CN115518640B - 一种锌铁负载改性碳复合材料的制备方法及应用 - Google Patents
一种锌铁负载改性碳复合材料的制备方法及应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000001721 carbon Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229960002413 ferric citrate Drugs 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 229910052596 spinel Inorganic materials 0.000 abstract description 4
- 239000011029 spinel Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000005447 environmental material Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/0229—Compounds of Fe
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Abstract
本发明属于环境材料领域,提供一种锌铁负载改性碳复合材料的制备方法及应用,包括改性碳载体的制备和锌铁负载碳基催化剂的制备。本发明制备的催化剂展现出尖晶石和碳共存结构。相比金属氧化物和混合相以及目前文献中报道的炭材料,本发明制备出的锌铁负载改性碳复合材料在VOCs和甲醛的去除中表现出较好的活性和稳定性,本方法原料来源广泛、工艺路线简单、操作方便,对各种应用场景适应能力强,具有较好的工业应用前景。
Description
技术领域
本发明涉及大气污染治理和环境材料的技术领域,具体涉及到一种锌铁负载改性碳复合材料的制备以及在VOCs催化和甲醛吸附材料方面的应用。
背景技术
VOCs排放是目前国内外重点关注的环境问题,将其热催化处理是主流的处理方法,可使用的催化剂中过渡金属氧化物催化剂研究较为广泛。Yong Jiang.等人在《Materials Letters》(2006,60(11), 1374-1378) 中报道,由钒和锌铁尖晶石构成的催化材料在各种VOC气体催化过程中都有一定的作用。并且负载型催化剂的特点在于它们之中通常存在着载体和活性物种之间的相互作用。
载体选材中,纳米碳材料具有比表面积大,孔隙率高,表面化学性质丰富,导电性和疏水性良好的优点。公开号为202111529798.5的发明专利曾公开了一种过渡金属负载生物炭活化过硫酸盐的高级氧化杀菌方法,研究了过渡金属负载生物炭材料,杀菌效果良好,证明过渡金属能负载于生物炭上起到一定作用。公开号为202210428806.5的发明专利曾公开了一种同时脱除VOCs和甲醛吸附剂的制备方法,制备的N掺杂生物炭基Fe&N双掺杂TiO2复合材料具有丰富的孔道结构和活性位点以及优异的催化降解能力。因此研究工作充分利用生物炭材料的优秀特性来增强催化剂的VOCs催化氧化性能和甲醛吸附性能。但是,如果更好将多种活性金属组分有效地结合在纳米碳材料上,形成有效的构效关系,同时保障催化剂的催化活性和稳定性存在一定的问题。
本发明专利提供了一种锌铁负载改性碳复合材料的制备方法在VOCs催化氧化方面和甲醛吸附方面的应用。发明专利以材料的多孔结构的制备作为技术路径,通过生物质高温转化合成出生物碳体,再由浸渍沉积方法形成锌铁尖晶石负载碳基复合材料。该复合材料的整体结构由尖晶石和生物炭组成,在材料的表面存在大量的晶界和有序的孔道结构。当应用于VOCs催化氧化领域时,该复合材料有非常好的催化性能,这归因于复合材料独特的晶体缺陷以及材料孔道之间的协同效应。当应用于甲醛去除领域时,该复合材料有非常好的吸附性能,这归因于复合材料独特的材料孔道之间的物理吸附和化学吸附。
发明内容
本发明公开一种锌铁负载改性碳复合材料的制备方法及应用。本发明利用以材料的多孔结构和尖晶石结构制备作为技术路径,通过生物质高温转化合成出生物碳体,再由浸渍沉积方法形成锌铁负载碳基复合材料。当作为VOCs催化材料时,独特的晶体缺陷以及材料孔道之间的协同效应能够极大地提高有机物的氧化性能,当作为甲醛吸附材料时,材料中蕴含丰富的孔道和表面金属组分产生的电子能够有效提升甲醛吸附能力,因此具有较为广泛的应用前景。
本发明目的在于提供一种锌铁负载改性碳复合材料的制备方法。
本发明的再一目的在于:提供一种上述制备方法制得的锌铁负载改性碳复合材料产品的应用。
本发明目的通过下述方案实现:一种锌铁负载改性碳复合材料的制备方法,其特征在于,具体步骤如下:
a、改性碳载体的制备:将生物质原料放入烘箱干燥24小时,破碎过筛后,加入一定量有机酸活化,过滤干燥后得到原料。将得到的原料放入管式炉中,通入惰性气体或氮气保护气在一定温度范围内烧制,烧制后的成品用乙醇洗涤数次后,烘干即得生物炭载体。
b、锌铁负载碳基催化剂的制备:称取一定比例的锌盐、铁盐、EDTA和步骤a中所得碳基载体,分散在去离子水中,通过氢氧化钠调节溶液pH得到沉淀物前驱体,随后将所得到的前驱体干燥12小时,在一定温度下焙烧4小时,待焙烧结束后可获得粉末。将得到的粉末通过乙醇和去离子水洗涤数次后,最后在烘箱里干燥18小时即得到锌铁负载改性碳复合材料。
步骤a所述的生物质种类为秸秆、椰壳、咖啡渣、污泥等;
步骤a所述的有机酸是指甲酸、醋酸、柠檬酸等;
步骤a所述的一定温度范围是指600~1100℃之间;
步骤b所述的一定比例是指锌铁摩尔比的比例为1:2~1:5;
步骤b所述的锌盐是指硝酸锌、乙酸锌、碳酸锌等;
步骤b所述的铁盐是指硝酸铁、乙酸铁、柠檬酸铁、碳酸铁等;
步骤b所述的一定温度控制为200~600℃;
本发明提供一种根据上述任一所述方法制备得到的锌铁负载改性碳复合材料在VOCs催化和甲醛吸附材料方面的应用。
与现有技术相比,本发明的技术特点是,以材料的多孔结构的制备作为技术路径,通过生物质高温转化合成出生物碳体,再通过有机酸改性,最后由浸渍沉积方法形成锌铁负载碳基复合材料。当作为VOCs催化材料时,独特的晶体缺陷以及材料孔道之间的协同效应能够极大地提高有机物的氧化性能,当作为甲醛吸附材料时,材料中蕴含丰富的孔道和表面金属组分产生的电子能够有效提升甲醛吸附能力,该复合材料的合成方法简单,具有良好的实际应用前景。
本发明制备的催化剂展现出尖晶石和碳共存结构。相比金属氧化物和混合相以及目前文献中报道的炭材料,本发明制备出的锌铁负载改性碳复合材料在VOCs和甲醛的去除中表现出较好的活性和稳定性,本方法原料来源广泛、工艺路线简单、操作方便,对各种应用场景适应能力强,具有较好的工业应用前景。
附图说明
图1为实施案例1所得的锌铁负载改性碳复合材料的扫描电镜图。
具体实施方式
本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1:
一种锌铁负载改性碳复合材料,按下述步骤制备:
a、改性碳载体的制备:
将秸秆放入烘箱干燥24小时,破碎过筛后,加入一定量甲酸活化,过滤干燥后得到原料;将得到的原料放入管式炉中,通入氮气保护气在700℃烧制,烧制后的成品用乙醇洗涤数次后,烘干即得生物炭载体;
b、锌铁负载碳基催化剂的制备:
称取乙酸锌、柠檬酸铁、EDTA和步骤a中所得生物炭载体,分散在去离子水中,锌铁摩尔比为1:2;通过氢氧化钠调节溶液pH得到沉淀物前驱体,随后将所得到的前驱体干燥12小时,在450℃焙烧4小时,待焙烧结束后可获得粉末;将得到的粉末通过乙醇和去离子水洗涤数次后,在烘箱里干燥18小时即得到锌铁负载改性碳复合材料。
进一步地催化测试能够表明,在反应条件为浓度1000 ppm甲苯混合气,空速为48000 mL/g/h的状态下,锌铁负载改性生物炭复合材料在300℃时去除88%甲苯,可见,锌铁负载改性生物炭复合材料显示出较好的VOCs催化氧化性能。
实施例2:
一种锌铁负载改性碳复合材料,按下述步骤制备:
a、改性碳载体的制备:
将咖啡渣放入烘箱干燥24小时,破碎过筛后,加入一定量乙酸活化,过滤干燥后得到原料;将得到的原料放入管式炉中,通入惰性气体或氮气保护气在900℃烧制,烧制后的成品用乙醇洗涤数次后,烘干即得生物炭载体;
b、锌铁负载碳基催化剂的制备:
称取硝酸锌、硝酸铁、EDTA和步骤a中所得生物炭载体,分散在去离子水中,锌铁摩尔比为1:4;通过氢氧化钠调节溶液pH得到沉淀物前驱体,随后将所得到的前驱体干燥12小时,在马弗炉中300℃焙烧4小时,待焙烧结束后可获得粉末;将得到的粉末通过乙醇和去离子水洗涤数次后,在烘箱里干燥18小时即得到锌铁负载改性碳复合材料。
进一步地催化测试能够表明,在25℃条件下,针对起始浓度为1.53 mg/m3的甲醛进行吸附实验,锌铁负载改性生物炭复合材料能够在6小时内吸附85%的甲醛,可见,锌铁负载碳基复合材料显示出较好的甲醛吸附性能。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种锌铁负载改性碳复合材料在VOCs催化和甲醛吸附材料方面的应用,其特征在于,所述的锌铁负载改性碳复合材料的制备方法包括下述步骤
a、改性碳载体的制备
将生物质原料放入烘箱干燥24小时,破碎过筛后,加入有机酸活化,过滤干燥后得到原料,所述的生物质原料为秸秆、椰壳、咖啡渣、污泥;将得到的原料放入管式炉中,通入惰性气体或氮气保护气在600~1100℃烧制,烧制后的成品用乙醇洗涤数次后,烘干即得生物炭载体;
b、锌铁负载碳基催化剂的制备
称取锌盐、铁盐、EDTA和步骤a中所得生物炭载体,分散在去离子水中,锌铁摩尔比为1:2~1;通过氢氧化钠调节溶液pH得到沉淀物前驱体,随后将所得到的前驱体干燥12小时,在200~600℃焙烧4小时,待焙烧结束后可获得粉末;将得到的粉末通过乙醇和去离子水洗涤数次后,在烘箱里干燥18小时即得到锌铁负载改性碳复合材料;其中,
步骤a所述的有机酸是指甲酸、醋酸、柠檬酸中的一种;
步骤b所述的锌盐是指硝酸锌或乙酸锌。
2.根据权利要求1所述的锌铁负载改性碳复合材料在VOCs催化和甲醛吸附材料方面的应用,其特征在于,步骤b所述的铁盐是指硝酸铁、乙酸铁、柠檬酸铁中的一种。
3.根据权利要求1至2任一项所述的锌铁负载改性碳复合材料在VOCs催化和甲醛吸附材料方面的应用,其特征在于,按下述步骤制备
a、改性碳载体的制备
将秸秆放入烘箱干燥24小时,破碎过筛后,加入甲酸活化,过滤干燥后得到原料;将得到的原料放入管式炉中,通入氮气保护气在700℃烧制,烧制后的成品用乙醇洗涤数次后,烘干即得生物炭载体;
b、锌铁负载碳基催化剂的制备
称取乙酸锌、柠檬酸铁、EDTA和步骤a中所得生物炭载体,分散在去离子水中,锌铁摩尔比为1:2;通过氢氧化钠调节溶液pH得到沉淀物前驱体,随后将所得到的前驱体干燥12小时,在450℃焙烧4小时,待焙烧结束后可获得粉末;将得到的粉末通过乙醇和去离子水洗涤数次后,在烘箱里干燥18小时即得到锌铁负载改性碳复合材料。
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