CN102390914A - 一种抑制有机废弃物厌氧过程中硫化氢释放的方法 - Google Patents
一种抑制有机废弃物厌氧过程中硫化氢释放的方法 Download PDFInfo
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Abstract
本发明公开了一种抑制有机废弃物厌氧过程中硫化氢释放的方法,是向有机废弃物中加入富含铁氧化物的物质,混合搅拌均匀,密封静置不少于20天;铁氧化物中铁的摩尔量与有机废弃物中硫的摩尔量之比为1∶2-2∶1。有机废弃物包括污水处理厂的污泥、养殖厂的畜禽粪便、富含有机硫的液体和富含硫酸盐的有机废水;富含铁氧化物的物质中Fe2O3的质量百分比不小于14%。本发明添加的富含铁氧化物的物质会和硫化氢作用生成铁硫化物,由于铁硫化物的形成,厌氧消化甲烷气中硫化氢的含量低,从而减少了沼气输送、储存***的腐蚀和燃烧尾气SO2的排放,同时也能消除硫化氢对厌氧消化***中微生物活性的抑制,提高消化效率和沼气产率。
Description
一、技术领域
本发明涉及一种抑制有机废弃物厌氧过程中硫化氢释放的方法。
二、背景技术
随着我国社会、经济发展,我国蓄禽养殖方式、结构、模式正在发生根本性的变化。近年来,我国农业科学技术的进步,特别是蓄禽产品价格持续上涨,引起社会资金大量转向养殖业投资,推动了蓄禽养殖快速向专业化、规模化转变,引起了我国蓄禽养殖模式发生根本性的转变。集约化养殖已经成为我国畜牧业发展的主导方向。但集约化养殖导致养殖废弃物大量集中产生,存在很多环境问题难以处理。蓄禽集约化养殖业的快速发展过程中,严重忽视了养殖污染的综合治理,治理技术研发相对滞后,致使众多养殖场成为一个不可忽视的污染源。畜禽养殖过程中会对大气环境、水环境、生态环境造成一定程度的污染。全国集约化畜禽养殖业粪便排放量已超过30亿吨,畜禽污染物波及面广且危害大。目前集约化养殖场粪便的处理主要有两种方式:堆肥和厌氧消化产沼气。无论哪种方式,粪便中的有机硫和无机硫都在微生物的作用下转化为硫化氢释放到大气或水中,引起空气、大气和水污染,产生严重的环境危害。畜禽养殖业畜禽粪便污染已成为与工业废水、生活污水相并列的三大污染源之一。
随着我国污水处理率的提高,剩余污泥的产量也大幅度提高,污泥恰当处理和处置防止二次污染正在成为重要的问题。污泥处理技术大致可归结为两大类:一是抛弃型技术,污泥作为废弃物不利用;二是资源化技术,充分利用污泥中的有用成分,实现变废为宝。后者符合可持续发展的战略方针,有利于建立循环型经济,近年来得到广泛关注。其中污泥堆肥和污泥消化制沼气是污泥资源化利用的两种重要途径。污泥中含有大量的有机质、氮、磷、钾等植物需要的养分,其含量高于常用牛羊猪粪等农家肥,可以与菜籽饼、棉籽饼等优质的有机农肥相媲美。污泥堆肥处理是利用微生物的作用,将不稳定的有机质降解和转化成稳定的有机质,便于贮存、运输和使用。污泥厌氧消化是应用最为广泛的污泥稳定化工艺,其优点是:产生可燃气甲烷;使最终需要处置的污泥体积减少30%~50%;消化污泥容易脱水,含有有机肥效成分,适用于改良土壤。
但是,无论是生活污水处理厂的污泥、集约化养殖场的粪便,还是其他有机废弃物,在厌氧过程中废弃物中的有机硫、无机硫都会转变为硫化氢释放到空气、水中。硫化氢向环境释放可能产生很多危害:人体健康危害、动物危害、环境危害、微生物活性抑制、金属腐蚀作用。硫化物的腐蚀作用包括对建筑物金属的腐蚀,影响建筑物的耐久性;对处理***管路、设备的腐蚀,影响***使用寿命,增加维护成本。
针对养殖场H2S存在的健康隐患,国内外学者进行了大量的研究,采用各种方法和工艺来控制养殖场中H2S的产生和排放,包括在粪坑投加化学添加剂、通过生物净化器中进行气体的处理等。如Barber等研究了过硫酸铵、高锰酸钾和硝酸钠对粪便中H2S的产生和释放的影响,在实验室规模的实验中,过硫酸铵有效地抑制了硫酸盐还原菌(SRB)和H2S的释放;高锰酸钾通过对溶解性硫化物的化学氧化减少了硫化物的释放,同时抑制了SRB但并没有消除它;硝酸钠部分抑制了SRB的活性,延缓了硫化物的产量。Clanton等发现氢氧化钙、氯化铁、氯化亚铁、硫酸亚铁、过氧化氢、高锰酸钾和氯化钠都能减少粪浆中50%的H2S排放。Predicala等通过往养殖场粪便堆肥中添加硝酸盐、钼酸盐,抑制了硫酸盐还原菌的还原作用,减少了硫化氢的释放,但是上述添加物成本很高。
三、发明内容
本发明旨在提供一种抑制有机废弃物厌氧过程中硫化氢释放的方法,所要解决的技术问题是提供一种成本低、效果好的方法固定有机废弃物厌氧过程中产生的硫化氢,从而减少硫化氢气体的排放量。
本发明解决技术问题采用如下技术方案:
本发明抑制有机废弃物厌氧过程中硫化氢释放的方法的特点在于:向有机废弃物中加入富含铁氧化物的物质,搅拌均匀后密封静置不少于20天,所加入富含铁氧化物的物料中铁的摩尔量与有机废弃物中硫的摩尔量之比为1∶2-2∶1;
所述有机废弃物包括污水处理厂的污泥、养殖厂的畜禽粪便、富含有机硫的液体和富含硫酸盐的有机废水;
所述富含铁氧化物的物质中Fe2O3的质量百分比不小于14%,富含铁氧化物的物质的粒径小于0.1mm。
所述富含铁氧化物的物质,包括富含铁氧化物的土壤、硫酸烧渣、铁氧化物矿石、低品位的铁矿石、钢铁厂烟尘处理产生的富铁污泥等。
本发明是通过向有机废弃物中添加廉价的含活性铁氧化物的物质,利用生物分解矿物的环境效应来固定硫化氢,生成不溶性沉淀物,从而控制硫化氢的释放,具体反应过程如下:
在厌氧发酵过程中,有机物中含有的蛋白质等含硫有机物分解,转化为无机硫化物,然后在硫酸盐还原菌的作用下,被还原为S2-,进而生成硫化氢。典型的反应为:
8H++SO4 2-+8e-→S2-+4H2O
6H++SO3 2-+6e-→S2-+3H2O
S0+2e-→S2-
2H++S2-→H2S
如果产生的H2S浓度过高,就会抑制厌氧过程的进行。
在缺氧条件下,铁氧化物中的三价铁,会因铁还原菌、硫酸盐还原菌的存在、H2S的作用以及厌氧过程中产氢细菌代谢产生的H2的作用,被还原为二价铁离子,二价铁离子与硫化氢反应形成铁硫化物。可能发生的反应方程为:
Fe2O3+6H++2e-→2Fe2++3H2O
4Fe2O3+H2S+14H+→8Fe2++SO4 2-+8H2O
Fe2O3+H2+4H+→2Fe2++3H2O
Fe2++H2S→FeS+2H+
除了生成铁硫化物,Fe2+还可能与磷酸盐反应形成磷酸亚铁(蓝铁矿)沉淀。反应方程为:
3Fe2++2PO4 3-+8H2O→Fe3(PO4)2·8H2O
在Fe2+、PO4 3-、S2-共存体系中,铁硫化物优先沉淀,由于加入的铁氧化物优先形成了铁硫化物,从而导致硫化氢含量降低,消除了体系中硫离子对微生物活性的抑制,因而铁氧化物加入到有机物消化***中可以促进消化产气速率,提高厌氧消化效率。
本发明中直接添加三氧化二铁存在来源不广、价格高的问题。富含铁氧化物的物质可以是一些很廉价的物质,甚至可以从自然界直接获取。
与已有技术相比,本发明的有益效果体现在:
1、本发明添加的富含铁氧化物的物质会和硫化氢作用生成铁硫化物,从而有效控制了硫化氢向空气中的排放量。
2、本发明添加的富含铁氧化物的物质会和硫化氢作用生成铁硫化物,由于铁硫化物的形成,厌氧消化甲烷气中硫化氢的含量低,从而减少了沼气输送、储存***的腐蚀和燃烧尾气SO2的排放,同时也能消除硫化氢对厌氧消化***中微生物活性的抑制,提高消化效率和沼气产率。
3、本发明反应过程中会有磷酸铁形成,能降低消化液中的磷酸盐浓度,减轻磷对水体的污染。
四、附图说明
图1是实施例1添加富含铁氧化物的物质后H2S浓度的变化曲线。
图2是富含铁氧化物的物质固定硫化氢形成的铁硫化物扫描电镜图。
五、具体实施方式
现以实验室模拟试验为例,非限定实施例叙述如下:
实施例1:
在7个1000mL棕色厌氧消化瓶中分别加入200g新鲜猪粪和300mL蒸馏水,接种甲烷菌液20mL(总菌量为2×107个/mL),根据猪粪中的初始硫含量,按照Fe加入量与有机物中S的摩尔比分别为0、0.5、0.75、1.0、1.25、1.5、2.0加入赤铁矿,即分别加入0g、1.50g、2.26g、3.01g、3.76g、4.51g、6.01g赤铁矿(三氧化二铁质量百分含量95%,粒径小于0.074mm),在测定初始pH后,将厌氧消化瓶密封,通入氮气排氧,放入35℃恒温水浴锅中进行恒温培养,每天定时震荡,使之完全混合。每2天用气密取样针抽取发酵瓶上方气体,测定气体中H2S浓度。实验条件完全不变重复一次,两次测试数据取平均值。
整个实验阶段测得各个反应器内发酵气体中H2S浓度变化如图1所示。从图1可以看出,各反应器内H2S的浓度均呈现先升后降的趋势。发酵的前4天H2S的浓度持续上升;第4-6天,未添加赤铁矿的消化瓶中H2S浓度保持不变;Fe∶S摩尔比为0.5的消化瓶中,H2S浓度仍有缓慢上升;而Fe∶S摩尔比大于0.75的消化瓶中,H2S浓度开始下降;6天后,所有实验中H2S浓度除偶尔出现少许上升外,大体上均呈逐渐降低的趋势。在整个实验过程的任一时间点,添加了赤铁矿的样品中H2S的浓度均比空白样品中低。实验结束时,添加赤铁矿越多的消化瓶H2S浓度越低。这些表明铁氧化物的加入抑制了发酵过程中H2S的产生或释放。硫化氢的排放量减少70%以上。
实施例2:
褐铁矿矿石(主要矿物为针铁矿,三氧化二铁质量百分含量为43%)粉碎过200目,把褐铁矿粉按照Fe∶S摩尔比为1∶1.2的比例加入到养殖场粪便中,混合均匀得混合物,密封堆存。
效果检测实验:取400mL混合物装入玻璃瓶中密封,玻璃瓶上部放置醋酸铅试纸(检测下限0.1mg/m3),25天后试纸没有变黑,说明厌氧过程中硫化氢的释放受到抑制,固体产物中有大量铁硫化物形成,即图2中叶片状颗粒。
实施例3:
褐铁矿矿石(主要矿物为针铁矿,三氧化二铁质量百分含量为43%)粉碎过320目筛,取400mL含硫酸盐的有机废水加入到500mL塑料瓶容器中,把褐铁矿粉按照Fe∶S摩尔比为1∶1的比例加入到上述含硫酸盐的有机废水中,接种厌氧菌液10mL(总菌量为1×107个/mL),放入磁转子,在瓶内上部放入醋酸铅试纸,密封。另一个反应器中不加含铁氧化物的物质,作为空白对照。把反应容器放在磁力搅拌搅拌器上,按照每分钟100转的速度搅拌混合。
效果检测实验:醋酸铅试纸(检测下限0.1mg/m3)25天后没有变黑,空白对照反应器中的醋酸铅试纸变黑,说明含硫酸盐的有机废水厌氧处理过程中硫化氢的释放受到抑制。
实施例4:
褐铁矿矿石(主要矿物为针铁矿,三氧化二铁质量百分含量为43%)粉碎过320目,取400mL污水处理厂压滤剩余污泥加入到500mL塑料瓶容器中,把褐铁矿粉按照Fe∶S摩尔比为1.5∶1的比例加入到上述容器中,混合均匀,在瓶内上部放入醋酸铅试纸,密封。另一个反应器中不加含铁氧化物的物质,作为空白对照。
效果检测实验:醋酸铅试纸(检测下限0.1mg/m3)25天后没有变黑,空白对照反应器中的醋酸铅试纸变黑,说明污泥厌氧发酵过程中硫化氢的释放受到抑制。
Claims (1)
1.一种抑制有机废弃物厌氧过程中硫化氢释放的方法,其特征在于:向有机废弃物中加入富含铁氧化物的物质,搅拌均匀后密封静置不少于20天,所加入富含铁氧化物的物料中铁的摩尔量与有机废弃物中硫的摩尔量之比为1∶2-2∶1;
所述有机废弃物包括污水处理厂的污泥、养殖厂的畜禽粪便、富含有机硫的液体和富含硫酸盐的有机废水;
所述富含铁氧化物的物质中Fe2O3的质量百分比不小于14%,富含铁氧化物的物质的粒径小于0.1mm。
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