CN111760549A - 一种造纸黑液制备多孔碳基吸附剂的方法 - Google Patents
一种造纸黑液制备多孔碳基吸附剂的方法 Download PDFInfo
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Abstract
本发明公开了一种造纸黑液制备多孔碳基吸附剂的方法,属于资源循环再生利用技术领域;首先通过在造纸黑液中投加可溶性金属盐,金属离子在碱性条件下与木质素螯合析出。然后通过气浮法进行固液分离,将分离出来的木质素螯合物于25‑40℃低温烘干,磨成粉末状。所得木质素粉末在离子液体中超声分散,在40‑400℃环境下加热0.5‑2h,在400‑900℃下通入水蒸气活化1‑5h,最终制成多孔碳基吸附剂,该法制备的吸附剂孔隙可调且性能优良,通用性高,可有效吸附重金属及有机物。
Description
技术领域
本发明涉及一种造纸黑液制备多孔碳基吸附剂的方法,属于资源循环再生利用技术领域。
背景技术
造纸工艺中的碱法制浆蒸煮废液,俗称黑液,含有大量的木质素、部分半纤维素和少量纤维素及色素、残碱、钾、氮、磷等物质,是制浆工艺中污染程度最高的物质。传统燃烧法热值低且存在二次污染的问题;生化处理法又存在处理周期长,处理不彻底的问题;若制成絮凝剂、分散剂等低附加值产物又需投加各种药剂且消耗量有限远远跟不上产生量。故造纸黑液的开发利用亟需进一步解决。
木质素本身存在多种活性官能团,具有一定吸附能力,可用于重金属及有机污染物的去除,所以将木质素向吸附剂方向进行开发利用存在很大的潜力。造纸黑液中木质素含量极高,从造纸黑液中提取木质素并进行高值化利用成为近几年的研究热点。
专利申请《一种使用造纸黑液木质素制备活性炭的方法》(公开号:CN106167263A)公开了一种以木质素为炭源,使用碱性活化剂,将木质素与活化剂球磨混合,通过炭化、活化形成活性炭的方法;该法使用的是常规活化方式的改良版,用的是木质素在碱性条件下易溶的原理,活化、碳化一步完成,虽然其操作简便,但制得的产品性能欠佳。
发明内容
针对现有技术存在的问题,本发明提供了一种造纸黑液制备多孔碳基吸附剂方法,即在造纸黑液中投加可溶性金属盐,使木质素在碱性条件下与金属离子螯合析出,然后通过气浮法进行固液分离,将分离出来的木质素螯合物低温烘干,磨成粉末状;所得粉末在离子液体中超声分散,在密闭环境下热解,过滤,活化,最终制得多孔碳基吸附剂。
本发明中分散良好的木质素-结合态金属螯合物更有利于孔隙结构的生成特别是石墨烯的生成,离子液体浸渍加热活化受热均匀,活化效果好,且除了被固体包覆带走的少量离子液体,浸渍用离子液体可循环利用;高温炭化同步水蒸气二次活化可进一步修饰孔隙结构及表面官能团,使其吸附效果更佳。
所述可溶性金属盐中含Fe3+、Fe2+、Zn2+、Al3+、Co2+、Ni2+、K+中一种或几种阳离子,含Cl-、SO42-、NO3-、Ac-中一种或几种阴离子,可溶性金属盐的添加量为0.05~0.1mol/L。
所述碱性条件为pH=8~14。
所述气浮法使用的气浮设备为常规气浮设备,所用气体可为空气、氧气、或含SO2、CO2、NO2的混合烟道气。
所述烘干温度为25~40℃。
所述离子液体的阳离子为烷基取代的咪唑阳离子、吡啶阳离子、季铵阳离子或季膦阳离子,阴离子为[BF4]-、[PF6]-、[CF3SO3]-、[Tf2N]-、[Ac]-、[SbF6]-、[FeCl4]-、[FeClBr3]-、[AsF6]- 、[C4F9SO3]-或[Co(CO)4]-。
所述热解温度为70~400℃,热解时间为0.5~2h。
所述活化方式为高温水蒸气活化,活化温度为400~900℃,停留时间为1~5h。
本发明的优点和效果如下:
(1)造纸黑液本身呈碱性,使用金属离子与木质素在碱性条件下螯合析出的方式与传统酸析法相比能节省酸液的投加,金属离子在碱性条件下与木质素的螯合效应占主导地位,主要原因在于碱性条件下金属离子的配位势高于氢离子的配位势,故金属离子可与木质素螯合析出;
(2)由于木质素本身具有多种活性官能团,所引入的金属离子与木质素螯合,其结合程度大于普通凝胶方式形成的凝胶基团;
(3)木质素本身也具有表面活性剂的功能,使得金属在木质素中分散性能良好;
(4)气浮法可采用空气和氧气,亦可采用烟道气,烟道气的余热可促进螯合,螯合物亦可吸收SO2、CO2等,可在造纸黑液资源化利用的同时实现烟气净化;
(5)使用离子液体热裂解,除离子液体本身具有良好的传热传质及催化功能,离子液体与木质素中的结合态金属可产生协同催化效应,可有效去除木质素中的纤维素和半纤维素及其他有机杂质,初步形成孔隙结构;
(6)在高温下使用水蒸气进行活化,这个温度超出了本发明所述离子液体的热稳定温度,固体孔道中残留的离子液体被进一步分解,有机成分气化消失,铁,钴等不能气化的元素附于孔壁上,以及一些磺酸基团,氟离子等会进一步在孔壁上形成新的活性官能团,提升吸附剂性能。
具体实施方式
下面通过实施例对本发明做进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1:取某小型造纸厂制浆蒸煮废液10L,初始pH约为11.51;
(1)用1mol/L NaOH将pH微调至12,投加硫酸铝水合物200g(投加比例为0.05mol/L废液),使木质素与金属离子螯合析出;
(2)使用7.2m3/h的微型真空泵泵入空气,取上层固体于40℃下烘干,研磨;
(3)将步骤②粉末置于[Hmim]FeCl4离子液体中超声30min后,在240℃下热解1h,过滤取得固体;
(4)使用氢燃烧水蒸气活化炉在700℃下对固体进行活化2h,最终制得多孔碳基吸附剂,测得吸附剂比表面积为3347m2/g。
(5)用该吸附剂处理1L含砷选矿废水,吸附剂投加量为15g,砷去除率为95.41%。
实施例2: 取自某小型造纸厂制浆蒸煮废液20L,初始pH约为10.88;
(1)用1mol/L NaOH将pH微调至11,投加氯化锌272g(投加比例约为0.1mol/L废液),使木质素与金属离子螯合析出;
(2)使用14.4m3/h的微型真空泵泵入空气,取上层固体于30℃下烘干,研磨;
(3)将步骤②粉末置于[Hmim]CF3SO3离子液体中超声30min,在180℃下热解1h,过滤取得固体;
(4)使用氢燃烧水蒸气活化炉在550℃下对固体进行活化4h,最终制得多孔碳基吸附剂,测得吸附剂比表面积为2834m2/g;
(5)用该吸附剂处理500mL铅锌矿含铬废水,吸附剂投加量为30g,Cr3+去除率为98.32%,Cr6+去除率为93.89%。
实施例3: 取自某小型造纸厂制浆蒸煮废液2L,初始pH约为11.19;
(1)用1mol/L NaOH将pH微调至12,投加十二水硫酸铝钾94.8g(投加比例约为0.1mol/L废液),使木质素与金属离子螯合析出;
(2)以2L/min的流量通入纯氧,取上层固体于30℃下烘干,研磨;
(3)将步骤②粉末置于[Hmim] Co(CO)4离子液体中超声30min,在300℃下热解30min,过滤取得固体;
(4)使用氢燃烧水蒸气活化炉在600℃下对固体进行活化3h,最终制得多孔碳基吸附剂,测得吸附剂比表面积为3123m2/g;
(5)用该吸附剂处理1L印染废水,吸附剂投加量为30g,COD去除率为88.56%。
实施例4: 取自某小型造纸厂制浆蒸煮废液1L,初始pH约为11.04;
(1)用1mol/L NaOH将pH微调至12,投加十二水硫酸铝钾47.4g(投加比例约为0.1mol/L废液),使木质素与金属离子螯合析出;
(2)按气体流量1L/min通入实验室模拟混合烟道气(含1%SO2、16%CO2、0.5%NO2的空气),取上层固体于30℃下烘干,研磨;末端烟气用烟气分析仪分析结果为,SO2平均值为51μg/m3,NO2平均值为44μg/m3;
(3)将步骤②粉末置于[Hmim] Co(CO)4离子液体中超声30min,在300℃下热解30min,过滤取得固体;
(4)使用氢燃烧水蒸气活化炉在600℃下对固体进行活化5h,最终制得多孔碳基吸附剂,测得吸附剂比表面积为2410m2/g;
(5)用该吸附剂处理1L含砷选矿废水,吸附剂投加量为15g,砷去除率为84.41%。
Claims (8)
1.一种造纸黑液制备多孔碳基吸附剂方法,其特征在于,包括以下步骤:
①在造纸黑液中投加可溶性金属盐,使木质素在碱性条件下与金属离子螯合析出;
②然后通过气浮法进行固液分离,将分离出来的木质素螯合物低温烘干,磨成粉末状;
③将步骤②粉末置于离子液体中超声分散,然后在密闭环境下热解,过滤,活化,最终制得多孔碳基吸附剂。
2.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:可溶性金属盐中含Fe3+、Fe2+、Zn2+、Al3+、Co2+、Ni2+、K+中一种或几种阳离子,含Cl-、SO42-、NO3-、Ac-中一种或几种阴离子,可溶性金属盐的添加量为0.05~0.1mol/L。
3.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:步骤①的碱性条件为pH=8~14。
4.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:步骤②的气浮法中所用气体为空气、氧气、或含SO2、CO2、NO2的混合烟道气。
5.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:步骤②中的烘干温度为25~40℃。
6.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:离子液体的阳离子为烷基取代的咪唑阳离子、吡啶阳离子、季铵阳离子或季膦阳离子,阴离子为[BF4]-、[PF6]-、[CF3SO3]-、[Tf2N]-、[Ac]-、[SbF6]-、[FeCl4]-、[FeClBr3]-、[AsF6]- 、[C4F9SO3]-或[Co(CO)4]-。
7.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:步骤③中热解温度为70~400℃,热解时间为0.5~2h。
8.根据权利要求1所述的造纸黑液制备多孔碳基吸附剂方法,其特征在于:步骤③中的活化方式为高温水蒸气活化,活化温度为400~900℃,停留时间为1~5h。
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