CN110484298A - 一种利用堆肥羊粪气化制备合成气的方法 - Google Patents

一种利用堆肥羊粪气化制备合成气的方法 Download PDF

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CN110484298A
CN110484298A CN201910785498.XA CN201910785498A CN110484298A CN 110484298 A CN110484298 A CN 110484298A CN 201910785498 A CN201910785498 A CN 201910785498A CN 110484298 A CN110484298 A CN 110484298A
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sheep dung
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宋英今
王彩玉
孟姝妍
陈冠益
钟磊
林法伟
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10J3/723Controlling or regulating the gasification process
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00Details of gasification apparatus
    • C10J2200/33Laboratory scale gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903Feed preparation
    • C10J2300/0906Physical processes, e.g. shredding, comminuting, chopping, sorting
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903Feed preparation
    • C10J2300/0909Drying
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0946Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale

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Abstract

本发明公开了一种利用堆肥羊粪制备合成气的方法,将堆肥羊粪进行55‑60℃干燥、粉碎、筛选获得0.18‑0.25mm的原料;采用空气作为气化剂,反应前10min采用0.2L/min流量通入反应装置,反应温度范围为800‑1000℃;采用管式炉作为气化装置,推动炉体至炉管3/4处制合成气。堆肥羊粪作为气化原料,丰富羊粪利用方式,增加合成气的产生来源;制得的合成气高于其它畜禽粪便热值,将其进行相应调整产煤气,合成氨原料气和甲醇合成气等,应用广泛。

Description

一种利用堆肥羊粪气化制备合成气的方法
技术领域
本发明属于生物质能源技术领域,具体涉及一种利用堆肥羊粪制取生物合成气的方法。
背景技术
我国羊粪的产量巨大,是一种潜在的生物质原料。目前羊粪处理方式大多数为堆肥,其产肥料运用于土壤中可显著提高土壤肥力;但在堆肥过程中可降低纤维素和半纤维素比例,提高木质素相应比例,为生物质气化提供相应基础。生物质气化是以空气、蒸汽和氧气等为气化介质,在高温条件下,生物质的大型聚合物分子分解成较轻的分子,最终变成永久性气体(CO、H2、CH4和较轻的碳氢化合物)、灰、焦炭、焦油和少量污染物;焦炭和焦油是生物质不完全转化的结果;所产合成气进行相应调整产煤气,合成氨原料气和甲醇合成气等。
生物质利用方式主要有三种:热化学方法,液相催化方法,生物化学方法。Shou-YuZhang等以堆肥的猪粪为研究对象,在Ni2Al2O3催化剂存在条件下,蒸汽气化HF酸洗的堆肥猪粪可以提高氢气和合成气的产量,促进焦油裂解成小分子物质;Agustín GarcíaBarneto等以银合欢和苜蓿为试验材料,银合欢和苜蓿堆肥前后木质素含量从25%、23%提高到31%、30%,慢加热速率(2.6℃/min)与堆肥均可以提高氢气的产量,两者结合提高氢气产量接近20%;Cao,Jing-Pei等对堆肥干猪粪(DPC)进行两级固定床的催化气化研究,在Ni/Al2O3催化剂存在条件下,热解产生的挥发物中的氮全部转变为N2,对NOx前体的减少有很重要的意义,可见,堆肥(生物化学方法)耦合气化(热化学方法)可以提高H2体积分数,气体产量和相应热值,适当减少NOX前体的产生,减少环境污染。因此,采用堆肥羊粪进行气化,一方面可以充分利用羊粪,提高生物质的利用率,避免生物质浪费与环境污染;另一方面丰富合成气来源,对合成气的产生和高效利用具有重要的意义。
发明内容
本发明的目的主要是提出一种利用堆肥羊粪制备合成气的方法。气化原料采用来源广泛的羊粪,可减缓畜禽粪便产生的环境污染与资源浪费,实现资源化利用。该方法不限制气化装置类型,操作方便,应用广泛。
本发明采用以下技术方案:
(1)预处理;
(2)气化;
(3)利用气相色谱仪中的外标法对合成气进行组分分析;采用低位热值计算公式进行计算。
步骤(1)预处理为:选用堆肥羊粪作为预处理原料,放置原料于55-60℃电热鼓风干燥箱中烘干24h,取出放入粉碎机中进行粉碎,过筛,获得0.18-0.25mm的试验原料,装入聚乙烯塑封袋中备用。
步骤(2)气化为:打开管式炉开关,设置升温程序至反应温度800-1000℃,达到反应温度前10min左右通入流量为0.2L/min的空气,分压为0.1Mpa,待管式炉升温至反应温度时,称取步骤(1)中原料5g于石英舟中,放置于炉管3/4处,将炉体推至原料所在区域进行反应,所产气体经过冷凝管,流量计收集于气袋中。
本发明的优点:
1.本发明提出利用气化技术处理堆肥羊粪,可实现生物质的充分利用,解决羊粪产量大,利用方式单一等问题;
2.本发明所提出的堆肥羊粪气化产生的合成气,其低位热值比一般禽畜粪便高,且气化过程产气体污染物较少,减少环境污染;
3.本发明所提出的利用堆肥羊粪气化制备合成气的方法,对气化装置没有要求,可采用下吸式固定床气化炉、管式炉、流化床等,皆可进行气化实验,操作简便,应用广泛。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。下面的实施例是为了使本领域的技术人员能够更好地理解本发明,但并不对本发明作任何限制。
堆肥羊粪取自山西某堆肥公司。
实施例1:
(1)选用堆肥羊粪作为预处理原料,放置原料于55℃电热鼓风干燥箱中烘干24h,取出放入粉碎机中进行粉碎,过筛,获得0.25mm的试验原料,装入聚乙烯塑封袋中备用。
(2)打开管式炉开关,设置升温程序至反应温度800℃,达到反应温度前10min左右通入流量为0.2L/min的空气,分压为0.1Mpa,待管式炉升温至反应温度时,称取步骤(1)中原料5g于石英舟中,放置于炉管3/4处,将炉体推至原料所在区域进行反应,所产气体经过冷凝管,流量计收集于气袋中。
(3)利用气相色谱仪中的外标法对合成气进行组分分析;采用低位热值计算公式进行计算。
本实施例所得氢气所占百分比为1.50%,合成气低位热值为0.632MJ/Nm3
实施例2:
(1)选用堆肥羊粪作为预处理原料,放置原料于57℃电热鼓风干燥箱中烘干24h,取出放入粉碎机中进行粉碎,过筛,获得0.212mm的试验原料,装入聚乙烯塑封袋中备用。
(2)打开管式炉开关,设置升温程序至反应温度900℃,达到反应温度前10min左右通入流量为0.2L/min的空气,分压为0.1Mpa,待管式炉升温至反应温度时,称取步骤(1)中原料5g于石英舟中,放置于炉管3/4处,将炉体推至原料所在区域进行反应,所产气体经过冷凝管,流量计收集于气袋中。
(3)利用气相色谱仪中的外标法对合成气进行组分分析;采用低位热值计算公式进行计算。
本实施例所得氢气所占百分比为6.55%,合成气低位热值为3.815MJ/Nm3
实施例3:
(1)选用堆肥羊粪作为预处理原料,放置原料于60℃电热鼓风干燥箱中烘干24h,取出放入粉碎机中进行粉碎,过筛,获得0.18mm的试验原料,装入聚乙烯塑封袋中备用。
(2)打开管式炉开关,设置升温程序至反应温度1000℃,达到反应温度前10min左右通入流量为0.2L/min的空气,分压为0.1Mpa,待管式炉升温至反应温度时,称取步骤(1)中原料5g于石英舟中,放置于炉管3/4处,将炉体推至原料所在区域进行反应,所产气体经过冷凝管,流量计收集于气袋中。
(3)利用气相色谱仪中的外标法对合成气进行组分分析;采用低位热值计算公式进行计算。
本实施例所得氢气所占百分比为7.44%,合成气低位热值为4.082MJ/Nm3。根据GC分析结果,得到实施案例1-3产气成分的百分比及产气热值如下表所示:
注:表中为气体所占百分比,热值的单位为MJ/Nm3
本发明所提出的堆肥羊粪气化产生的合成气高于一般畜禽粪便产合成气热值,产合成气进行相应调整产煤气,合成氨原料气和甲醇合成气等。
以上内容不能认定本发明的具体实施只局限这些说明,凡是依照本发明申请专利范围内所做的均等变化和修饰,皆应属于本发明所提交的权利要求书确定的专利保护范围以内。

Claims (2)

1.一种利用堆肥羊粪气化制备合成气的方法,其特征是,包括如下步骤:
(1)预处理;
(2)气化;
所述步骤(1)预处理步骤为:选用堆肥羊粪作为预处理原料,放置原料于55-60℃电热鼓风干燥箱中烘干24h,取出放入粉碎机中进行粉碎,过筛,获得0.18-0.25mm的试验原料;
所述步骤(2)气化步骤为:打开管式炉开关,设置升温程序至反应温度800-1000℃,达到反应温度前通入流量为0.2L/min的空气,分压为0.1Mpa,待管式炉升温至反应温度时,称取步骤(1)中原料5g于石英舟中,放置于炉管3/4处,将炉体推至原料所在区域进行反应,所产气体经过冷凝管,流量计收集于气袋中。
2.根据权利要求1所述的方法,其特征是,利用气相色谱仪中的外标法对合成气进行组分分析;采用低位热值计算公式进行计算。
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