CN115155547A - 一种沼渣原位利用作为沼气脱硫剂的方法 - Google Patents
一种沼渣原位利用作为沼气脱硫剂的方法 Download PDFInfo
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Abstract
本发明提供一种沼渣原位利用作为沼气脱硫剂的方法。本发明的沼渣原位利用的方法,是将厌氧发酵产生的副产物沼渣作为原料,经预处理、活化、炭化、有机胺负载等步骤制得沼气脱硫剂,使用所述沼气脱硫剂用于厌氧发酵产物沼气的脱硫净化。本发明提出的将沼渣应用到沼气脱硫的方法,一方面有效解决了厌氧发酵副产物沼渣的消纳问题,拓宽了沼渣的高值化利用途径;另一方面,将沼渣原位应用于厌氧发酵产物沼气的脱硫净化过程中,实现清洁沼气的获取,同时满足了厌氧发酵后续工艺中沼渣消纳、沼气净化的需求。
Description
技术领域
本发明属于沼渣资源化和沼气净化技术领域,具体涉及一种沼渣原位利用作为沼气脱硫剂的方法。
背景技术
厌氧发酵技术在处理有机废弃物上有着重要应用,是一种产能、有效的生物处理工艺,目前已经广泛应用在厨余垃圾、农业秸秆、园林垃圾、市政污泥等有机废弃物处理等领域中,具有良好的经济和环境效益。可降解有机质在缺氧或无氧条件下通过微生物发酵转化,其核心产物——沼气,是一类清洁、高效的可再生能源,对于解决化石燃料的依存具有重要价值,全国的厌氧发酵设施也在可再生能源的需求增加、国家政策的支持等条件下得到了迅猛的发展。
沼气的主要成分为甲烷(CH4)和二氧化碳(CO2),但也存在少量的硫化氢(H2S)、氨气(NH3)等杂质,其中H2S受有机质来源和工艺的影响,在沼气中含量变化在50~5000ppm。由于H2S有毒,且对管道、设备有较强的腐蚀性,以及二次燃烧会产生大气污染物,限制了沼气的回收和高值化利用。因此在沼气利用前需要对其进行脱硫处理,降低沼气中的H2S浓度。目前,沼气中H2S脱除方法主要包括了干法、湿法和生物法,以干法和湿法脱硫的应用较为广泛。干法主要是利用固体脱硫剂(如沸石、炭材料)的吸附或吸收作用脱除沼气中的H2S。湿法则是利用液相吸收剂(如碱性或弱碱性溶液)或氧化剂将H2S反应脱除。例如CN106753638B提出了一种基于纳米零价铁的沼气干式脱硫方法,在170~300℃下实现沼气中H2S的去除。CN111592920A公开了一种含有水、络合铁、络合铁、络合亚铁、N,N-二羟乙基哌嗪、7-二乙氨基-4-甲基香豆素、2-羟基甲基-15-冠醚-5、碳酸钠及碳酸氢钠缓冲体系的沼气脱硫剂。CN108602952B提出了一种新型多胺吸收液,用于选择性去除0.1~1巴分压条件下的H2S。但现有研究中的干式或湿式脱硫剂存在原料成本高、沼气条件适用性差、脱硫剂再生难度高等缺点。
另一方面,厌氧发酵产沼工艺中会产生大量的副产物沼渣,随着我国沼气设施的大规模发展,沼渣产生量大、消纳量低、多进行填埋或焚烧处理,其低位利用降低了有机废弃物厌氧发酵资源化技术的经济和环境效益。而厌氧发酵对于有机废弃物中的木质纤维类物质转化率较低,沼渣中高木质纤维类含量使其具有制备炭材料的应用潜能。例如CN111302340A公开了将沼渣经盐酸活化、研磨过筛、氮气炭化、氯化铁活化等步骤的生物炭制备方法。CN110371971A也公开了一种利用畜禽粪污厌氧发酵后沼渣,通过高温高压水热碳化、氢氧化钾活化的方式制备水热碳,并将水热碳投加到厌氧发酵过程中应用。但现有制备的沼渣源炭材料,受较差的孔隙度和缺少表面官能团的影响,难以用于气体吸附领域中,特别是像沼气中H2S浓度较低(50~5000ppm),存在吸附效果和选择性较差等问题。
发明内容
鉴于现有技术中存在的问题,结合厌氧发酵工艺中沼气脱硫净化和副产物沼渣消纳的双重需求,本发明提出了一种沼渣原位利用作为沼气脱硫剂的方法,以有机废弃物厌氧发酵副产物沼渣为原料制备脱硫剂,并在厌氧发酵工艺中原位用作沼气的脱硫净化,其对沼气中低浓度的H2S具有良好的吸附性能。
本发明的目的在于提供一种沼渣原位利用的方法,将副产物沼渣原位资源化利用在厌氧发酵系统中,拓展沼渣的高值化利用途径。
进一步地,本发明的目的还在于提供一种沼气脱硫剂的制备方法,以沼渣为原料,原料来源广、成本低,所制备的沼气脱硫剂具有沼气条件适用性强、易于再生等优势。
本发明通过如下技术方案实现上述目的:
一种沼渣原位利用作为沼气脱硫剂的方法,具体是将厌氧发酵产生的副产物沼渣作为原料,经烘干、活化、炭化、有机胺负载步骤制备得到沼气脱硫剂,应用于厌氧发酵沼气的脱硫净化。
所述的副产物沼渣,来源于厨余垃圾、果蔬垃圾、园林垃圾、农业废弃物厌氧发酵沼渣的一种或两种以上的组合。
所述的有机胺为四乙烯五胺、五乙烯六胺、聚乙烯亚胺中的一种或两种以上的组合。
所述的沼渣原位利用作为沼气脱硫剂的方法,包括如下具体步骤:
1)将厌氧发酵副产物沼渣烘干得到干燥沼渣;
2)将干燥沼渣,浸泡于活化试剂溶液中并搅拌;将搅拌均匀的混合物离心;
3)取离心后的沉淀物在惰性氛围下高温炭化,洗涤烘干,得到多孔炭;
4)将有机胺溶于醇或水溶液中,加入步骤3)中制得的多孔炭,搅拌浸渍直至溶剂挥发,真空干燥后得到所述沼气脱硫剂。
上述步骤2)中所述活化试剂选自氢氧化钠、氢氧化钾或氯化锌,所述干燥沼渣与所述活化试剂的质量比为0.8~1.5:1。
上述步骤4)中所述有机胺和所述多孔炭的质量比为0.1~0.5:1。
上述方法制备得到的沼气脱硫剂,沼气脱硫剂能在30~60℃的沼气温度下吸附50~5000ppm浓度范围的H2S气体。
上述方法制备得到的沼气脱硫剂,沼气脱硫剂在使用后可以通过变温或变压操作实现再生并循环利用。
本发明的优势在于:
(1)本发明提出的将厌氧发酵副产物沼渣原位利用作为沼气脱硫剂的方法,属于沼渣原位消纳的资源化方式,并应用于厌氧发酵沼气的脱硫净化中,在厌氧发酵系统中既实现了沼渣的高值化利用,也减少脱硫剂的额外采购,具备良好的经济和环境效益;
(2)本发明通过对沼渣源炭材料的制备方法的优化,同时在多孔炭中负载有机胺,利用有机胺与H2S的化学结合能力,解决了传统沼渣源炭材料吸附效果和选择性较差的问题;
(3)本发明以沼渣为原料制备的沼气脱硫剂,能够在沼气温度(30~60℃)和H2S浓度(50~5000ppm)条件内选择性吸附H2S,适用性较好;且由于有机胺与H2S的反应放热可逆,因此可通过变温或变压操作实现沼气脱硫剂的再生与循环利用,具有极强的应用前景。
附图说明
图1为本发明以厌氧发酵沼渣为原料制备沼气脱硫剂的制备流程图。
图2为干燥沼渣、未活化和活化后多孔炭的N2吸附脱附曲线图(图2(a))和孔径分布图(图2(b))。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明不限于所述内容。本发明不限于以下说明的各构成,在发明请求保护的范围内可以进行各种变更,而适当组合不同实施方式、实施例中各自公开的技术手段而得到的实施方式、实施例也包含在本发明的技术范围中。
本发明针对的是厌氧发酵副产物沼渣,提供一种沼渣原位利用作为沼气脱硫剂的方法,将沼渣通过预处理、活化、炭化、有机胺负载等步骤制备获得沼气脱硫剂,以实现厌氧发酵沼渣利用和沼气脱硫净化的双重目的,具体参见图1的制备流程图。
在本发明的具体实施方式中,所述的副产物沼渣为有机废弃物厌氧发酵后的残余固体物质,具体来源于厨余垃圾、果蔬垃圾、园林垃圾、农业废弃物厌氧发酵沼渣的一种或两种以上的组合。由于该类有机废弃物厌氧发酵后的沼渣富含木质素和纤维素,炭化率相对更高。
在本发明的具体实施方式中,所述的有机胺为含有胺基的有机物质,具体为四乙烯五胺、五乙烯六胺、聚乙烯亚胺中的一种或两种以上的组合。相较于其他类型有机胺(如芳香胺类、醇胺类),所选的有机胺具有较高的胺基密度;且沸点在250℃以上,具有较好的热稳定性。
在本发明的具体实施方式中,活化步骤中所述的活化试剂选自氢氧化钠、氢氧化钾或氯化锌,进一步地优选为氢氧化钾;干燥沼渣与活化试剂的质量比为0.8~1.5:1,进一步地优选为1.0~1.2:1。通过该活化方法可有效提高沼渣多孔炭的比表面积和孔容积,更有利于有机胺的负载。
在本发明的具体实施方式中,有机胺负载步骤中所述的有机胺和多孔炭的质量比为0.1~0.5:1。质量比过低将无法达到对低浓度H2S的吸附效果,而质量比过高会造成多孔炭孔隙结构的堵塞,同样不利于气体吸附。
在本发明的具体实施方式中,所述的沼气脱硫剂在沼气脱硫纯化中的应用,由于厌氧发酵工艺(中温或高温厌氧发酵)与原料组成的差异,通常沼气温度和H2S浓度存在一定程度的波动,通常在30~60℃和50~5000ppm。
在本发明的具体实施方式中,利用负载上的有机胺和H2S的化学反应(反应方程式如下式(1)到(3)所示),即使在低浓度范围(50~5000ppm)内也具有吸附性能优势。且由于该反应放热可逆,因此本发明的沼气脱硫剂具备通过变温或变压的方式进行材料再生进而循环使用的特点。
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售获得的常规产品。
实施例1
根据本发明提出的方法,以厌氧发酵沼渣为原料,首先通过预处理、活化、炭化等步骤制备多孔炭,具体实施方式如下:
1)采用的原料为厨余垃圾、果蔬垃圾、园林垃圾联合厌氧发酵后产生的沼渣,将沼渣在105℃的温度下干燥10h,以挥发原料中的水分;烘干后的沼渣待用,命名为“干燥沼渣”;
2)称取10.0g氢氧化钾(KOH),加水溶解配置成0.2g/mL的KOH溶液;取10.0g干燥沼渣,与KOH溶液混合,在常温(25±5℃)下以300rpm的转速磁力搅拌5h;搅拌均匀的混合物在8000rpm转速下离心10min;
3)取离心后的沉淀物置于600℃的管式炉中,在氮气氛围中高温炭化4h,后冷却至室温;冷却后材料用去离子水洗涤至中性,洗涤后在105℃的温度下干燥10h,制备获得沼渣源多孔炭,命名为“活化多孔炭”(即本发明的多孔炭)。
对实施例1中的干燥沼渣和活化多孔炭的孔隙结构进行表征,所用仪器为比表面积和孔隙度分析仪(型号ASAP2020,Micromeritics),实验结果如表1和图2(图2(a)是N2吸附解吸等温线、图2(b)是孔径分布曲线图)所示。其中比表面积采用Brunauer-Emmett-Teller(BET)模型和Langmuir模型计算,总孔容积采用相对压力为0.99时的N2吸附量计算,孔径分布曲线采用Barrett-Joyner-Halenda(BJH)模型计算。实施例1中活化多孔炭的比表面积和孔容积相比于干燥沼渣明显提高,BET比表面积、Langmuir比表面积和总孔容积分别从4.58m2/g、6.65m2/g和0.02cm3/g提升至137.94m2/g、187.31m2/g和0.26cm3/g,提供了更多可用于有机胺负载的孔隙。
表1材料的孔隙结构参数
对比例1
将不采用活化方法得到的多孔炭与活化多孔炭形成对比,具体实施方式如下:
1)采用的原料为厨余垃圾、果蔬垃圾、园林垃圾联合厌氧发酵后产生的沼渣,将沼渣在105℃的温度下干燥10h,以挥发原料中的水分;烘干后的沼渣待用,命名为“干燥沼渣”;
2)不进行活化;
3)取干燥沼渣置于600℃的管式炉中,在氮气氛围中高温炭化4h,后冷却至室温;冷却后材料用去离子水洗涤至中性,洗涤后在105℃的温度下干燥10h,制备获得沼渣源多孔炭,命名为“未活化多孔炭”。
采用相同方法表征对比例1中的未活化多孔炭的孔隙结构,结果如表1和图2所示。未活化多孔炭的比表面积和孔体积相比于活化多孔炭明显更低,BET比表面积、Langmuir比表面积和总孔容积分别仅有31.88m2/g、43.58m2/g和0.07cm3/g,不利于后续有机胺的负载。结果验证了活化方法对于以沼渣制备沼气脱硫剂的必要性。
实施例2
根据本发明提出的方法,以厌氧发酵沼渣为原料,通过预处理、活化、炭化、有机胺负载等步骤制备沼气脱硫剂,具体实施方式如下:
步骤1)~3)与实施例1相同;
4)称取0.22g四乙烯五胺(TEPA),溶解于15mL甲醇中,在常温(25±5℃)下以300rpm的转速磁力搅拌至TEPA完全溶解;称取2.0g上述活化多孔炭,与TEPA溶液混合,混合物在40℃下以300rpm的转速磁力搅拌至溶剂完全挥发,后放于真空干燥箱中在55℃下真空干燥3h,制备得到的材料命名为“沼气脱硫剂①”。
实施例3
根据本发明提出的方法,以厌氧发酵沼渣为原料,通过预处理、活化、炭化、有机胺负载等步骤制备沼气脱硫剂,具体实施方式如下:
步骤1)~3)与实施例1相同;
4)称取0.22g聚乙烯亚胺(PEI),溶解于15mL甲醇中,在常温(25±5℃)下以300rpm的转速磁力搅拌至PEI完全溶解;称取2.0g上述活化多孔炭,与PEI溶液混合,混合物在40℃下以300rpm的转速磁力搅拌至溶剂完全挥发,后放于真空干燥箱中在55℃下真空干燥3h,制备得到的材料命名为“沼气脱硫剂②”。
实施例4
根据本发明提出的方法,以厌氧发酵沼渣为原料,通过预处理、活化、炭化、有机胺负载等步骤制备沼气脱硫剂,具体实施方式如下:
步骤1)~3)与实施例1相同;
4)称取0.86g四乙烯五胺(TEPA),溶解于15mL甲醇中,在常温(25±5℃)下以300rpm的转速磁力搅拌至TEPA完全溶解;称取2.0g上述活化多孔炭,与TEPA溶液混合,混合物在40℃下以300rpm的转速磁力搅拌至溶剂完全挥发,后放于真空干燥箱中在55℃下真空干燥3h,制备得到的材料命名为“沼气脱硫剂③”。
对上述实施例2~4中制备得到的活化多孔炭和沼气脱硫剂,采用热重分析仪(型号TGA/DSC 2STARe,Mettler Toledo)测试不同条件下的H2S吸附量。结果如表2所示。可以看出,有机胺负载前的活化多孔炭的H2S吸附量最高仅有5.1g/kg。而通过在活化多孔炭中负载有机胺,能有限提高材料的H2S吸附性能。本发明以厌氧发酵沼渣为原料制备的沼气脱硫剂,可以在50~5000ppm的低浓度范围内吸附13.0~31.7g/kg的H2S,且操作温度处于中温或高温厌氧发酵的范围内,对沼气条件的适用性较好。
表2实施例中所制备的沼气脱硫剂在不同条件下的H2S吸附量
需要说明的是,本发明并不局限于前述的具体实施方式,以上实施例的结果和说明是用于帮助理解本发明涉及的方法和应用效果。根据本发明所述的沼渣原位利用作为沼气脱硫剂的方法,只要不偏离本发明的结构和权利要求书中所规定的参数范围,均在本发明的保护范围内。
Claims (8)
1.一种沼渣原位利用作为沼气脱硫剂的方法,其特征在于,将厌氧发酵产生的副产物沼渣作为原料,经烘干、活化、炭化、有机胺负载步骤制备得到沼气脱硫剂,应用于厌氧发酵沼气的脱硫净化。
2.根据权利要求1所述的沼渣原位利用作为沼气脱硫剂的方法,其特征在于,所述沼渣来源于厨余垃圾、果蔬垃圾、园林垃圾、农业废弃物厌氧发酵沼渣的一种或两种以上的组合。
3.根据权利要求1所述的沼渣原位利用作为沼气脱硫剂的方法,其特征在于,所述有机胺为四乙烯五胺、五乙烯六胺、聚乙烯亚胺中的一种或两种以上的组合。
4.根据权利要求1所述的沼渣原位利用作为沼气脱硫剂的方法,其包括如下具体步骤:
1)将厌氧发酵产生的副产物沼渣烘干得到干燥沼渣;
2)将干燥沼渣,浸泡于活化试剂溶液中并搅拌;将搅拌均匀的混合物离心;
3)取离心后的沉淀物在惰性氛围下高温炭化,洗涤烘干,得到多孔炭;
4)将有机胺溶于醇或水溶液中,加入步骤3)中制得的多孔炭,搅拌浸渍直至溶剂挥发,得到所述沼气脱硫剂。
5.根据权利要求4所述的沼渣原位利用作为沼气脱硫剂的方法,其特征在于,所述活化试剂选自氢氧化钠、氢氧化钾或氯化锌,所述干燥沼渣与所述活化试剂的质量比为0.8~1.5:1。
6.根据权利要求4所述的沼渣原位利用作为沼气脱硫剂的方法,其特征在于,所述有机胺和所述多孔炭的质量比为0.1~0.5:1。
7.一种用于权利要求1~6任一项所述方法的沼气脱硫剂,其特征在于,所述沼气脱硫剂能在30~60℃的沼气温度下吸附50~5000ppm浓度范围的硫化氢气体。
8.根据权利要求7所述的沼气脱硫剂,其特征在于,所述沼气脱硫剂在使用后可以通过变温或变压操作实现再生并循环利用。
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