CN104261570B - 一种畜禽养殖厌氧污水净化剂 - Google Patents
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Abstract
本发明涉及一种污水净化剂,更具体涉及一种畜禽养殖厌氧污水净化剂。所述畜禽养殖厌氧污水净化剂由复合微生物菌株与活性炭载体组成,所述活性炭载体为煤质柱状活性炭,是以2-10目的煤质活性炭经过定型制成的实心圆柱状活性炭。该净化剂具备低成本、高效吸附和能够高效降解畜禽养殖厌氧污水中污染物的特点,而且制备过程相对简单。得到的净化剂稳定性强,微生物活性高,具有高效吸附和降解污染物的特点,而且对环境友好,不会造成二次污染。
Description
技术领域
本发明涉及一种污水净化剂,更具体涉及一种畜禽养殖厌氧污水净化剂。
背景技术
活性炭是用生物有机物质经过炭化、活化等过程制成的一种无定形炭。大部分含碳物质如木材、竹材、煤类、果壳、城市垃圾等废弃物均可制备活性炭。
活性炭具有巨大的比表面积(500-1000m2·克-1)、发达的孔隙结构,独特的表面活性官能团及稳定的化学性能,能耐酸耐强碱,可经受水渍、高温、高压,是一种优良的吸附剂,能在它的表面上吸附气体、液体或胶态固体,对于气体、液体,吸附物质的质量可接近于活性炭本身的质量,但是也存在吸附易饱和、再生成本高等问题。
根据活性炭的吸附特点,活性炭被广泛应用于工农业的各个方面,主要用于除去水中的污染物、脱色、过滤净化液体、气体,还用于对空气的净化处理、废气回收(如在化工行业里对气体"苯"的回收)、贵重金属的回收及提炼(比如对黄金的吸收)。
根据炭材料具有矿物质和丰富的孔隙,有助于一些微生物在其中生长,而不同微生物可以降解不同物质的原理,可以将炭材料和微生物结合,达到既具高效吸附,又具降解的目的。固定化微生物技术是20世纪80年代兴起的一种新型生物技术,可以大幅度地提高参加反应的微生物浓度,增强微生物的耐环境冲击性,可根据需要选择适宜的微生物,可降低二次污染等。传统的固定化方法虽然具有自身的优势,但同时都存在难以克服的缺陷。比如吸附法制备容易,载体可再生,但被吸附的微生物活性相对较低,微生物与载体的结合程度不够牢固,需较长时间完成初始化固定过程;包埋法的微生物细胞固定化程度高,物化稳定性强,不易被分解,能抗有毒物质的侵害,但是微生物细胞与基质间的扩散阻力增大,准备工艺较复杂,可能会导致部分细胞活性丧失,并且不适于大分子污染物质的分解;交联固定化法可使微生物细胞高度密集,使稳定度得到提高,但是制备较困难,交联剂会使细胞活性降低,并且费用较昂贵。
目前已有研究报道活性炭经化学或物理改性,活性炭通过改性使其表面的官能团发生变化,改变其孔道结构及表面积,提高活性炭的吸附性能,虽然此举
能提高活性炭的孔径比,在一定程度上提高其吸附性能,但是其制备工艺复杂,制作成本和周期都较长,因此在推广应用上存在一定的难度。
发明内容
本发明的目的在于提供一种畜禽养殖厌氧污水净化剂,该净化剂具备低成本、高效吸附和能够高效降解畜禽养殖厌氧污水中污染物的特点,而且制备过程相对简单。
本发明采取的技术方案如下:
本发明涉及到的畜禽养殖厌氧污水净化剂,由复合微生物菌株与活性炭载体组成,所述复合微生物菌株包括汉堡硝化杆菌((Nitrobacterhamburgensis))、枯草芽孢杆菌(Bacillus subtilis)、小球藻(Chlorella vulgaris)、施氏假单胞菌(Pseudomonas stutzeri)和排硫硫杆菌(Thiobacilus thioparus),所述活性炭载体为煤质柱状活性炭,是以2-10目的煤质活性炭经过定型制成的实心圆柱状活性炭。更优选地,是以6目的煤质活性炭经过定型制成的实心圆柱状活性炭。
其制备方法如下:
将微生物菌株分别活化、培养菌株至对数生长期,离心收集菌体,用无菌生理盐水洗涤、稀释、混合制备复合菌株悬浮液,使复合菌株悬浮液中各菌株菌数含量为1~8×108个/ml,再加入到活性炭载体中,按10重量份活性炭载体、6~8重量份复合菌株悬浮液的比例混匀,共同置于30-37℃培养条件下振荡培养48~72h,最后捞出活性炭载体置于30-37℃的恒温箱里烘干即完成畜禽养殖厌氧污水净化剂的制备。
上述原料中采用的菌种可以由本领域技术人员通过常规菌种鉴定分离方法方便地从自然界分离得到的,或通过商业渠道公开购买的菌种。本发明采用的菌种可从中国微生物菌种网-北京北纳创联生物技术研究院等供应商处购买获得。
上述菌种根据现有常规方法培养:
Ⅰ 汉堡硝化杆菌的培养基: NaCl 0.3 g、NaHCO3 0.5g、MgSO4
0.5g、FeSO4 0.04g、NaNO2 1.0g、K2
HPO4 0.3g, pH 7.5,蒸馏水 1000
mL。
Ⅱ 枯草芽孢杆菌的培养基:蛋白胨 5.0g,牛肉膏 10g,酵母膏 5.0g,葡萄糖 5.0g,Nacl 5.0g,蒸馏水 1000 mL,pH 7.0。
Ⅲ小球藻常用培养液配方: NH4NO3 50-100 mg,K2HPO4 5 mg, ⅣFeC6H5O7 0.1-0.5
mg,海水 1000mL。
Ⅳ 施氏假单胞菌的培养基:葡萄糖1.0g、酵母浸膏1.0g、K2HPO4
0.3g、KH2PO4 0.25g、MgSO4·7H2O
0.2g、蒸馏水 1000 mL,调pH
6.5。
Ⅴ 排硫硫杆菌的培养基:Na2S2O3・5H2O 10.0g、KH2PO44.0g、K2HPO44.0g、MgSO4・7H2O 0.8g、NH4Cl 0.4 g、微量元素10mL、蒸馏水 1000 mL。
本发明的显著优点:
本发明采用吸附法制备畜禽养殖厌氧污水净化剂,制备方法简单、成本低,得到的净化剂稳定性强,微生物活性高,具有高效吸附和降解污染物的特点,而且对环境友好,不会造成二次污染。
附图说明
图1为实施例1采用的活性炭载体。
图 2为不同菌株在不同浓度污水中的COD降解率。
具体实施方式
实施例1
一、材料与方法
1、选择最佳活性炭材料
煤质活性炭具有从微孔到大孔的各种孔径,因此,对高分子有机物有较好的吸附能力。活性炭吸附能力的大小不仅与本身性质有关,还与被吸附物质的分子结构、溶解性和离子化程度等有关。本发明的目的是利用活性炭制备净化剂去除畜禽养殖污水中的污染物,根据污水成分的性质,选用煤质活性炭。
将煤质活性炭固定成一定形状,不但利于微生物的的吸附生长,而且方便后期对活性炭的打捞处理。本发明采用的活性炭如图1所示为实心圆柱状,具有较大吸附表面积。活性炭技术性能参数如表1所示。
表1 活性炭技术性能参数
2、作用对象:畜禽养殖厌氧污水。
畜禽养殖厌氧污水的技术指标:化学需氧量(CODcr)的范围为2.14×103~3.02×103 mg/L;生化需氧量(BOD5)的范围为160~1000 mg/L。
3、方法与步骤
(1)、微生物菌株的复壮及培养
接种活化后的菌种于培养基中,培养菌株至对数生长期,在4℃,3000r/min-1条件下离心10
min收集菌体,用无菌生理盐水洗涤、离心,重复三次,再用无菌生理盐水稀释、混合制备菌株混悬液,使各菌株的菌数含量为1~8×108个/ml以上。
(2)、活性炭与微生物菌株的结合制备畜禽养殖厌氧污水净化剂
将上述步骤制得的菌株混悬液加入到活性炭载体中,按10重量份活性炭载体、6~8重量份菌株悬浮液的比例混匀,共同置于30-37℃培养条件下振荡培养48~72h,最后取出活性炭置于30-37℃的恒温箱里烘干即完成污水净化剂的制备。
二、实验结果
1
、菌株对不同浓度的养殖厌氧污水处理实验
将这几株菌株培养到对数生长期,按步骤(1)的方法制备菌株混悬液,将70mL的微生物菌悬液投入到10L不同浓度的养殖厌氧污水中,测定污水的技术指标,计算其降解率。实验结果见图2(1#汉堡硝化杆菌,2# 枯草芽孢杆菌,3# 小球藻,4#施氏假单胞菌,5# 排硫硫杆菌)。实验结果表明,菌株对厌氧污水处理效果的排序如下:CODcr
2620mg/L > CODcr 3540 mg/L > CODcr 1450 mg/L,由此可以看出菌株在 CODcr在2620
mg/L的养殖厌氧污水中能较好的生长,说明在这个浓度的污水中营养成分适合菌株的生长。
、几种菌株的拮抗实验
将单一菌株培养到对数生长期,即菌数含量达1×108个/ml以上,按比重将单一或混合菌株的菌液进行等比例混合,再投入到CODcr为2620 mg/L养殖污水中进行处理,测定污水的技术指标,计算其降解率,实验数据见表2(1#汉堡硝化杆菌,2# 枯草芽孢杆菌,3# 小球藻,4#施氏假单胞菌,5# 排硫硫杆菌)。实验结果表明5种菌株的联合作用对污水的处理效果较好,联合作用明显。因此,我们选用上述5种菌株作为制备畜禽养殖厌氧污水净化剂的菌株来源。
表 2 菌株拮抗实验数据
3.不同形状的活性炭对污水处理效果的比较
将不同形状的活性炭投入到畜禽养殖厌氧污水中处理,对其净化效果进行比较。分别称取100g各种形状的活性炭(即颗粒状煤质活性炭A、球状煤质活性炭B、实心圆柱状煤质活性炭C),投入到10L的养殖厌氧污水,以未处理的污水为对照,3.5d后分别测定其CODcr、BOD5等技术指标,计算活性炭对畜禽养殖厌氧污水的降解率,实验结果见表3。从实验结果可以看出,实心圆柱状煤质活性炭的处理效果较佳,因此选用实心圆柱状煤质活性炭作为制备净化剂的微生物固定化载体。
表3 不同形状的活性炭对污水处理效果
3、不同孔径大小的活性炭的吸附性能比较
选择三种不同孔径1#(2-4目)、2#(6目)、3#(8-10目)的粉末状煤质活性炭按(一)中的方法与微生物菌株结合制备污水净化剂,分别投入到养殖厌氧污水中进行污水处理进行试验。将净化剂重复使用三次,并测定净化剂在使用前以及使用后的有效活菌数,结果见表4。从实验结果可以看出2#活性炭制备而成的净化剂,与活性炭结合的菌株数量比1#和3#多,而且在重复使用的过程中,虽然菌株的有效数量有所下降,但是相对比1#和3#活性炭稳定,净化剂在使用三次后,其菌株的数量趋于稳定,没有出现大幅度的下降。综上所述,选择2#活性炭制备污水净化剂。
表 4净化剂在污水处理前后的有效活菌数
4
、不同量的畜禽养殖厌氧污水净化剂对污水的处理效果
以在静置状态下的原养殖厌氧污水做对照,将50g、75g、100 g、125 g污水净化剂,分别投入到10 L养殖场厌氧污水中,处理3.5d后,测试污水CODcr、BOD5指标,计算CODcr、BOD5降解率,确定污水净化剂处理污水的最佳量,实验结果见表5。
由表5可以看出不同量的污水净化剂对污水的处理效果,随着净化剂投入量的增加,污水的CODcr、BOD5降解率呈逐渐上升的趋势,当净化剂的量为100g时污水的CODcr、BOD5降解率分别为86.9 %、77.1 %;当净化剂的量为120g时污水的CODcr、BOD5降解率达到最高分别为88.2
%、79.1 %,而且随着炭量的进一步增加,CODcr、BOD5降解率略微升高,主要原因是活性炭对污水中有机物等的吸附量已接近饱和,净化剂量的增加并不能使污水的CODcr、BOD5指标大幅度降低。因此,从成本、处理效果等综合考虑,当污水为10 L时,污水净化剂的最佳投入量为100g。
表 5不同量的畜禽养殖厌氧污水净化剂处理效果
5
、畜禽养殖厌氧污水净化剂的最佳更换周期
对已经使用过的污水净化剂进行重复循环使用,测试污水净化剂的处理效果。实验设计的次数分别为1、2、3、4。将100g不同循环利用次数的的污水净化剂投入到10L养殖场厌氧污水中,处理3.5d后,测试污水的CODcr、BOD5指标,判断污水净化剂可重复使用的次数,进而确定净化剂最佳更换周期,实验结果见表6。
表 6 畜禽养殖厌氧污水净化剂的不同循环利用次数效果
由表6可以看出畜禽养殖厌氧污水净化剂不同循环利用次数的处理效果,随着使用次数的增加,污水的CODcr、BOD5降解率呈逐渐下降的趋势。循环利用的次数对CODcr的降解效果影响较小,但是对BOD5的降解效果影响较大,在第四次利用时,BOD5的降解率就已经降到54.2%,从BOD5的数据,可以初步判断净化剂的吸附已达到饱和。因此,可根据处理后的厌氧污水利用情况选择较佳的重复循环利用次数,即可确定畜禽养殖厌氧污水净化剂的最佳更换周期。
、污水净化剂的再生利用
本产品的再生主要采用目前应用最多、工业上最成熟的活性炭再生方法热再生法,活性炭活化再生后就可以继续再利用,结合微生物菌株制备成净化剂,再次重复利用。
应用效果试验
实例一
以在静置状态下的原养殖厌氧污水做对照,将1kg污水净化剂,投入到100 L养殖场厌氧污水中,处理3.5d后,测试污水的CODcr、BOD5指标,计算污水的CODcr、BOD5降解率,具体结果见下表。
实例二
以在静置状态下的原养殖厌氧污水做对照,将10kg污水净化剂,分别投入到1t的养殖场厌氧污水中,处理3.5d后,测试污水的CODcr、BOD5指标,计算污水的CODcr、BOD5降解率,具体结果见下表。
实例三
以在静置状态下的原养殖厌氧污水做对照,将100kg污水净化剂,分别投入到10t的养殖场厌氧污水中,处理3.5d后,测试污水的CODcr、BOD5指标,计算污水的CODcr、BOD5降解率,具体结果见下表。
。
Claims (2)
1.一种畜禽养殖厌氧污水净化剂,其特征在于:所述畜禽养殖厌氧污水净化剂由复合微生物菌株与活性炭载体组成,所述活性炭载体为煤质柱状活性炭,是以6目的煤质活性炭经过定型制成的实心圆柱状活性炭;制备方法如下:将微生物菌株分别活化、培养菌株至对数生长期,离心收集菌体,用无菌生理盐水洗涤、稀释、混合制备复合菌株悬浮液,使复合菌株悬浮液中各菌株菌数含量为(1~8)×108个/ml,再加入到活性炭载体中,按10重量份活性炭载体、6~8重量份复合菌株悬浮液的比例混匀,共同置于30-37℃培养条件下振荡培养48~72h,最后捞出活性炭载体置于30-37℃的恒温箱里烘干。
2.根据权利要求1所述的畜禽养殖厌氧污水净化剂,其特征在于:所述复合微生物菌株包括汉堡硝化杆菌(Nitrobacterhamburgensis)、枯草芽孢杆菌(Bacillus subtilis)、小球藻(Chlorella vulgaris)、施氏假单胞菌(Pseudomonas stutzeri)和排硫硫杆菌(Thiobacilus thioparus)。
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