CN114887590A - 一种富含碱性位点的多孔生物炭制备方法及其在臭气吸附中的应用 - Google Patents
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Abstract
本发明涉及生物质资源利用技术领域,具体涉及一种富含碱性位点的多孔生物炭制备方法及其在臭气吸附中的应用。本发明将木屑、造孔剂和含氮模板剂混合均匀后球磨成固体混合物,采用热解法在保护性气体中将混合物制备成多孔生物炭。该制备方法不但可以丰富生物炭的孔隙结构,还可以在表面形成更多的缺陷位点,有利于引入碱性的含氮官能团,提高吸附臭气中酸性气体组分的效率。同时,本发明还公开了一种多孔生物炭在臭气吸附中的应用,通过将制备的生物炭和分子筛组合形成组合吸附剂,实现物理吸附和化学吸附的双重吸附,从而达到大幅度提高臭气吸附效率的目的。
Description
技术领域
本发明涉及生物质资源利用技术领域,具体涉及一种富含碱性位点的多孔生物炭制备方法及其在臭气吸附中的应用。
背景技术
近年来,对于城市垃圾填埋场的大量填埋气,其清洁和安全的处理与能源化利用成为当前的研究热点。微生物厌氧消化会产生垃圾填埋气,含有的成分包括了甲烷、二氧化碳、氮气、水以及含硫的有害气体(SO2、H2S)等,合理运用可再生能源技术来处理填埋气,不但可以大幅度降低大气污染物的排放,而且还可以获得生物天然气资源,有环保的经济效益。
填埋气生成过程中会产生臭气(以H2S为主的酸性气体),在存在水和氧气的环境下,臭气中的酸性气体会腐蚀管道、阀门、压缩机、储气罐等设备,降低设备使用寿命,同时硫化物的泄漏排放会严重污染环境影响生物安全,因此脱除H2S等酸性气体是填埋气利用过程中的关键步骤。至今为止,国内外的学者对臭气吸附进行了广泛的研究,主要包括物理吸附法和化学吸附法。物理吸附主要是采用活性炭、分子筛等大比表面积的活性介质,通过范德华力将气体分子吸附在多孔介质里,达到去除臭味的目的,其特点是活化能小,吸附速率快和脱附容易。虽然物理吸附剂对臭气的吸附量大,但是物理吸附没有选择性,在低浓度臭气环境下的吸附效果差。化学吸附是指由分子间形成化学键而产生的吸附,其特点是选择性强,对低浓度臭气吸附也有很好的效果,但是大部分的化学吸附剂对臭气的吸附量比较小。最常见的化学吸附剂是掺杂碱性化合物(如KOH、NaOH等)的负载型吸附剂,丰富的碱性官能团能够高效吸附臭气中的酸性组分,但是其强碱性同时也会腐蚀设备,造成二次污染。因此,制备既高效又无腐蚀性的化学吸附剂是一大挑战。
生物炭是一种当前广泛使用于化学吸附的材料,具有来源充足、成本低廉和可再生的优点,得到了行业的高度关注。生物炭材料由生物质原料直接炭化得到,其孔隙结构少、比表面积小,为了改善生物炭的孔道和比表面积特性,可以在炭化过程中添加造孔剂,丰富孔隙结构,增大比表面积。中国发明专利申请CN110935280A公开了一种氮掺杂介孔竹基生物炭及其应用,以废弃一次性竹筷为前驱体,经过预处理、炭化、空气氧化、尿素掺氮等步骤制得介孔竹基生物炭,但该活性炭孔隙结构较差、比表面积有限,没有碱性位点。中国发明专利申请CN113231013A公开了用于吸附多组分有机污染物的酒糟基生物炭及其制备方法,其制备出微孔结构丰富和比表面积大的酒糟基生物炭,但其使用的是KOH、NaOH等碱性化学药品作为活化剂,其强碱性会腐蚀设备。但目前的生物炭材料仍然存在孔隙结构少、比表面积有限和腐蚀性的问题,因此需要研发微孔结构丰富、比表面积大和无腐蚀性的改性生物炭材料。
发明内容
为了克服上述现有技术的不足,本发明的目的是提供一种富含碱性位点的多孔生物炭制备方法及其在臭气吸附中的应用,本发明所制备的富含碱性位点的多孔生物炭的微孔结构丰富、比表面积大和无腐蚀性,采用热解木屑、造孔剂和含氮模板剂的方法使生物炭表面形成大量的碱性位点,提高吸附臭气中酸性气体组分的效率,解决了目前的生物炭材料仍然存在孔隙结构少、比表面积有限和腐蚀性的问题。
为了实现上述目的,本发明所采用的技术方案是:
本发明提供了一种富含碱性位点的多孔生物炭制备方法,该方法包括以下步骤:
S1、将木屑、造孔剂和含氮模板剂混合均匀,后粉碎成均一的固体混合物;
S2、将固体混合物在惰性气氛下进行热解反应;
S3、所得固体产物中加入沸水搅拌均匀去除杂质,后过滤并干燥滤渣得到富含碱性位点的微孔生物炭。
优选地,步骤1中,所述木屑包括竹屑、杉木木屑;所述造孔剂包括氯化钾、氯化钠;所述含氮模板剂包括三聚氰胺、氯化铵、磷酸尿素。进一步地,所述木屑为竹屑,所述造孔剂为氯化钠,所述含氮模板剂为三聚氰胺。
优选地,步骤1中,木屑、造孔剂和含氮模板的混合质量比为(2~3):(1~2):(0.5~1)。
优选地,步骤1中,所述固体混合物的粒径小于30目。
优选地,步骤2中,所述热解反应的详细步骤为以升温速率3~5℃/min,升温至300~350℃反应1~2h;然后以升温速率1~3℃/min,升温至750~850℃反应2~3h。进一步地,所述热解反应的详细步骤为以升温速率3℃/min,升温至300℃反应1h;然后以升温速率1℃/min,升温至750℃反应2h。
优选地,步骤2中,所述惰性气体为氮气。
本发明还提供了采用上述的制备方法制备得到的富含碱性位点的多孔生物炭,所述富含碱性位点的多孔生物炭应用于臭气化学吸附。将制备的多孔生物炭和分子筛组合形成组合吸附剂,应用于臭气物理和化学的吸附。
与现有技术相比,本发明的有益效果是:
本发明提供了一种富含碱性位点的多孔生物炭制备方法及其在臭气吸附中的应用,采用热解法在保护性气体中将木屑、造孔剂和含氮模板剂混合均匀粉碎的固体混合物制备成多孔生物炭。利用热解法和造孔剂丰富生物炭的孔隙结构,并在表面形成更多的缺陷位点,含氮模板剂提供碱性官能团并形成碱性位点,提高吸附臭气中酸性气体组分的效率。本发明制备的生物炭微孔结构丰富,比表面积大和无腐蚀性,能应用于臭气化学吸附,再结合分子筛应用能实现臭气物理和化学的双重吸附,大幅度提高臭气吸附效率。
附图说明
图1a~d为生物炭的电镜扫描图,其中(a)和(b)为生物炭C,(c)和(d)为NMC-1;
图2为生物炭耦合分子筛的四种填充小型吸附塔的示意图,其中(a)为分子筛:生物炭:分子筛=1:1:1的填料比例填充的小型吸附塔;(b)为分子筛:生物炭:分子筛=1:4:1的填料比例填充的小型吸附塔;(c)为分子筛:生物炭=1:1的填料比例均匀混合的小型吸附塔;(d)为分子筛:生物炭:分子筛=3:1:2的填料比例填充的小型吸附塔。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
下述实施例中的实验方法,如无特殊说明,均为常规方法,下述实施例中所用的试验材料,如无特殊说明,均为可通过常规的商业途径购买得到。
实施例1NMC-1的制备和其组合吸附剂
(1)将3g竹屑,2g氯化钾和1.5g三聚氰胺搅拌均匀,将混合物和直径分别为1mm和5mm氧化锆球放置于100mL的聚四氟乙烯球磨罐中,经行星式球磨机以270rpm的转速球磨12小时后分离物料,后用30目筛过滤得到均一的粉状固体混合物;
(2)将粉状固体混合物转入管式炉中,在氮气的气氛下热解,以3℃/min的升温速率升到300℃后反应1h,然后以1℃/min的升温速率升到750℃后反应2小时,后冷却至室温得到固体产物;
(3)将所得固体产物加进500mL沸水中,搅拌均匀后进行抽滤;将滤渣再用2L去离子水分5次抽滤洗涤至滤液为中性,最后将滤渣放入60℃的烘箱中干燥12小时,得到富含碱性位点的多孔生物炭,记为NMC-1;
(4)NMC-1与分子筛组合的吸附剂的制备:
1、将①0.1g 13X分子筛、②0.1g NMC-1和③0.1g 13X分子筛按照1:1:1的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX1,吸附剂填料方式如图2(a);
2、将①0.05g 13X分子筛、②0.2g NMC-1和③0.05g 13X分子筛按照1:4:1的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX2,吸附剂填料方式如图2(b);
3、将①0.15g13X分子筛、②0.15g NMC-1按照1:1的填料比例均匀混合填充在小型吸附塔中,记为MIX3,吸附剂填料方式如图2(c);
4、将①0.15g 13X分子筛、②0.05g NMC-1和③0.1g 13X分子筛按照3:1:2的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX4,吸附剂填料方式如图2(d)。
实施例2NMC-2的制备和其组合吸附剂
制备方法同实施例1,与实施例1不同的是,所用木屑为杉木木屑,制备得到含碱性位点的微孔木基生物炭,记为NMC-2;
NMC-2与分子筛组合的吸附剂的制备:
1、将①0.1g 13X分子筛、②0.1g NMC-2和③0.1g 13X分子筛按照1:1:1的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX5,吸附剂填料方式如图2(a);
2、将①0.05g 13X分子筛、②0.2g NMC-2和③0.05g 13X分子筛按照1:4:1的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX6,吸附剂填料方式如图2(b);
3、将①0.15g13X分子筛、②0.15g NMC-2按照1:1的填料比例均匀混合填充在小型吸附塔中,记为MIX7,吸附剂填料方式如图2(c);
4、将①0.15g 13X分子筛、②0.05g NMC-2和③0.1g 13X分子筛按照3:1:2的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX8,吸附剂填料方式如图2(d)。
对比例1生物炭C的制备和其组合吸附剂
制备方法同实施例1,与实施例1不同的是,没有添加氯化钾和三聚氰胺,制备得到生物炭C;
生物炭C与分子筛组合的吸附剂的制备:称取①0.1g 13X分子筛、②0.1g生物炭C和③0.1g 13X分子筛按照1:1:1的填料比例填充在小型吸附塔中,且填料顺序按照称取序号从下往上排列,记为MIX9,吸附剂填料方式如图2(a)。
对比例2分子筛吸附剂
采用分子筛进行纯物理吸附臭气实验,称取0.3g 13X分子筛全部填充在小型吸附塔中,记为MIX10。
实施例1生物炭的结构表征和组合吸附剂的吸附能力测试
(1)结构表征
对NMC-1和生物炭C进行电镜扫描分析,扫描图如图1所示,从图1a-b观察到生物炭C的表面形态相对平坦无孔,表明它的比表面积和孔体积都很小;,从图1c-d观察到NMC-1生物炭的表面具有丰富的孔隙结构。
对NMC-1、NMC-2和生物炭C采用全自动比表面积与孔径分析仪测定活性炭的比表面积、孔容和孔径分布,不同生物炭的比表面积和孔道特性如表1所示:
表1不同生物炭的比表面积和孔道特性表征结果
从表1得出,利用造孔剂氯化钠能大幅增加生物炭的比表面积和孔容,丰富生物炭的孔隙结构(如微孔、介孔),使表面形成更多的缺陷位点,有利于引入含氮官能团的碱性位点。
(2)组合吸附剂的吸附能力测试
将MIX1-10在室温下进行固定床吸附穿透实验。分别将吸附剂装填在内径为10mm的石英管中,设置进口硫化氢浓度为500ppm,进气速度控制在100mL/min。穿透吸附容量是以出口气体的某一浓度为判断指标,当出口气体的浓度达到这一指标时单位质量吸附剂所能吸附的气体分子质量。本实验中认为当出口硫化氢浓度为1ppm时开始穿透,根据下列公式计算出穿透硫容AC,
式中:
AC:单位质量的吸附剂开始穿透时所吸附的硫化氢的质量,mg/g;
V:入口气体流速,mL/min;
t:时间,min;定义出口硫化氢浓度为1ppm的穿透时间;
Cin:进口硫化氢浓度,ppm;
Cout:出口硫化氢浓度,ppm;
M:硫化氢的分子量,34g/mol;
Vmol:摩尔体积,22.45mol/L(25℃,1atm);
m:吸附剂质量,g;
各组合吸附剂穿透硫容AC结果如表2所示:
表2不同组合吸附剂的穿透硫容
从表2得出,MIX1-8的穿透硫容比单一生物炭有大幅增加,表明通过造孔剂在表面形成大量的缺陷位点,借此引入大量含氮官能团的碱性位点,能大幅度增加碱性位点与酸性气体的接触和吸附,从而提高臭气化学吸附的效率。
综上所述,本发明用木屑、造孔剂和含氮模板剂热解形成的多孔生物炭,有丰富的生物炭的孔隙结构(如微孔、介孔),比表面积大,并在表面形成大量含氮官能团的碱性位点,大幅度增加碱性位点与酸性气体的接触和吸附,从而提高臭气化学吸附的效率,且无腐蚀性,能减少对设备的损害;通过将多孔生物炭和分子筛组合成组合吸附剂,实现物理吸附和化学吸附的双重吸附,从而达到大幅度提高臭气吸附效率的目的。
以上对本发明的实施方式作了详细说明,但本发明不限于所描述的实施方式。对于本领域的技术人员而言,在不脱离本发明原理和精神的情况下,对这些实施方式进行多种变化、修改、替换和变型,仍落入本发明的保护范围内。
Claims (8)
1.一种富含碱性位点的多孔生物炭的制备方法,其特征在于,包括以下步骤:
S1、将木屑、造孔剂和含氮模板剂混合均匀,后粉碎成均一的固体混合物;
S2、将固体混合物在惰性气氛下进行热解反应;
S3、所得固体产物中加入沸水搅拌均匀去除杂质,后过滤并干燥滤渣得到富含碱性位点的微孔生物炭。
2.根据权利要求1的一种富含碱性位点的多孔生物炭的制备方法,其特征在于,步骤1中,所述木屑包括竹屑、杉木木屑;所述造孔剂包括氯化钾、氯化钠;所述含氮模板剂包括三聚氰胺、氯化铵、磷酸尿素。
3.根据权利要求1的一种富含碱性位点的多孔生物炭的制备方法,其特征在于,步骤1中,木屑、造孔剂和含氮模板的混合质量比为(2~3):(1~2):(0.5~1)。
4.根据权利要求1的一种富含碱性位点的多孔生物炭的制备方法,其特征在于,步骤1中,所述固体混合物的粒径小于0.6mm。
5.根据权利要求1的一种富含碱性位点的多孔生物炭的制备方法,其特征在于,步骤2中,所述热解反应的详细步骤为以升温速率3~5℃/min,升温至300~350℃反应1~2h;然后以升温速率1~3℃/min,升温至750~850℃反应2~3h。
6.根据权利要求1的一种富含碱性位点的多孔生物炭的制备方法,其特征在于,步骤2中,所述惰性气体为氮气。
7.如权利要求1~6任一所述的制备方法所制备的富含碱性位点的多孔生物炭。
8.权利要求7所述的富含碱性位点的多孔生物炭应用于臭气吸附。
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