CN113769719A - 木质素基超交联多孔树脂球及其制备方法和应用 - Google Patents
木质素基超交联多孔树脂球及其制备方法和应用 Download PDFInfo
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- CN113769719A CN113769719A CN202111141505.6A CN202111141505A CN113769719A CN 113769719 A CN113769719 A CN 113769719A CN 202111141505 A CN202111141505 A CN 202111141505A CN 113769719 A CN113769719 A CN 113769719A
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- lignin
- porous resin
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
本发明提供一种木质素基超交联多孔树脂球及其制备方法和应用,以木质素为原料,先后采用悬浮聚合及超交联聚合两步反应,制备了木质素基超交联多孔树脂球应用于染料吸附分离,在第一步中,木质素富含大量的酚羟基引入共聚物,得到极性可调的木质素基树脂球前体,第二步中,通过原位Friedel‑Crafts反应赋予聚合物超交联特性,从而制备出具有高比表面、孔隙丰富可调、具有选择性吸附特点的多孔木质素基树脂球,其对环境污染物吸附效果好,特别是小分子染料的吸附,染料去除率高,易回收,循环性能好。该木质素基超交联多孔树脂球制备简单,绿色环保,在污染物吸附领域中具有广阔的应用前景。
Description
技术领域
本发明属于生物质资源利用及生物质材料技术领域,具体涉及一种木质素基超交联多孔树脂球及其制备方法和应用。
背景技术
由于城市的快速发展、工业规模的扩大生产、能源的过度开发利用导致水污染问题愈发严重。然而地球上的淡水资源有限,开发绿色高效的水处理技术势在必行。纺织工业消耗的有机染料占世界染料消耗的60%,有10~25%的水溶性染料在染色过程中流失,2~20%的染料在染色后作为废水排放到水系统中。因此,如何经济有效地从工业废水中去除这些有毒的染料已成为人们关注的热点。吸附法被认为是一种替代传统的化学和生物相结合的方法来从水溶液中去除染料。各种吸附剂对染料的吸附被认为主要是通过π相互作用、氢键和静电相互作用进行的。沸石、木质纤维素基质、活性炭、石墨烯、和氧化石墨烯等材料已被研究,并显示对废水中的有机染料有不同的吸附活性。然而,低成本可再生的绿色生物质基吸附剂在该领域的应用还很少见,迫切需要进一步的研究。
木质素是一种高芳香低价值的生物质残渣,可用于化工、燃料和材料生产。由于木质素本身的可再生性、高碳含量以及酚醛功能化结构等特点,近年来木质素碳质多孔材料的研究得到了广泛的应用。然而,世界范围内可利用木质素的开发利用率仅为5%,如何用绿色化学方法开发木质素吸附剂,从而产生附加价值的过程仍有很大的机遇和挑战。
发明内容
本发明的目的在于提供木质素基超交联多孔树脂球及其制备方法和应用,旨在制得具有极性和微孔、介孔结构可调的木质素基树脂球。
具体技术方案为:
木质素基超交联多孔树脂球,由以下的制备方法所得制备方法,制备方法包括以下步骤:
步骤(1):将包含分散剂的水相及包含木质素、芳基乙烯类单体、交联剂和引发剂的油相混合进行自由基聚合反应,得到极性可调木质素基树脂球前体;所述的芳基乙烯类单体的芳基上带有能进行傅克烷基化和/或傅克酰基化反应的功能基团;
步骤(2):将木质素基树脂球前体在聚合物内进行原位Friedel-Crafts反应,从而得到所述具有孔结构可调和选择性吸附的木质素基超交联多孔树脂球。
目前木质素提取方法多种多样,加上木质素的定义不清晰导致提取纯度也没有统一标准,但很明确的是最终目的是为了木质素的高值化利用。本发明针对木质纤维绿色提取木质素,进行了的功能化修饰,采用悬浮聚合形成功能化及极性可调的木质素基树脂球前体,克服了传统超高交联树脂由于强疏水性导致需要用极性试剂预处理和水溶液中极性物质吸附量小的缺陷,合成的球状树脂可以简单高效的分离回收;结合原位Friedel-Crafts反应对前体树脂球进行结构内的芳环交联,在前体树脂球内原位构建刚性交联桥,实现木质素基树脂球具有丰富的孔结构,特别是填补了木质素基材料缺乏微孔的技术空白。
本发明发现通过极性和孔结构调控可以改善聚合物在吸附方面的物理、化学和选择性能,且合成的树脂球易分离。
本发明中,采用有机溶剂酸催化法预先将木质素从木质纤维中提取,通过悬浮聚合将木质素和所述的具有傅克反应功能基团的芳基乙烯类单体进行自由基聚合反应获得极性可调的木质素基树脂球前体,再结合前体树脂球结构内原位Friedel-Crafts反应,成功实现木质素基树脂球微孔孔结构构建、使其具有选择性吸附性能。
本发明中,基于所述的交联共聚,且在聚合物分子结构中原位修饰有Friedel-Crafts反应的功能基团,进一步配合后的Friedel-Crafts反应,实现聚合物分子内的刚性连接,改善聚合物的结构和活性基团的取向,最终改善材料在吸附方面的性能,例如改善材料的吸附率以及循环稳定性。
本发明一种优选的木质素基超交联多孔树脂球的制备方法,采用有机溶剂法从木质纤维中提取木质素后进行功能化修饰,通过悬浮聚合形成功能化及极性可调的木质素基树脂球前体,并结合原位Friedel-Crafts反应对前体树脂球进行结构内的芳环交联,在聚合物结构内原位构建刚性交联桥,实现木质素微球具有丰富的孔结构,将其作为吸附剂捕获环境中的污染物如有机染料等。具体操作步骤如下:
(1)、将绝干的木质纤维原料放入圆底烧瓶中,再加入乙醇和水的混合溶剂,2M酸催化下,在90℃油浴锅中反应3~10h,冷凝回流;自然冷却至室温,0.45um有机滤膜过滤,用乙醇和水的混合溶液洗涤得滤液;60℃旋转蒸发,待有沉淀析出即可停止,将旋转蒸发液迅速倒入冰水混合物中,进一步析出木质素;过滤,用纯水洗涤至中性,将固体放入真空冷冻干燥24h,获得固体即为有机木质素待用。
混合溶剂中的有机溶剂为乙醇、丙酮、二甲基亚砜、1,4-二氧六环、四氢呋喃中的至少一种。所述的酸为H2SO4、HCl、路易斯酸中的至少一种,优选HCl。
所述的酸为H2SO4、HCl、HNO3中的至少一种。
所述木质纤维、有机溶剂、水和酸的质量比为1~9:5~1:5~0.1:0.5,优选1:8:2:0.2。
所述提取温度范围为60~100℃,时间范围为3~10h,优选90℃,6~8h。
(2)、步骤(1)中获得的有机木质素通过超声充分溶于有机溶剂中,经过0.45um滤膜过滤得木质素有机溶液;木质素有机溶液中加入适量的芳基乙烯类单体、交联剂和引发剂作为油相,再配制含分散剂的水相,水相和油相混合搅拌,程序升温反应获得极性及孔结构可调的木质素基树脂球。
所述的交联剂为对二乙烯基苯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、二丙烯酸-1,4-丁二酯、N,N-亚甲基双丙烯酰胺,优选二乙烯基苯;
所述的引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化十二酰、过氧化叔戊酸叔丁酯,优选偶氮二异丁腈;
所述的自由基聚合反应的溶剂为乙酸乙酯、二甲基亚砜、乙醇、邻苯二甲醇,优选乙酸乙酯;其中,木质素与溶剂的质量比为1:10~1:100,优选1:50。
所述的水相中包含分散剂为聚乙烯醇、多元醇脂肪酸酯、碳酸镁、碳酸钙、磷酸盐、明胶、海藻胶、蛋白、纤维素衍生物、中的至少一种,优选聚乙烯醇,水相中分散剂质量浓度为5~15%。
所述水相和油相的体积比为10:1~2:1,优选9:1。
所述转速为200~600r/min,温度为程序升温0~3h为70~80℃,3~6h为80~90℃,2~10h为95℃,优选300r/min,程序升温为75℃保持3h,升温至75℃保持3h,再升温至95℃保持2h。
(3)、步骤(2)中获得的木质素基树脂球前体聚合物在溶剂中溶胀6-12h,升温至40~45℃后加入催化剂搅拌溶解,再升温至60~80℃反应6-12h,用40~50%乙醇和水溶液终止反应,获得木质素基超交联多孔树脂球。
所述木质素基树脂球前体溶剂为1,2-二氯乙烷、1,2-二氯甲烷、硝基苯,优选1,2-二氯乙烷。
所述木质素基树脂球前体和溶剂的质量比为1:5~1:20,优选1:10。
所述催化剂为AlCl3,FeCl3,SnCl4,ZnCl2等路易斯酸,催化剂用量与前体树脂球的质量比为1:5~3:2,优选催化剂FeCl3,催化剂用量1:1。
所述反应温度范围为40~85℃,反应时间范围为3~12h,优选80℃,10h。
本发明还提供了一种所述的制备方法制得的具有极性及孔结构可调的木质素基树脂球,其具有极性和微孔、介孔可调。
优选地,接触角可调范围95~65°;微孔含量为40~85%;介孔含量为15~60%;比表面积为500~1200m2/g。
本发明制得的具有极性及孔结构可调的木质素基树脂球的应用,将其用作吸附材料,用于脱除环境中的有害成分。例如,吸附水体中的有机染料,或者吸附气体中的挥发性有害成分。
所述的有害物质为小分子污染物,优选为CO2气体、重金属离子、有机染料中的至少一种;更优选为小分子有机染料。
有益效果:
本发明一种极性及孔结构可调的木质素基树脂球制备及其染料选择性吸附应用,通过从木质纤维中有机提取木质素和所述的特殊功能化的单体预先进行自由基聚合和超交联聚合反应,制备极性可调的木质素基前体聚合物,克服了传统超高交联树脂球由于强疏水性导致需要用极性试剂预处理和水溶液中极性物质吸附量小的缺陷,更好的适应多变的环境条件;再利用前体聚合物预先修饰的功能基团,在聚合物结构内进行原位Friedel-Crafts反应,原位构建刚性连接桥,并调控活性基团的长度和密度,如此可制备高比表面积、孔结构可调的木质素基多孔树脂球;研究发现,该制备方法获得的聚合物可在物理、化学等多种方面协同改善环境污染物吸附效果。例如,本发明所述的材料对对硝基苯酚的吸附量达248mg/g,且易分离脱附,去除率高达95%,可再生循环使用;其制备方法简单,条件温和,绿色环保,具有降低成本和环境兼容性,且能使工业废弃木质素得到资源化、高值化利用。
本发明制得的材料具有良好的化学和物理稳定性,其在具有良好选择性吸附的前提下,还具有优异的循环稳定性。
附图说明
图1为本发明的制备方法流程图;
图2a为实施例制备的木质素的实物图;
图2b为实施例制备的木质素基树脂球前体的实物图;
图2c为实施例制备的木质素基超交联多孔树脂球的实物图;
图3a为实施例制备的木质素的电镜图;
图3b为实施例制备的木质素基树脂球前体的电镜图;
图3c为实施例制备的木质素基超交联多孔树脂球的电镜图;
图4为实施例1~4接触角测量图;其中,由左至右,第一图为XP-1,接触角为86.2°;第二图为XP-2,接触角为77.9°;第三图为XP-3,接触角为67.2°;第四图为OL,接触角为64.6°;
图5为实施例制备的木质素基超交联多孔树脂球对氮气吸附-脱附等温线;
图6为实施例制备的不同木质素含量的木质素基超交联多孔树脂球(XF)对有机染料对硝基苯酚等温吸附测定;
图7为实施例制备的不同木质素含量的木质素基超交联多孔树脂球(XF)对有机染料对硝基苯酚和罗丹明B吸附对比实验;
图8为实施例制备的木质素基超交联多孔树脂球(XF)对有机染料选择性吸附实验;
图9为实施例制备的不同聚合方法合成的木质素基超交联聚合物对罗丹明B和对硝基苯的选择性吸附对比实验;
图10a实施例制备的XF聚合物的分离结果;
图10b为对比例OLHCP聚合物的分离结果。
具体实施方式
以下结合实施例旨在进一步说明本发明,而非限制本发明。
以下实施例的制备方法如图1所示。
实施例1
木质素的有机溶剂酸催化提取,取10g绝干酸爆杨木放入500mL圆底烧瓶中,再加入200mL乙醇和水(V:V=4:1)的混合溶剂,3.384mL HCl;放入90℃油浴锅中,反应5h,冷凝回流;自然冷却至室温,0.45um有机滤膜过滤,200mL乙醇和水的混合溶(V:V=4:1)液洗涤得滤液;60℃旋转蒸发,待有沉淀析出即可停止,将旋转蒸发液迅速倒入400mL冰水混合物中,进一步析出木质素;过滤,用纯水洗涤至中性(约500mL水),将固体放入真空冷冻干燥24h,获得固体即为有机溶木质素,如图2a所示。
实施例2
悬浮聚合制备木质素基树脂球前体,水相:90mL水+10mL 1%PVA升温至45℃;油相:0.25g有机木素溶于25mL乙酸乙酯,超声3min使其充分溶解,过滤得滤液;然后将4.0gVBC和1g DVB和0.1g AIBN引发剂和滤液混合加入水相中;升温至75℃反应3h,升温至85℃反应3h,再升温至95℃反应2h;停止反应冷却至室温,用乙醇和水交替洗涤至无色,60℃真空干燥一晚得木质素基树脂球前体,将其命名为XP-1。通过接触角测定呈现极性可调,如图4所示。
Friedel-Crafts反应制备木质素基超交联多孔树脂球,将3g前体加入30mL 1,2-二氯乙烷溶剂中充分溶胀10h;然后升温至45℃,加入0.9g无水FeCl3,搅拌30min至完全溶解;接着升温至80℃反应10h;等体积50%乙醇水溶液终止反应,2mol/L HCl和乙醇交替洗涤至无色后用纯水洗至中性;乙醇抽提24h,60℃真空干燥一晚得木质素基超交联多孔树脂球,将其命名为XF-1。测定其比表面积为969m2/g,孔结构测定,呈现微孔、介孔多孔结构,如图5所示,微孔含量(75%)、介孔含量(25%)。
木质素基超交联多孔树脂球(XF)对染料吸附性能测定,称取20mg XF分别放入浓度为500mg/L对硝基苯酚20mL溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF-1对对硝基苯酚的吸附量为213.9mg/g,如图6所示。
实施例3
悬浮聚合制备木质素基树脂球前体,水相:90mL水+10mL 1%PVA升温至45℃;油相:0.5g有机木素溶于25mL乙酸乙酯,超声3min使其充分溶解,过滤得滤液;然后将4.0gVBC和1g DVB和0.1g AIBN引发剂和滤液混合加入水相中;升温至75℃反应3h,升温至85℃反应3h,再升温至95℃反应2h;停止反应冷却至室温,用乙醇和水交替洗涤至无色,60℃真空干燥一晚得木质素基树脂球前体,如图2b所示,将其命名为XP-2。通过接触角测定,如图4所示呈现极性可调。
Friedel-Crafts反应制备木质素基超交联多孔树脂球,将3g前体加入30mL 1,2-二氯乙烷溶剂中充分溶胀10h;然后升温至45℃,加入0.9g无水FeCl3,搅拌30min至完全溶解;接着升温至80℃反应10h;等体积50%乙醇水溶液终止反应,2mol/L HCl和乙醇交替洗涤至无色后用纯水洗至中性;乙醇抽提24h,60℃真空干燥一晚得木质素基超交联多孔树脂球,如图2c所示,将其命名为XF-2。测定其比表面积为793m2/g,孔结构测定,呈现微孔、介孔多孔结构,如图5所示,微孔含量(80%)、介孔含量(20%)。
木质素、木质素基树脂球前体、木质素基超交联多孔树脂球的电镜图分别如图3a到图3c。
木质素基超交联多孔树脂球(XF)对染料吸附性能测定,称取20mg XF-2分别放入浓度为500mg/L对硝基苯酚20mL溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF-2对对硝基苯酚的吸附量为155.8mg/g,如图6所示。
实施例4
悬浮聚合制备木质素基树脂球前体,水相:90mL水+10mL 1%PVA升温至45℃;油相:0.75g有机木素溶于25mL乙酸乙酯,超声3min使其充分溶解,过滤得滤液;然后将4.0gVBC和1g DVB和0.1g AIBN引发剂和滤液混合加入水相中;升温至75℃反应3h,升温至85℃反应3h,再升温至95℃反应2h;停止反应冷却至室温,用乙醇和水交替洗涤至无色,60℃真空干燥一晚得木质素基树脂球前体,将其命名为XP-3。通过接触角测定,如图4所示,呈现极性可调。
Friedel-Crafts反应制备木质素基超交联多孔树脂球,将3g前体加入30mL 1,2-二氯乙烷溶剂中充分溶胀10h;然后升温至45℃,加入0.9g无水FeCl3,搅拌30min至完全溶解;接着升温至80℃反应10h;等体积50%乙醇水溶液终止反应,2mol/L HCl和乙醇交替洗涤至无色后用纯水洗至中性;乙醇抽提24h,60℃真空干燥一晚得木质素基超交联多孔树脂球,将其命名为XF-3。测定其比表面积为662m2/g,孔结构测定,呈现微孔、介孔多孔结构,如图5所示,微孔含量(83%)、介孔含量(17%。
木质素基超交联多孔树脂球(XF)对染料吸附性能测定,称取20mg XF-3分别放入浓度为500mg/L对硝基苯酚20mL溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF-3对对硝基苯酚的吸附量为130.3mg/g,如图5所示。
实施例5
木质素基超交联多孔树脂球(XF)对染料吸附性能测定,称取20mg XF-1、XF-2、XF-3分别放入20mL浓度为500mg/L对硝基苯酚、罗丹明B溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF-1、XF-2、XF-3对对硝基苯酚吸附量为223.9、185.2、130.3mg/g,罗丹明B的吸附量为86.2、76.5、72.9mg/g,如图7所示。
实施例6
木质素基超交联多孔树脂球(XF)对染料选择性吸附性能测定,称取20mg XF-2分别放入20mL浓度为500mg/L对硝基苯酚(139.11)、甲基红(269.30)、亚甲基蓝(319.86)、罗丹明B(479.01)、溴甲酚绿(698.05)溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF-2对不同分子量大小的染料的吸附量依次为244.4、70.4、34.3、86.2、138.3mg/g,如图8所示。
对比例1
不同聚合方法合成的聚合物对罗丹明B和对硝基苯的选择性吸附比较,分别采用悬浮聚合法和溶液聚合法制备木质基超交联聚合物,其中木质素加入量均为0.5g,获得聚合物分别命名为XF和OLHCP,比较不同聚合物制备方法对不同分子量大小的染料吸附,称取20mg XF和OLHCP分别放入20mL浓度为500mg/L对硝基苯酚(139.11)、甲基红(269.30)、亚甲基蓝(319.86)、罗丹明B(479.01)、溴甲酚绿(698.05)溶液中,在30℃,150r/min小瓶中吸附24h,即达到吸附平衡后紫外分光光度计测定含量变化,计算出XF和OLHCP对不同分子量大小的染料的吸附量,如图9所示,可明显看出XF对小分子染料具有选择性吸附而OLHCP对大分子染料具有选择性吸附。
对比例2
不同聚合方法合成聚合物的分离比较,分别采用悬浮聚合法和溶液聚合法制备木质基超交联聚合物,其中木质素加入量均为0.5g,获得聚合物分别命名为XF和OLHCP,比较木质基超交联聚合物在溶液中分离的难易程度,悬浮聚合获得的微球静置1h即可固液分离,而溶液聚合获得的粉末静置24h后任然呈浑浊状态,如图10a和图10b所示,需要高速离心进行分离。
Claims (9)
1.一种木质素基超交联多孔树脂球的制备方法,其特征在于,包括以下步骤:
步骤(1):通过悬浮聚合法将包含分散剂的水相及包含木质素、芳基乙烯类单体、交联剂、致孔剂和引发剂的油相混合进行自由基聚合反应,得到极性可调的木质素基树脂球前体;
步骤(2):将木质素基树脂球前体进行原位Friedel-Crafts反应,从而得到木质素基超交联多孔树脂球。
2.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,所述的水相中包含的分散剂为聚乙烯醇、多元醇脂肪酸酯、碳酸镁、碳酸钙、磷酸盐、明胶、海藻胶、蛋白、纤维素衍生物中的至少一种;
分散剂占水相总质量的5%~15%。
3.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,所述的木质素为混合溶剂在酸催化作用下提取的有机溶木质素;
提取有机溶木质素的混合溶剂中木质纤维、有机溶剂、水和酸的质量比为1~9:5~1:5~0.1:0.5;有机溶剂为乙醇、丙酮、二甲基亚砜、1,4-二氧六环、四氢呋喃中的至少一种;
酸为H2SO4、HCl、HNO3中的至少一种;
提取温度为60~100℃,时间为3~10h。
4.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,油相中木质素、芳基乙烯类单体、致孔剂、交联剂、引发剂的质量比为1~5:1~10:2~10:1~5:0.1~0.3。
5.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,水相和油相的体积比为10:1~2:1。
6.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,步骤(1)中,悬浮聚合法中,悬浮聚合的转速为200~600r/min,温度为程序升温:0~3h为65~75℃,3~6h为80~90℃,2~10h为95℃。
7.根据权利要求1所述的木质素基超交联多孔树脂球的制备方法,其特征在于,所述的原位Friedel-Crafts反应是在木质素基树脂球前体内部发生,催化剂为AlCl3、FeCl3、SnCl4、ZnCl2中的至少一种。
8.一种木质素基超交联多孔树脂球,其特征在于,由权利要求1~7任一项所述的制备方法制得。
9.根据权利要求8所述的木质素基超交联多孔树脂球的应用,其特征在于,用于脱除水中的有机染料。
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