CN112760118A - 一种混杂布碎热解制备富芳烃化合物的方法 - Google Patents

一种混杂布碎热解制备富芳烃化合物的方法 Download PDF

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CN112760118A
CN112760118A CN202011479752.2A CN202011479752A CN112760118A CN 112760118 A CN112760118 A CN 112760118A CN 202011479752 A CN202011479752 A CN 202011479752A CN 112760118 A CN112760118 A CN 112760118A
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pyrolysis
aromatic
molecular sieve
mixed cloth
mixed
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袁浩然
张军
顾菁
王舒笑
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Guangzhou Institute of Energy Conversion of CAS
Southern Marine Science and Engineering Guangdong Laboratory Guangzhou
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Guangzhou Institute of Energy Conversion of CAS
Southern Marine Science and Engineering Guangdong Laboratory Guangzhou
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1003Waste materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明公开了一种混杂布碎热解制备富芳烃化合物的方法,将混杂布碎和分子筛按质量比1:1~1:15混合,在惰性气氛环境、450~750℃下进行催化热解以制备芳烃化合物;所述的分子筛选自MCM‑41、ZSM‑5、ZSM‑35、SBA‑15、Hβ沸石中的一种以上,所述的芳烃化合物包括苯、甲苯、萘和2‑甲基萘,本发明利用分子筛催化混杂布碎选择性热转化,既有助于特定芳烃化合物的高效合成,又能够实现混杂布碎的资源化利用与减容减量化,芳烃总收率可达60%以上。此外,本发明简单、易行,可进一步推广应用于其它含纤维类有机固体废物的资源化利用。

Description

一种混杂布碎热解制备富芳烃化合物的方法
技术领域:
本发明属于固废物综合利用领域,具体涉及一种混杂布碎热解制备富芳烃化合物的方法。
背景技术:
我国每年产生的废旧纺织品可达2000万吨,而混杂布碎是废旧纺织品重要组成部分,其化学组成主要包括化纤类和天然纤维类。当前,针对这一类有机固体废物的高值资源化利用研究相对较少,主要侧重于作为固体燃料使用和化学法纤维再生。中国发明专利CN109251777A报道采用废布条与污泥共混造粒的方式制备燃料颗粒,CN 111270354A公开了一套无纺布或废布料中纤维分离的装置,而利用热解方式将混杂布碎转化为高值化学品的研究尚未见报道。相关专利CN 106431802A、CN 103484142B等均报道了生物质类有机废弃物热解制备芳烃化合物的研究,但是该转化过程均需要富含氢的化合物(聚乙烯、聚丙烯、废塑料等)参与,以促进芳烃类物质的产生。而且在CN 106431802A专利中发明人提出掺入具有芳香环结构的木质素、聚苯乙烯等作为原料,以进行热解聚获得芳烃化合物。
发明内容:
本发明的目的是提供一种混杂布碎热解制备富芳烃化合物的方法,利用混杂布碎选择性催化热解制备芳烃类物质,实现其高值资源化利用。
本发明是通过以下技术方案予以实现的:
一种混杂布碎热解制备富芳烃化合物的方法,包括以下步骤:将混杂布碎和分子筛按质量比1:1~1:15,优选为1:10~1:15,最优选为1:15混合,在惰性气氛环境、450~750℃,优选为550-750℃,最优选为750℃下进行催化热解以制备芳烃化合物;所述的分子筛选自MCM-41、Z SM-5、ZSM-35、SBA-15、Hβ沸石中的一种以上;升温至设定热解温度的升温速率为102~104℃/s,优选为102~103℃/s,最优选为102℃/s,所述的芳烃化合物包括苯、甲苯、萘和2-甲基萘。
本发明的有益效果为:本发明利用分子筛催化混杂布碎选择性热转化,既有助于特定芳烃化合物的高效合成,又能够实现混杂布碎的资源化利用与减容减量化。其中,混杂布碎催化热解产物以苯、甲苯、萘和2-甲基萘等芳烃为主,总收率可达60%以上。此外,本发明方法简单、易行,可进一步推广应用于其它含纤维类有机固体废物的资源化利用。
具体实施方式:
以下是对本发明的进一步说明,而不是对本发明的限制。
实施例1:
将混杂布碎与ZSM-5以质量比1:1进行均匀研磨混合,在热解温度450℃,升温速率104℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯7.5%、甲苯21.4%、萘4.5%和2-甲基萘9.8%。
实施例2:
将混杂布碎与ZSM-5以质量比1:5进行均匀研磨混合,在热解温度750℃,升温速率102℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯15.5%、甲苯26.2%、萘6.8%和2-甲基萘12.4%。
实施例3:
将混杂布碎与MCM-41以质量比1:12进行均匀研磨混合,在热解温度550℃,升温速率104℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯7.5%、甲苯20.2%、萘4.1%和2-甲基萘5.5%。
实施例4:
将混杂布碎与ZSM-35以质量比1:15进行均匀研磨混合,在热解温度750℃,升温速率103℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯11.7%、甲苯15.7%、萘7.0%和2-甲基萘8.1%。
实施例5:
将混杂布碎与ZSM-35沸石以质量比1:10进行均匀研磨混合,在热解温度650℃,升温速率104℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯9.3%、甲苯12.1%、萘6.0%和2-甲基萘7.0%。
实施例6:
将混杂布碎与Hβ沸石以质量比1:5进行均匀研磨混合,在热解温度650℃,升温速率104℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯15.1%、甲苯16.4%、萘4.9%和2-甲基萘7.5%。
实施例7:
将混杂布碎与SBA-15沸石以质量比1:10进行均匀研磨混合,在热解温度750℃,升温速率103℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯9.5%、甲苯10.1%、萘3.9%和2-甲基萘8.1%。
实施例8:
将混杂布碎与SBA-15沸石以质量比1:15进行均匀研磨混合,在热解温度650℃,升温速率104℃/s,热解气氛为氩气下进行热解,热解时间20s,通过气相色谱-质谱联用仪分析热解产物相对含量,其中苯13.3%、甲苯8.3%、萘4.4%和2-甲基萘7.4%。

Claims (3)

1.一种混杂布碎热解制备富芳烃化合物的方法,其特征在于,包括以下步骤:将混杂布碎和分子筛按质量比1:1~1:15混合,在惰性气氛环境、450~750℃下进行催化热解以制备芳烃化合物;所述的分子筛选自MCM-41、ZSM-5、ZSM-35、SBA-15、Hβ沸石中的一种以上;升温速率为102~104℃/s,所述的芳烃化合物包括苯、甲苯、萘和2-甲基萘。
2.根据权利要求1所述的混杂布碎热解制备富芳烃化合物的方法,其特征在于,混杂布碎和分子筛按质量比1:10~1:15;催化热解温度为550~750℃;升温速率为102~103℃/s。
3.根据权利要求1所述的混杂布碎热解制备富芳烃化合物的方法,其特征在于,混杂布碎和分子筛按质量比为1:15混合,催化热解温度为750℃,升温速率为102℃/s。
CN202011479752.2A 2020-12-15 2020-12-15 一种混杂布碎热解制备富芳烃化合物的方法 Pending CN112760118A (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824330A (zh) * 2010-04-30 2010-09-08 中国科学技术大学 木质素催化热裂解的方法
CN102083943A (zh) * 2008-04-23 2011-06-01 Gpi专利控股有限责任公司 制备烃燃料的方法和设备
CN103384713A (zh) * 2011-01-05 2013-11-06 莱斯拉有限公司 有机质的加工
CN102015969B (zh) * 2008-03-04 2015-05-27 马萨诸塞大学 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102015969B (zh) * 2008-03-04 2015-05-27 马萨诸塞大学 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物
CN102083943A (zh) * 2008-04-23 2011-06-01 Gpi专利控股有限责任公司 制备烃燃料的方法和设备
CN101824330A (zh) * 2010-04-30 2010-09-08 中国科学技术大学 木质素催化热裂解的方法
CN103384713A (zh) * 2011-01-05 2013-11-06 莱斯拉有限公司 有机质的加工

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Application publication date: 20210507