millimeter wave)、亚毫米波(=submillimeter wave)。大多使用在国际上分配作为工业用的2450MHz,但并不限于此。本发明所用的微波,使用在微波炉等上所用的微波发生装置产出,根据需要对凝聚分离处理过的涂料废水照射。照射时间可以根据废水中的有机物的浓度、照射光的强度等适当选择,但照射时间通常优选1分钟-60分钟左右。
通过微波的照射,废水发热,但一般温度越高,有机物分解的速度也上升,因此,在没有废水沸腾和有机溶剂挥散这些作业上的危险的范围,不特别需要冷却。另外,为了提高分解效率,也可以加温。
只照射微波将有机物质分解直到成为无害的物质并不能说在经济上是理想的,微波的照射作为有机物分解的辅助手段是有效的。例如,在含氧气体的供给下,使用特定的固体催化剂,进行湿式氧化处理时,能够照射微波。
作为固体催化剂,可以无特别限制地使用以往公知的催化剂,例如,可以使用从钛、硅、锆、锰、铁、钴、镍、钨、铈、铜、银、金、铂、钯、铑、钌、铱及钙等碱土类金属等中选择的金属元素的不溶性或难溶性的化合物、例如氧化物和氢氧化物、或复氧化物、或担载这些金属的无机氧化物、活性炭、沸石等粒状物等。
在本发明中,在照射微波的前后工序的某处根据需要可进行生物处理。特别是通过上述微波的照射,将废水中的难分解性物质的一部分或者全部分解直至成为生物容易收获的易分解性物质后,进行生物处理为佳。由此,与未照射微波的场合比,能够大幅度地提高生物处理效率。
作为生物处理方法,可以使用历来公知的方法、例如活性污泥法和载体投入型生物处理法等来进行,特别是使用了微生物固定化载体的后者的生物处理为佳。
上述载体投入型生物处理法,是使用有机或无机的载体的方法,是使该载体担载微生物,通过该微生物分解废水中的有机物的方法,因此比活性污泥法效率高。作为载体形状,可以是板状体、纤维状体、圆筒等特殊形状体、海绵状体、粒·块状体等任何形状,但优选容易确保流动性和表面积的微小的粒状体。作为载体的材质,例如,可列举出光固化性树脂、聚氨酯、聚乙烯醇、聚乙烯、聚丙烯酰胺、聚酯、聚丙烯、琼脂、藻酸、角叉(菜)胶(carrageenan)、纤维素(cellulose)、匍聚糖、琼脂糖(agarose)、离子交换树脂、粒状活性炭、破碎活性炭、木炭、沸石、云母、砂粒、硅胶等多孔质陶瓷、无烟煤(anthracite)、在上述树脂载体中混入活性炭等所成的物质等,它们可以并用。从处理容易度和有效表面积的观点看,载体的粒径为0.3-15mm,优选0.5-10mm左右。
在需氧下进行上述载体投入型生物处理的情况下,向生物处理槽内供给纯氧和空气等含氧气体,或者设置氧溶解槽,将在其中使氧溶解到接近饱和状态的排水供给生物处理槽,等等。
另一方面,在厌氧下的生物处理,使用脱氮菌的脱氮处理是可能的。本发明的生物处理,也可以并用在需氧下的生物处理和在厌氧下的生物处理,例如,在需氧下的生物处理后,进行在厌氧下的生物处理,或者在厌氧下的生物处理后,进行在需氧下的生物处理,进一步地,可以使这些处理循环等等。
作为在生物处理中使用的微生物,从以往公知的需氧菌和厌氧菌中适当选择即可。作为需氧菌,例如可列举出假单胞菌(Pseudomonas)属、醋酸杆菌(Acetobacter)属等。另外,作为厌氧菌,例如可列举出假单胞菌(Pseudomonas)属所代表的脱氮菌、甲烷细菌、梭状芽孢杆菌(Clostridium)属等。
上述生物处理,例如可以在处理温度10-40℃、pH6.0-9.0、水理学滞留时间(HRT)24-48小时的条件下进行。
本发明,还可以根据需要,适当并用其他的排水处理装置、例如臭氧分解处理装置、UV处理装置、采用活性炭的吸附处理装置等。
以下使用附图说明本发明的优选的实施方案。
图1是表示本发明方法的一个实施方案的流程图。根据需要,将进行了凝聚分离处理的涂料废水供给具有微波照射装置4的微波处理槽1,向该废水照射微波。得到的微波处理废水被导到有散气管3的生物分解槽2,在需氧下进行生物处理。处理了的废水一部分送回到处理槽2,一部分作为处理水取出。通过调整向处理槽2的送回量,能够调整所取出的处理水的CODMn、或TOC的浓度。所取出的废水通到活性炭处理槽后被排出。
以下举出实施例和比较例来更具体地说明本发明。
实施例1
将汽车用水性涂料的喷漆废水作为涂料废水使用。该涂料废水(A)的CODMn为8500mg/升,TOC为11000mg/升。向1升该涂料废水(A)中添加15000mg凝聚剂KURISTUCK B100(栗田工业公司制)、1500mg KURISTUCK B450(栗田工业公司制),搅拌后放置1天,去除凝聚物。该凝聚处理后的处理液(B)的CODMn为5800mg/升,TOC为6800mg/升。向该处理液(B)照射5分钟微波(频率2.45GHz、功率500W)。
接着,将得到的微波处理水装到生物反应槽中,使用有假单胞菌(pseudomonas)属、醋酸杆菌(acetobacter)属、红球菌(Rhodococcus)属、芽孢杆菌(bacillus)属、念珠菌(candida)属及镰刀菌(fusarium)属的需氧性菌的活性污泥,在处理温度20-25℃、pH7-8.5及水理学滞留时间48小时的条件下进行生物处理后,过滤生物处理水。得到的处理水(C)的CODMn为1300mg/升,TOC为1750mg/升。
实施例2
代替上述实施例1中的照射频率2.45GHz及功率500W的微波5分钟,照射频率200GHz及功率500W的微波(毫米波)5分钟,除此以外与实施例1同样地进行处理。得到的处理水(C)的CODMn为900mg/升,TOC为1200mg/升。
实施例3
向实施例1中使用的凝聚分离处理液(B)照射5分钟微波(频率2.45GHz、功率500W)。
接着,将得到的微波处理水装到生物反应槽中,使用附着固定假单胞菌(pseudomonas)属、醋酸杆菌(acetobacter)属、红球菌(Rhodococcus)属、芽孢杆菌(bacillus)属、念珠菌(candida)属及镰刀菌(fusarium)属的需氧性菌的球形(直径4mm)的“K P pear”(关西涂料公司制,主成分为聚乙烯醇的载体),在处理温度20-25℃、pH7-8.5及水理学滞留时间48小时的条件下进行生物处理后,过滤生物处理水。得到的处理水(C)的CODMn为1300mg/升,TOC为1600mg/升。
实施例4
除了不进行实施例1中的凝聚分离处理以外,其他与实施例1同样地进行处理。得到的处理水(C)的CODMn为4000mg/升,TOC为5000mg/升。
比较例1
除了不照射实施例1中的微波以外,其他与实施例1同样地进行处理。得到的处理水(C)的CODMn为2000mg/升,TOC为2500mg/升。
比较例2
代替在实施例1中照射微波,采用500W的氙灯照射5分钟紫外线,除此以外,与实施例1同样地进行处理。得到的处理水(C)的CODMn为2000mg/升,TOC为2500mg/升。
比较例3
除了不照射实施例4中的微波以外,其他与实施例4同样地进行处理。得到的处理水(C)的CODMn为4700mg/升,TOC为5800mg/升。
归纳上述实施例和比较例的废水处理实验的结果,如下面表1所示。
表1
实施例 | 比较例 | ||||||
1 | 2 | 3 | 4 | 1 | 2 | 3 | |
凝聚处理 | 有 | 有 | 有 | 无 | 有 | 有 | 无 |
电磁波处理 | 微波 | 微波(毫米波) | 微波 | 微波 | 无 | 紫外线 | 无 |
生物处理 | 活性污泥处理 | 活性污泥处理 | 固定化载体处理 | 活性污泥处理 | 活性污泥处理 | 活性污泥处理 | 活性污泥处理 |
CODMn(mg/l) | 1300 | 900 | 1300 | 4000 | 2000 | 2000 | 4700 |
TOC(mg/l) | 1750 | 1200 | 1600 | 5000 | 2500 | 2500 | 5800 |
根据本发明方法,通过微波的照射能够促进涂料废液中的有机物的分解,特别是作为生物处理的前处理通过照射微波,能够高效率地分解涂料废液中的难分解性有机物,对喷漆废液和涂料废液的处理极为有用。
Claims (4)
1.一种涂料废水的处理方法,其特征在于,向涂料废水照射微波,将废水中所含的难分解性物质分解直到成为易分解性物质后,将得到的处理水供给到生物反应槽,在需氧或厌氧下进行生物处理。
2.根据权利要求1所述的涂料废水的处理方法,其中照射波长0.1-1000mm的电磁波1分钟-60分钟。
3.根据权利要求1或2所述的涂料废水的处理方法,其中,生物处理是使用了微生物固定化载体的生物处理。
4.根据权利要求1或2所述的涂料废水的处理方法,其中,在向涂料废水照射微波之前,进行采用凝聚剂或电解处理的凝聚分离处理。
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