CN115445588A - 生物质基多孔碳复合材料及制备与在co2吸附中的应用 - Google Patents
生物质基多孔碳复合材料及制备与在co2吸附中的应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000002028 Biomass Substances 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000004537 pulping Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 26
- 229920005610 lignin Polymers 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
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- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
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- 238000010000 carbonizing Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种生物质基多孔碳复合材料及制备与在CO2吸附中的应用,生物质基多孔碳复合材料以制浆造纸黑液固形物为前驱体,通过电弧处理后得到,具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种,所述多孔碳结构以所述前驱体中的木质素为碳源,以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂,受电弧热炭化并自活化后得到,所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。还涉及一种生物质基多孔碳复合材料在CO2吸附中的应用。本发明实现了制浆造纸黑液全利用,获得兼具CO2吸附物理位点和化学位点的高性能多孔碳复合材料,避免从黑液中分离、提取、纯化木质素的步骤及成本。
Description
技术领域
本发明涉及碳基复合材料,尤其是一种生物质基多孔碳复合材料及制备与在CO2吸附中的应用。
背景技术
利用可再生的生物质资源制备高品质生物炭是现如今的发展趋势和研究热点,生物炭一般通过热解炭化和水热炭化两种方法制备得到,生物质水热炭的炭化程度不及热解炭,一般只能应用于如水体污染物吸附剂等底端应用场合中,高端应用往往需要二次热解炭化。由于生物质的特征属性,其在炭化过程中一般需要借助模板剂造孔,所得炭化产物还需进一步活化,以获得高端应用所需的性能。总体而言,生物质炭化存在工艺过程复杂、能耗高、副产物多(VOC、有机废水等)、成本高、产品需进一步精制等问题,严重制约了其规模化生产与应用。
木质素是木质纤维类生物质的三大组成之一,其碳含量高,且丰富的芳香结构使得其更易制备高性能生物炭,利用工业木质素为原料制备生物炭能同步实现工业废弃物的无害化处理与高值化利用,意义重大。
现有技术中,木质素基生物炭大多以纯化的工业木质素为原料,通过添加模板剂、活化剂制备得到(期刊论文ACS Sustainable Chemistry&Engineering 6(2018)10454-10462、期刊论文ChemSusChem 8(2015)428-432、学位论文“模板法制备木质素基中孔碳材料及电化学性能研究[D],中国林业科学研究院,2018”、学位论文“造纸黑液木质素活性炭的制备、表征及吸附应用[D],山东大学,2018”、学位论文“以木质素为碳源介孔碳及其复合材料制备和电化学中的应用[D],浙江工业大学,2015”、专利ZL201210207757.9、专利ZL201811376052.3等),忽视了工业木质素的来源问题,避开了从制浆造纸黑液中提取、纯化木质素的成本及使用化学药剂带来的环境负担。专利CN202010522079.X、专利CN201610697874.6和专利ZL201210207757.9虽然提及了黑液木质素多孔碳,但也只是以制浆造纸黑液为原材料,实质还是先分离得到木质素,再进行后续的多孔碳制备。虽然,木质素是制浆造纸黑液的主要固形物成分,但制浆造纸黑液固形物中还包含其他有机质(碳水化合物降解物)和无机成分,现有的木质素多孔碳制备都忽略了对制浆造纸黑液的全组分直接利用。
CO2在多孔碳表面的吸附得益于其比表面积和孔体积,即主要利用多孔碳中的微孔和介孔进行物理吸附,通过调控多孔碳的制备工艺可以获得更多的微孔和介孔结构,进而提高CO2的吸附量,但单纯的物理吸附存在吸附瓶颈、难以大幅突破。为进一步增加多孔碳对CO2的吸附量,通常在多孔碳中引入杂原子(S、N、P等)创造碱性位点,或与其他碱性材料组合成复合材料,使CO2更易吸附在多孔碳的表面;然而这些额外的试剂和材料无疑增加了多孔碳吸附CO2的成本。
发明内容
针对现有技术的不足,本发明提供一种生物质基多孔碳复合材料及制备与在CO2吸附中的应用,目的是实现制浆造纸黑液全利用,获得兼具CO2吸附物理位点和化学位点的高性能多孔碳复合材料,避免从黑液中分离、提取、纯化木质素的步骤及成本。
本发明采用的技术方案如下:
本发明提供了一种生物质基多孔碳复合材料,以制浆造纸黑液固形物为前驱体,通过电弧处理后得到,具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种,所述多孔碳结构以所述前驱体中的木质素为碳源,以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂,受电弧热炭化并自活化后得到,所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
所述多孔碳结构可通过改变炭化工况进行调控。
本发明还提供了一种所述的生物质基多孔碳复合材料的制备方法,包括:
将制浆造纸黑液干燥成黑液固形物;
在惰性气体保护下,电弧处理所述黑液固形物,得到固体产物;
将所述固体产物研磨,即得生物质基多孔碳复合材料。
电弧处理过程中电弧电流为10-1000A,处理时间为1s-10min。
所述将制浆造纸黑液干燥成黑液固形物,包括:
将制浆造纸黑液搅拌均匀,在搅拌状态下将制浆造纸黑液浸入液氮中,使制浆造纸黑液快速冷冻,然后采用冷冻干燥法进行干燥,获得黑液固形物。
所述制浆造纸黑液为烧碱法制浆黑液、烧碱-蒽醌法制浆黑液、硫酸盐法制浆黑液、有机溶剂法制浆黑液、化学机械法制浆黑液、纸浆洗涤所得黑液中的至少一种。
所述制浆造纸黑液为实验室制浆黑液、制浆厂稀黑液、制浆厂浓黑液中的至少一种。
本发明还提供一种所述的生物质基多孔碳复合材料在CO2吸附中的应用。
本发明的有益效果如下:
本发明利用电弧产生的高温区实现生物质炭化,相比于传统的热解炭化和水热炭化法相比,具有能耗低、效率高、能极快速实现生物质炭化等优势,且工艺灵活、操作简单、设备占地面积小,非常适用于规模化生产。
本发明以制浆造纸黑液固形物全组分为原料,一步炭化即得高性能多孔碳复合材料,区别于从黑液中分离、提取、纯化得到木质素,再添加模板剂、活化剂等实现炭化造孔的传统方法,工艺路线短、操作简单。
本发明利用黑液固形物中原有的氢氧化钠、钠盐、寡糖等作为木质素炭化造孔的模板剂和活化剂及CO2吸附的碱性物质来源,无需额外添加模板剂和活化剂及其他碱性物种和碱性材料,成本低、经济效益高。
本发明所得多孔碳复合材料兼具CO2物理吸附的多孔结构及CO2化学吸附的碱性物种,无需二次处理,能大幅提高CO2吸附量。且多孔碳孔隙结构发达,以微孔和介孔为主,具有高比表面积和孔容,富含表面氧官能团,为制浆造纸黑液的高值化利用提供了新的思路,突破了传统焚烧处理法的局限。
本发明在均匀搅拌状态下快速冷冻,能使有机物和无机物混合均匀,便于后期炭化时均匀造孔,且冷冻产生的冰晶也具有模板的作用,使获得的固形物疏松多孔,更有益于终端多孔碳结构的形成。
本发明的其它特征和优点将在随后的说明书中阐述,并且,部分地从说明书中变得显而易见,或者通过实施本发明而了解。
附图说明
图1是本发明实施例3所得生物质基多孔碳复合材料在0℃时的CO2吸附曲线。
图2是本发明实施例3所得生物质基多孔碳复合材料的氮气吸脱附曲线。
具体实施方式
以下结合附图说明本发明的具体实施方式。
本申请提供一种生物质基多孔碳复合材料,以制浆造纸黑液固形物为前驱体,通过电弧处理后得到,具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种,所述多孔碳结构以所述前驱体中的木质素为碳源,以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂,受电弧热炭化并自活化得到,所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
所述多孔碳结构可通过改变炭化工况进行调控,例如炭化时长、电弧电流等。
本申请还提供一种生物质基多孔碳复合材料的制备方法,包括:
将制浆造纸黑液干燥成黑液固形物;
在惰性气体保护下,电弧处理所述黑液固形物,得到固体产物;
将所述固体产物研磨,即得生物质基多孔碳复合材料。
其中,电弧处理过程中电弧电流为10-1000A,处理的时间为1s-10min。
其中,所述将制浆造纸黑液干燥成黑液固形物,包括:
将制浆造纸黑液搅拌均匀,在搅拌状态下将制浆造纸黑液浸入液氮中,使制浆造纸黑液快速冷冻,然后采用冷冻干燥法进行干燥,获得黑液固形物。
本申请还提供一种生物质基多孔碳复合材料在CO2吸附中的应用。
本申请以制浆造纸黑液固形物为前驱体、通过电弧一步炭化获得用于CO2吸附的多孔碳复合材料,避免了从黑液中分离、提取、纯化木质素的步骤及成本,实现了制浆造纸黑液全利用,获得的多孔碳复合材料兼具CO2吸附物理位点和化学位点,性能优异。
以下以具体实施例进一步说明本申请生物质基多孔碳复合材料的制备方法的技术方案。
实施例1:
以制浆厂硫酸盐法制浆浓黑液为原料,采用冷冻干燥法将其制成黑液固形物,而后在二氧化碳氛围下于10A电弧区炭化10min,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为11.05mmol/g。
实施例2:
以制浆厂硫酸盐法制浆浓黑液为原料,采用冷冻干燥法将其制成黑液固形物,而后在氦气氛围下于100A电弧区炭化1min,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为13.99mmol/g。
实施例3:
以制浆厂硫酸盐法制浆浓黑液为原料,采用真空干燥法将其制成黑液固形物,而后在氖气氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为15.65mmol/g。
实施例4:
以制浆厂硫酸盐法制浆浓黑液为原料,采用真空干燥法将其制成黑液固形物,而后在氩气氛围下于1000A电弧区炭化1s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为8.63mmol/g。
实施例5:
以制浆厂烧碱法制浆浓黑液为原料,采用真空干燥法将其制成黑液固形物,而后在二氧化碳氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为12.98mmol/g。
实施例6:
以制浆厂烧碱-蒽醌法制浆稀黑液为原料,采用真空干燥法将其制成黑液固形物,而后在二氧化碳氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为12.03mmol/g。
实施例7:
以实验室有机溶剂法制浆稀黑液为原料,采用真空干燥法将其制成黑液固形物,而后在二氧化碳氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为5.53mmol/g。
实施例8:
以制浆厂化学机械法制浆稀黑液为原料,采用真空干燥法将其制成黑液固形物,而后在二氧化碳氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为9.62mmol/g。
实施例9:
以制浆厂纸浆洗涤所得稀黑液为原料,采用真空干燥法将其制成黑液固形物,而后在二氧化碳氛围下于200A电弧区炭化30s,将固体产物研磨,即得多孔碳复合材料;该多孔碳复合材料在0℃时的CO2吸附量为6.96mmol/g。
以上各实施例中,电弧处理可采用电弧炉等设备进行具体实施,电弧区即指采用电弧炉的电弧热辐射区域,也即黑液固形物受电弧热处理的区域。
如图1和图2所示,在氦气氛围下于100A电弧区炭化1min所得多孔碳复合材料能在0℃时于1bar压力下等温吸附15.65mmol/g的CO2,其多孔碳孔隙结构发达,以微孔和介孔为主,且高比表面积高达2001.52m2/g。
此外,除非权利要求中明确说明,本发明所述处理元素和序列的顺序、数字字母的使用、或其他名称的使用,并非用于限定本申请流程和方法的顺序;尽管上述披露中通过各种示例讨论了一些目前认为有用的发明实施例,但应当理解的是,该类细节仅起到说明的目的,附加的权利要求并不仅限于披露的实施例,相反,权利要求旨在覆盖所有符合本申请实施例实质和范围的修正和等价组合;例如,虽然以上所描述的系统组件可以通过硬件设备实现,但是也可以只通过软件的解决方案得以实现,如在现有的服务器或移动设备上安装所描述的系统。
最后,应当理解的是,本发明中所述实施例仅用以说明本发明实施例的原则;其他的变形也可能属于本发明的范围;因此,作为示例而非限制,本发明实施例的替代配置可视为与本发明的教导一致;相应地,本发明的实施例不限于本发明明确介绍和描述的实施例。
Claims (8)
1.一种生物质基多孔碳复合材料,其特征在于,以制浆造纸黑液固形物为前驱体,通过电弧处理后得到,具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种,所述多孔碳结构以所述前驱体中的木质素为碳源,以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂,受电弧热炭化并自活化后得到,所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
2.根据权利要求1所述的生物质基多孔碳复合材料,其特征在于,所述多孔碳结构可通过改变炭化工况进行调控。
3.一种如权利要求1所述的生物质基多孔碳复合材料的制备方法,其特征在于,包括:
将制浆造纸黑液干燥成黑液固形物;
在惰性气体保护下,电弧处理所述黑液固形物,得到固体产物;
将所述固体产物研磨,即得生物质基多孔碳复合材料。
4.根据权利要求3所述的生物质基多孔碳复合材料的制备方法,其特征在于,电弧处理过程中电弧电流为10-1000A,处理时间为1s-10min。
5.根据权利要求3所述的生物质基多孔碳复合材料的制备方法,其特征在于,所述将制浆造纸黑液干燥成黑液固形物,包括:
将制浆造纸黑液搅拌均匀,在搅拌状态下将制浆造纸黑液浸入液氮中,使制浆造纸黑液快速冷冻,然后采用冷冻干燥法进行干燥,获得黑液固形物。
6.根据权利要求3所述的生物质基多孔碳复合材料的制备方法,其特征在于,所述制浆造纸黑液为烧碱法制浆黑液、烧碱-蒽醌法制浆黑液、硫酸盐法制浆黑液、有机溶剂法制浆黑液、化学机械法制浆黑液、纸浆洗涤所得黑液中的至少一种。
7.根据权利要求3所述的生物质基多孔碳复合材料的制备方法,其特征在于,所述制浆造纸黑液为实验室制浆黑液、制浆厂稀黑液、制浆厂浓黑液中的至少一种。
8.一种如权利要求1所述的生物质基多孔碳复合材料在CO2吸附中的应用。
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