CN110201977B - 一种大型海藻水热碳化液资源化利用的方法 - Google Patents
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Abstract
本发明提供了一种大型海藻水热碳化液资源化利用的方法,属于环境工程固废资源化技术领域。在大型海藻水热碳化过程中通过水热碳化液循环利用,在提高水热炭产量的同时,可强化抑制性有机物热化学转化,再通过水热炭强化甲烷发酵进一步处理后,发酵液联合水热炭修复滨海污染土壤。本发明效果和益处是可实现大型海藻水热碳化产物的完全资源化利用,有效地克服水热碳化液常规厌氧消化处理时产甲烷效率和甲烷纯度低的技术瓶径,而且产生的高纯度甲烷和水热炭均可用于水热反应器的加热,实现能量自给,在海藻废弃物资源化利用以及滨海土壤和湿地污染修复中具有广阔的应用前景。
Description
技术领域
本发明属于环境工程固废资源化技术领域,涉及一种大型海藻水热碳化液资源化利用的方法。
背景技术
近海养殖大型海藻在海洋生态系统中发挥着重要的作用,可以增加海洋对二氧化碳的吸收能力,降低二氧化碳对全球温室效应造成的影响。同时,大型海藻可大量吸收水体中有机物、氮、磷等,提高物质循环能力,改善海域富营养化,是近海生态环境的有效修复策略。然而,如果处置不当,大型海藻会在海洋中大量自然衰亡,带来一系列环境问题。另外,在以大型海藻为原料制备高附加值产品过程中会不可避免地产生大量海藻残渣,不仅浪费生物质资源,而且易造成二次污染。
水热碳化技术不受原料含水率的制约、制备过程简单、反应条件温和、效率高、成本低;所得水热炭产量较高且具有丰富官能团等优点,可以作为燃料以及环境修复材料等,被认为是高含水率生物质制备生物炭较为理想的方法。目前在大型海藻水热碳化技术中,主要用于制备水热炭材料。丁宜强等人利用浒苔制备了浒苔基水热炭,并用于偶氮染料废水吸附处理(鲁东大学硕士学位论文,2016);窦鑫等人利用铜藻制备了炭基固体酸催化剂,用于催化酯化反应(浙江工业大学硕士学位论文,2016);在发明专利CN201610487013.5中,王宗花等人采用巨藻为碳源,一步法水热碳化制备荧光碳纳米点;在发明专利CN201610480531.4中,桂日军等人直接水热碳化海带制备荧光碳纳米颗粒。
然而,利用海藻生物质制备水热炭材料的同时,也产生大量的水热碳化液。目前大型海藻水热碳化液主要作为难降解有机废水,通过净化处理后排放。由于海藻水热碳化液中含有大量的抑制性有机物,故采用常规厌氧消化处理时产甲烷效率较低,阻碍了其资源化利用。
发明内容
本发明的目的是针对大型海藻水热碳化中液相部分资源化效率低的技术瓶径,提供一种经济高效的大型海藻水热碳化液资源化利用方法。
本发明的技术解决方案是在大型海藻水热碳化过程中通过水热碳化液循环利用,在提高水热炭产量的同时,可强化抑制性有机物热化学转化;再通过水热炭强化甲烷发酵进一步处理后,发酵液联合水热炭修复滨海污染土壤。
本发明的技术方案:
一种大型海藻水热碳化液资源化利用的方法,步骤如下:
步骤1.水热碳化
收集沿海废弃大型海藻或海藻加工废渣,用水清洗去除杂质,自然晾干,粉碎后作为水热碳化的原料;调节原料与水的质量比为1:10-20,将此混合物放入水热反应器中,控制反应温度为200-230℃,反应时间为1.5-3h,得到海藻基水热碳化产物;将上述得到的海藻基水热碳化产物经过固液分离后,回收水热炭,收集液相产物作为下一轮水热碳化的液相;水热碳化循环8-10轮后的液相部分即为水热碳化液;
步骤2.水热炭强化水热碳化液甲烷发酵
将步骤1得到的水热炭与厌氧污泥投加至厌氧反应器中,控制污泥浓度为10-20g/L,水热炭与污泥质量比为1:1-1.5;用水或步骤3得到的上清液稀释步骤1得到的水热碳化液至COD为2000-5000mg/L,作为反应器进水,控制水力停留时间为18-48h,反应器温度为35-37℃,反应器溶解氧为0-0.2mg/L;反应器连续运行,收集甲烷和发酵液,甲烷纯度为85-90%,发酵液COD为500-1500mg/L,pH为7.5-9.0;
步骤3.发酵液联合水热炭修复滨海污染土壤
将步骤1得到的水热炭加入50-60℃水中,控制水热炭与水的质量比为1:10,清洗时间为5-10min,固液分离后,收集上清液和水热炭;将得到的水热炭加入到滨海污染土壤中,控制水热炭与土壤的质量比为0.002-0.02,再加入步骤2得到的发酵液,控制土壤湿度为50-60%,混合后在静置条件下修复40-60d,修复期间每隔2天翻土一次,并通过补加步骤2得到的发酵液控制土壤湿度为50-60%。
本发明的有益效果:
(1)海藻水热碳化液适当循环利用可节能,提高水热碳产量,促进毒性有机物的转化,而且水热炭可作为燃料用于水热反应器加热,也可作为功能性材料应用于环境治理领域。
(2)可以克服水热碳化液常规厌氧消化处理时产甲烷效率和甲烷纯度低的技术瓶径,产生的高纯度甲烷可用于水热反应器的加热,实现能量自给,也可收集外用。
(3)可实现大型海藻水热碳化产物的完全资源化利用,为滨海污染土壤的修复改良提供一种新方法,并为海藻其他水热处理技术中废水资源化利用提供借鉴。
附图说明
图1是本发明提供的发酵液联合水热炭修复滨海石油污染土壤的曲线图。
图中:纵坐标表示总石油烃去除率,单位为%;横坐标表示时间,单位为天。—■—代表添加发酵液和水热炭体系;—▲—代表添加发酵液体系;—○—代表添加水热炭体系;—◆—代表添加水的对照体系。图中表明发酵液联合水热炭修复滨海石油污染土壤60天后,总石油烃去除率达到78.3%,比对照提高3.1倍。
具体实施方式
下面结合技术方案和附图对本发明作进一步说明,但本发明并不限于下述实施例。
实施例1
(1)水热碳化
收集沿海废弃海带,用水清洗去除泥沙等杂质,自然晾干,粉碎后作为水热碳化的原料;调节原料与水的比列为1:20,将此混合物放入水热反应器中,控制反应温度为220℃,反应时间为2h,得到海藻基水热碳化产物;将上述得到的海藻基水热碳化产物经过固液分离后,回收水热炭,收集液相产物作为下一轮水热碳化的液相;水热碳化循环10轮后的液相部分即为水热碳化液;
(2)水热炭强化水热碳化液甲烷发酵
将步骤(1)得到的水热炭与厌氧污泥投加至厌氧反应器中,控制污泥浓度为15g/L,水热炭与污泥质量比为1:1;用水或步骤(3)得到的上清液稀释步骤(1)得到的水热碳化液至COD为2000mg/L,作为反应器进水,控制水力停留时间为18h,反应器温度为35-36℃,反应器溶解氧为0-0.1mg/L;反应器连续运行,收集甲烷和发酵液,甲烷纯度为90%,发酵液COD为510mg/L,pH为8.6;
(3)发酵液联合水热炭修复滨海污染土壤
将步骤(1)得到的水热炭加入50℃水中,控制水热炭与水质量比为1:10,清洗时间为10min,固液分离后,收集上清液和水热炭;将步骤(3)得到的水热炭加入到滨海石油污染土壤中,控制水热炭与土壤的质量比为0.01,总石油烃浓度为9.6g/kg土壤,再加入步骤(2)得到的发酵液,控制土壤湿度为50-55%,混合后在静置条件下修复60d,修复期间每隔2天翻土一次,并通过补加步骤(2)得到的发酵液控制土壤湿度为50-55%。
实施例2
(1)水热碳化
收集海带提取多糖后的藻渣,用水清洗去除泥沙等杂质,自然晾干,粉碎后作为水热碳化的原料;调节原料与水的比列为1:15,将此混合物放入水热反应器中,控制反应温度为210℃,反应时间为2.5h,得到海藻基水热碳化产物;将上述得到的海藻基水热碳化产物经过固液分离后,回收水热炭,收集液相产物作为下一轮水热碳化的液相;水热碳化循环9轮后的液相部分即为水热碳化液;
(2)水热炭强化水热碳化液甲烷发酵
将步骤(1)得到的水热炭与厌氧污泥投加至厌氧反应器中,控制污泥浓度为12g/L,水热炭与污泥质量比为1:1;用水或步骤(3)得到的上清液稀释步骤(1)得到的水热碳化液至COD为3000mg/L,作为反应器进水,控制水力停留时间为24h,反应器温度为35-36℃,反应器溶解氧为0-0.2mg/L;反应器连续运行,收集甲烷和发酵液,甲烷纯度为88%,发酵液COD为690mg/L,pH为8.7;
(3)发酵液联合水热炭修复滨海污染土壤
将步骤(1)得到的水热炭加入60℃水中,控制水热炭与水质量比为1:10,清洗时间为5min,固液分离后,收集上清液和水热炭;将步骤(3)得到的水热炭加入到滨海石油污染土壤中,控制水热炭与土壤的质量比为0.02,总石油烃浓度为9.6g/kg土壤,再加入步骤(2)得到的发酵液,控制土壤湿度为50-55%,混合后在静置条件下修复50d,修复期间每隔2天翻土一次,并通过补加步骤(2)得到的发酵液控制土壤湿度为50-55%。
实施例3
(1)水热碳化
收集沿海废弃海带,用水清洗去除泥沙等杂质,自然晾干,粉碎后作为水热碳化的原料;调节原料与水的比列为1:20,将此混合物放入水热反应器中,控制反应温度为230℃,反应时间为1.5h,得到海藻基水热碳化产物;将上述得到的海藻基水热碳化产物经过固液分离后,回收水热炭,收集液相产物作为下一轮水热碳化的液相;水热碳化循环10轮后的液相部分即为水热碳化液;
(2)水热炭强化水热碳化液甲烷发酵
将步骤(1)得到的水热炭与厌氧污泥投加至厌氧反应器中,控制污泥浓度为15g/L,水热炭与污泥质量比为1:1;用水或步骤(3)得到的上清液稀释步骤(1)得到的水热碳化液至COD为4000mg/L,作为反应器进水,控制水力停留时间为30h,反应器温度为36-37℃,反应器溶解氧为0-0.2mg/L;反应器连续运行,收集甲烷和发酵液,甲烷纯度为87%,发酵液COD为985mg/L,pH为8.5;
(3)发酵液联合水热炭修复滨海污染土壤
将步骤(1)得到的水热炭加入50℃水中,控制水热炭与水质量比为1:10,清洗时间为10min,固液分离后,收集上清液和水热炭;将步骤(3)得到的水热炭加入到有机-重金属复合污染滨海土壤中,控制水热炭与土壤的质量比为0.02,总石油烃浓度为7.5g/kg土壤,铅平均浓度为119mg/kg土壤,再加入步骤(2)得到的发酵液,控制土壤湿度为50-55%,混合后在静置条件下修复50d,修复期间每隔2天翻土一次,并通过补加步骤(2)得到的发酵液控制土壤湿度为50-55%。
Claims (1)
1.一种大型海藻水热碳化液资源化利用的方法,其特征在于,步骤如下:
步骤1.水热碳化
收集沿海废弃大型海藻或海藻加工废渣,用水清洗去除杂质,自然晾干,粉碎后作为水热碳化的原料;调节原料与水的质量比为1:10-20,将此混合物放入水热反应器中,控制反应温度为200-230℃,反应时间为1.5-3h,得到海藻基水热碳化产物;将上述得到的海藻基水热碳化产物经过固液分离后,回收水热炭,收集液相产物作为下一轮水热碳化的液相;水热碳化循环8-10轮后的液相部分即为水热碳化液;
步骤2.水热炭强化水热碳化液甲烷发酵
将步骤1得到的水热炭与厌氧污泥投加至厌氧反应器中,控制污泥浓度为10-20g/L,水热炭与污泥质量比为1:1-1.5;将步骤1得到的水热炭加入50-60℃水中,控制水热炭与水的质量比为1:10,清洗时间为5-10min,固液分离后,收集上清液和水热炭;用水或得到的上清液稀释步骤1得到的水热碳化液至COD为2000-5000mg/L,作为反应器进水,控制水力停留时间为18-48h,反应器温度为35-37℃,反应器溶解氧为0-0.2mg/L;反应器连续运行,收集甲烷和发酵液,甲烷纯度为85-90%,发酵液COD为500-1500mg/L,pH为7.5-9.0;
步骤3.发酵液联合水热炭修复滨海污染土壤
将步骤2得到的水热炭加入到滨海污染土壤中,控制水热炭与土壤的质量比为0.002-0.02,再加入步骤2得到的发酵液,控制土壤湿度为50-60%,混合后在静置条件下修复40-60d,修复期间每隔2天翻土一次,并通过补加步骤2得到的发酵液控制土壤湿度为50-60%。
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