CN107890871B - 木质素磺酸盐催化解聚制取芳香基化合物的方法 - Google Patents
木质素磺酸盐催化解聚制取芳香基化合物的方法 Download PDFInfo
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- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 40
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 53
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Abstract
本发明涉及的是木质素磺酸盐催化解聚制取芳香基化合物的方法,这种木质素磺酸盐催化解聚制取芳香基化合物的方法:一、纳米层状MgFe水滑石复合金属氧化物固体碱的制备;二、利用纳米层状MgFe水滑石复合金属氧化物固体碱催化解聚木质素磺酸盐制取芳香基化合物;三、解聚后离心分离出反应后残渣和复合金属氧化物,得到液相粗产品;四、液相粗产品萃取分离,通过旋转蒸发仪除去萃取剂,得到纯液相产物‑芳香基化合物。本发明制备的MgFe固体碱催化剂解聚催化木质素磺酸盐,解决了传统方法中木质素磺酸盐解聚转化率低、催化剂与液体产物不易分离、催化剂不能重复利用等问题,木质素磺酸盐解聚率达90‑98%。液体产物收率达90%以上。
Description
技术领域
本发明涉及生物质废弃物资源化和高值化利用领域,具体涉及一种利用纳米层状MgFe水滑石催化解聚木质素磺酸盐制取芳香基化合物的方法。
背景技术
木质素是自然界中除纤维素外第二大生物质资源,是自然界中唯一可直接提供芳香基化合物的可再生能源。造纸过程中将木质素和少部分的半纤维素脱除,剩下的就是造纸用的纸浆,再对废液进行化工处理,分离出来的就是木质素磺酸盐,主要阳离子有钠离子、钙离子、铵根离子等。木质素磺酸盐是亚硫酸法制浆造纸废液回收提取的工业原料,用途广泛,可用于作减水剂、粘合剂、分散剂、精炼助剂、选矿剂等,均为低附加值利用。从结构上来说,木质素是由愈创木基、紫丁香基、对羟基苯基为结构单元,通过C-C、C-O-C键连接而成的具有三维网状结构的无定型高聚物,在其芳香结构侧链含有大量活性含氧基团(如酚羟基),因此通过解聚断裂木质素聚合单元之间的连接键可以生产高附加值化学品和化工原料,有利于缓解能源危机。在化石能源短缺日益严重的今天,有效利用生物质能源对我国资源可持续发展具有重要的意义。
木质素磺酸盐资源化和高值化利用的关键点在于解聚木质素制取小分子芳香基化合物,化学法是目前木质素解聚转化利用的有效途径之一,主要有高温热裂解法、氢解法、氧化法、水解法等。高温热裂解法能耗较高,结焦严重;氢解法需要额外的氢源,反应条件苛刻,成本较高;氧化法需要氧化剂,部分氧化剂毒性较大;水解法反应温度较低,液相产物产率高,单酚类产物选择性较好,该法有望成为一种最具前景的木质素高效催化转化途径。木质素催化水解包括酸水解和碱水解法,碱水解木质素催化剂不会腐蚀反应装置,因此应用较为广泛,均相碱催化解聚木质素虽然转化率高,但是均相碱不易与产物分离,大量的碱液无法回收重复利用,增加了成本且污染了环境。与均相碱一样固体碱同样具有碱活性位,而且反应结束后固体碱易与产物分离,可重复使用,因此使用固体碱代替均相碱成为解决这一问题的有效方法。
水滑石固体碱是一种具有层状结构的阴离子化合物,为六方晶系,其结构类似于水镁石,水镁石的结构单元为MgO6八面体,其中氧是以羟基形式存在。水滑石可以看作是与Mg2+相近的Al3+将其替代进入八面体结构中形成的水镁石的衍生物。水滑石是一类可调控的无机功能材料,层板阳离子可由与Mg2+半径接近的离子,如Ni2+、Fe2+、Co2+、Fe3+等代替。水滑石层板金属阳离子和层间阴离子具有可调控性,因而可以将具有不催化活性的金属组分***到水滑石层板中或将不同阴离子引入到水滑石层间制备功能性层状材料。水滑石最直观的性质为碱性,其层板上及层间含有OH-,其强碱性体现在其焙烧后的复合金属氧化物(LDO),其含有的O2-显现出强碱性。由于其层板组成具有多样性,层间阴离子具有可交换性,因此其在碱催化领域具有较好的前景。
发明内容
本发明的一个目的是提供木质素磺酸盐催化解聚制取芳香基化合物的方法,这种木质素磺酸盐催化解聚制取芳香基化合物的方法用于解决目前解聚木质素磺酸盐反应条件苛刻、液相产物收率低、催化剂不能重复利用等问题。
本发明解决其技术问题所采用的技术方案是:这种木质素磺酸盐催化解聚制取芳香基化合物的方法:
一、纳米层状MgFe水滑石复合金属氧化物固体碱的制备:
(1)分别配制浓度为0.05-2mol/L的Mg(NO3)2溶液、Fe(NO3)3溶液,使 Mg/Fe摩尔比为1:10-10:1;
(2)将上述Mg(NO3)2溶液、Fe(NO3)3溶液搅拌混合均匀,逐滴滴加1.0-3.0mol/L的NaOH溶液,使得混合溶液的pH在9-11为止;
(3)向上述混合溶液中添加空间位阻剂,添加量为溶液总质量的0.1-20%,空间位阻剂为乙二醇、丙三醇、环己醇、乙醇胺、二乙醇胺、三乙醇胺、氨甲基丙醇、聚乙烯醇、聚乙烯吡咯烷酮等中的一种或几种;
(4)进行分段晶化合成, 140℃-220℃晶化0.5h-6h,然后在70℃-120℃水热合成12h-36h;
(5)用去离子水洗涤并离心分离,干燥,得到硝酸根型纳米层状MgFe水滑石;
(6)将得到的纳米层状MgFe水滑石在500-650℃焙烧3-12h得到纳米层状MgFe水滑石复合金属氧化物固体碱;
二、利用纳米层状MgFe水滑石复合金属氧化物固体碱催化解聚木质素磺酸盐制取芳香基化合物;
三、解聚后离心分离出反应后残渣和纳米层状MgFe水滑石复合金属氧化物固体碱,得到液相粗产品;
四、液相粗产品萃取分离,通过旋转蒸发仪除去萃取剂,得到纯液相产物-芳香基化合物。
上述方案中木质素磺酸盐为木质素磺酸钙、木质素磺酸钠、木质素磺酸铵中的一种或两种。
上述方案中利用纳米层状MgFe水滑石复合金属氧化物固体碱催化解聚木质素磺酸盐制取芳香基化合物的方法:
(1)将木质素磺酸盐与纳米层状MgFe水滑石复合金属氧化物固体碱加入到乙醇水溶液中,木质素磺酸盐与纳米层状MgFe水滑石复合金属氧化物固体碱质量比为1:10-10:1,液固比为240:1-10:1 mL/g,乙醇体积浓度为10-75%;
(2)反应前采用N2吹扫10min以除去反应体系中O2;
(3)反应在高压反应釜中进行,反应温度为200-350℃,反应时间为1-24h。
上述方案中纳米层状MgFe水滑石复合金属氧化物固体碱催化的作用下,木质素磺酸盐解聚率达90-98%。
上述方案中芳香基化合物产物的收率达90%以上,芳香基化合物产物包括芳烃类、苯酚类、愈创木酚类、紫丁香基类、邻苯二酚类、香草醛类和甲氧基芳香类化合物。
上述方案中反应后的纳米层状MgFe水滑石复合金属氧化物固体碱经分离,在空气气氛下, 500-650oC焙烧4-12h,实现再生,再生后的催化剂循环使用。
本发明具有以下有益效果:
1、本发明提供了一种利用纳米层状MgFe水滑石催化木质素磺酸盐制取芳香基化合物的方法。开辟了木质素磺酸盐生产芳香基化学品的新途径,有利于实现造纸废液中木质素磺酸盐废弃物的资源化和高值化利用。
2、本发明MgFe水滑石合成方法简单,通过对水滑石晶粒尺寸和金属组成的调控可以提高木质素磺酸盐的催化活性和芳香基化合物产物的收率。
3、本发明制备的MgFe固体碱催化剂解聚催化木质素磺酸盐,解决了传统方法中木质素磺酸盐解聚转化率低、催化剂与液体产物不易分离、催化剂不能重复利用等问题,本发明木质素磺酸盐解聚率可达90-98%。液体产物收率可达90%以上。
4、本发明通过解聚获得芳香基化合物产物包括:芳烃类、苯酚类、愈创木酚类、紫丁香基类、邻苯二酚类、香草醛类和甲氧基苯类化合物等高附加值化学品。
附图说明
图1为本发明实施例1中MgFe水滑石焙烧后复合金属氧化物的扫描电镜照片。
图2为本发明实施例3中MgFe水滑石焙烧后复合金属氧化物的扫描电镜照片。
具体实施方式
下面结合附图对本发明作进一步的说明:
实施例1
称取2.0512g的Mg (NO3)2•6H2O和1.01g的 Fe(NO3)3•9H2O(Mg/Fe=3.2:1)溶于60mL去离子水中。逐滴滴加3mol/L的NaOH溶液直至混合溶液pH达到10为止,添加溶液总质量3%的三乙醇胺,在200r/min下搅拌30min,并将混合溶液转移到水热反应釜中于180℃晶化4h,然后在100℃继续晶化(水热合成)24h;取出反应釜中内混合物,用去离子水洗涤并离心分离,干燥,得到纳米层状MgFe水滑石。将得到的水滑石放入马弗炉中在600℃下焙烧6h得到纳米层状MgFe水滑石复合金属氧化物固体碱。
称取0.25g 上述纳米层状MgFe水滑石复合金属氧化物固体碱和0.5g木质素磺酸钠放入高压反应釜中,添加60mL乙醇水溶液,乙醇体积浓度为50%,液固比为80:1;反应前用N2吹扫10min以除去反应器中O2,在270℃条件下反应4h。反应结束后将混合物经离心进行固液分离,得到的液体用乙酸乙酯进行3-5次萃取,分离出的萃取液通过无水硫酸镁进一步除水,然后通过旋转蒸发仪分离出目的产物芳香基化合物。
通过称量反应后剩余的木质素磺酸钠质量,计算出木质素磺酸钠转化率为95%,通过收集液体产物,计算出液体产物收率为91.2%,通过色质联用分析液体产物组成,其主要包括:芳烃类(12.4%)、苯酚类(26%)、愈创木酚类(7.3%)、紫丁香基类(13.4%)、邻苯二酚类(11.6%)、香草醛类(16.7%)和甲氧基苯类化合物(12.6%)。
实施例2
称取2.0512g的Mg (NO3)2•6H2O和0.404g的 Fe(NO3)3•9H2O(Mg/Fe=8:1)溶于60 mL去离子水中。逐滴滴加2mol/L的NaOH溶液直至混合溶液pH达到10.5为止,添加溶液总质量5%的聚乙烯吡咯烷酮,在200r/min下搅拌30min,并将混合溶液转移到水热反应釜中于160℃晶化6h,然后在90℃继续晶化(水热合成)24h;取出反应釜中内混合物,用去离子水洗涤并离心分离,干燥,得到纳米层状MgFe水滑石。将得到的水滑石放入马弗炉中在600℃下焙烧6h得到纳米层状MgFe水滑石复合金属氧化物固体碱。
称取0.5g 上述纳米层状MgFe水滑石复合金属氧化物固体碱和0.5g木质素磺酸钙放入高压反应釜中,添加60mL乙醇水溶液,乙醇体积浓度为50%,液固比为60:1;反应前用N2吹扫10min以除去反应器中O2,在300℃条件下反应6h。反应结束后将混合物经离心进行固液分离,得到的液体用乙酸乙酯进行3-5次萃取,分离出的萃取液通过无水硫酸镁进一步除水,然后通过旋转蒸发仪分离出目的产物芳香基化合物。
通过称量反应后剩余的木质素磺酸钙质量,计算出木质素磺酸钙转化率为96.4%,通过收集液体产物,计算出液体产物收率为92.6%,通过色质联用分析液体产物组成,其主要包括:芳烃类(10.4%)、苯酚类(28.1%)、愈创木酚类(7.6%)、紫丁香基类(13.7%)、邻苯二酚类(10.3%)、香草醛类(18.5%)和甲氧基苯类化合物(11.4%)。
实施例3
称取2.0512g的Mg (NO3)2•6H2O和0.808g的 Fe(NO3)3•9H2O(Mg/Fe=4:1)溶于80 mL去离子水中。逐滴滴加1.5mol/L的NaOH溶液直至混合溶液pH达到9.5为止,添加溶液总质量3%的环己醇,在200r/min下搅拌30min,并将混合溶液转移到水热反应釜中于180℃晶化6h,然后在90℃继续晶化(水热合成)24h;取出反应釜中内混合物,用去离子水洗涤并离心分离,干燥,得到纳米层状MgFe水滑石。将得到的水滑石放入马弗炉中在600℃下焙烧6h得到纳米层状MgFe水滑石复合金属氧化物固体碱。
称取0.75g 上述纳米层状MgFe水滑石复合金属氧化物固体碱和0.25g木质素磺酸钙放入高压反应釜中,添加50mL乙醇水溶液,乙醇体积浓度为50%,液固比为50:1;反应前用N2吹扫10min以除去反应器中O2,在280℃条件下反应8h。反应结束后将混合物经离心进行固液分离,得到的液体用乙酸乙酯进行3-5次萃取,分离出的萃取液通过无水硫酸镁进一步除水,然后通过旋转蒸发仪分离出目的产物芳香基化合物。
通过称量反应后剩余的木质素磺酸钙质量,计算出木质素磺酸钙转化率为97.3%,通过收集液体产物,计算出液体产物收率为93.1%,通过色质联用分析液体产物组成,其主要包括:芳烃类(14.2%)、苯酚类(20.3%)、愈创木酚类(9.6%)、紫丁香基类(13.5%)、邻苯二酚类(10.8%)、香草醛类(17.7%)和甲氧基苯类化合物(13.9%)。
实施例4
称取2.0512g的Mg (NO3)2•6H2O和3.232g的 Fe(NO3)3•9H2O(Mg/Fe=1:1)溶于60 mL去离子水中。逐滴滴加3mol/L的NaOH溶液直至混合溶液pH达到10为止,添加溶液总质量5%的聚乙烯醇,在200r/min下搅拌30min,并将混合溶液转移到水热反应釜中于200℃晶化2h,然后在90℃继续晶化(水热合成)12h;取出反应釜中内混合物,用去离子水洗涤并离心分离,干燥,得到纳米层状MgFe水滑石。将得到的水滑石放入马弗炉中在600℃下焙烧4h得到纳米层状MgFe水滑石复合金属氧化物固体碱。
称取0.75g 上述纳米层状MgFe水滑石复合金属氧化物固体碱和0.75g木质素磺酸钙放入高压反应釜中,添加60mL乙醇水溶液,乙醇体积浓度为50%,液固比为40:1;反应前用N2吹扫10min以除去反应器中O2,在320℃条件下反应4h。反应结束后将混合物经离心进行固液分离,得到的液体用乙酸乙酯进行3-5次萃取,分离出的萃取液通过无水硫酸镁进一步除水,然后通过旋转蒸发仪分离出目的产物芳香基化合物。
通过称量反应后剩余的木质素磺酸钙质量,计算出木质素磺酸钙转化率为97.8%,通过收集液体产物,计算出液体产物收率为94.3%,通过色质联用分析液体产物组成,其主要包括:芳烃类(20.4%)、苯酚类(19.1%)、愈创木酚类(6.4%)、紫丁香基类(10.2%)、邻苯二酚类(8.6%)、香草醛类(20.5%)和甲氧基苯类化合物(14.8%)。
Claims (6)
1.一种木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:
一、纳米层状MgFe水滑石复合金属氧化物固体碱的制备:
(1)分别配制浓度为0.05-2mol/L的Mg(NO3)2溶液、Fe(NO3)3溶液,使 Mg/Fe摩尔比为1:10-10:1;
(2)将上述Mg(NO3)2溶液、Fe(NO3)3溶液搅拌混合均匀,逐滴滴加1.0-3.0mol/L的NaOH溶液,使得混合溶液的pH在9-11为止;
(3)向上述混合溶液中添加空间位阻剂,添加量为溶液总质量的0.1-20%,空间位阻剂为乙二醇、丙三醇、环己醇、乙醇胺、二乙醇胺、三乙醇胺、氨甲基丙醇、聚乙烯醇、聚乙烯吡咯烷酮中的一种或几种;
(4)进行分段晶化合成, 140℃-220℃晶化0.5h-6h,然后在70℃-120℃水热合成12h-36h;
(5)用去离子水洗涤并离心分离,干燥,得到硝酸根型纳米层状MgFe水滑石;
(6)将得到的纳米层状MgFe水滑石在500-650℃焙烧3-12h得到纳米层状MgFe水滑石复合金属氧化物固体碱;
二、利用纳米层状MgFe水滑石复合金属氧化物固体碱催化解聚木质素磺酸盐制取芳香基化合物;
三、解聚后离心分离出反应后残渣和纳米层状MgFe水滑石复合金属氧化物固体碱,得到液相粗产品;
四、液相粗产品萃取分离,通过旋转蒸发仪除去萃取剂,得到纯液相产物-芳香基化合物。
2.根据权利要求1所述的木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:所述的木质素磺酸盐为木质素磺酸钙、木质素磺酸钠、木质素磺酸铵中的一种或两种。
3.根据权利要求2所述的木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:所述的利用纳米层状MgFe水滑石复合金属氧化物固体碱催化解聚木质素磺酸盐制取芳香基化合物的方法:
(1)将木质素磺酸盐与纳米层状MgFe水滑石复合金属氧化物固体碱加入到乙醇水溶液中,木质素磺酸盐与纳米层状MgFe水滑石复合金属氧化物固体碱质量比为1:10-10:1,液固比为240:1-10:1 mL/g,乙醇体积浓度为10-75%;
(2)反应前采用N2吹扫10min以除去反应体系中O2;
(3)反应在高压反应釜中进行,反应温度为200-350℃,反应时间为1-24h。
4.根据权利要求3所述的木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:所述的纳米层状MgFe水滑石复合金属氧化物固体碱催化的作用下,木质素磺酸盐解聚率达90-98%。
5.根据权利要求4所述的木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:所述的芳香基化合物产物的收率达90%以上,芳香基化合物产物包括芳烃类、苯酚类、愈创木酚类、紫丁香基类、邻苯二酚类、香草醛类和甲氧基芳香类化合物。
6.根据权利要求5所述的木质素磺酸盐催化解聚制取芳香基化合物的方法,其特征在于:所述的反应后的纳米层状MgFe水滑石复合金属氧化物固体碱经分离,在空气气氛下,500-650oC焙烧4-12h,实现再生,再生后的催化剂循环使用。
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