工程科学学报，第39卷，第3期：443-448,2017年3月 Chinese Journal of Engineering,Vol.39,No.3:443-448,March 2017 DOI:10.13374/j.issn2095-9389.2017.03.017:http://journals.ustb.edu.cn 变压吸附空分用椰壳基炭分子筛的制备 李兴伟，徐绍平四，丛媛媛 大连理工大学化工与环境生命学部，大连116024 ☒通信作者，E-mail:huizixu(@hotmail.com 摘要提出以椰壳预炭化料为骨料、酚醛树脂为黏结剂制备变压吸附空分制氮用炭分子筛的新工艺路线，包括成型、炭化、 水蒸气活化、两步苯气相碳沉积调孔等主要工序；完善了炭分子筛的变压吸附空分评价手段，即以变压吸附空分为基本手段， 结合变压吸附脱附尾气总量及其中O,浓度等参数分析，准确表征炭分子筛制备过程中样品的微孔孔容和孔径变化，从而实 现对炭分子筛制备工艺参数的精确控制.所得的椰壳基炭分子筛具有较高的抗压强度，其变压吸附空分性能接近商业炭分 子筛产品 关键词炭分子筛：变压吸附：椰壳：空气分离 分类号T0424.1 Preparation of coconut shell-based carbon molecular sieves for air separation by pressure swing adsorption LI Xing-wei,XU Shao-ping,CONG Yuan-yuan Faculty of Chemical,Environmental and Biological Science and Technology,Dalian University of Technology,Dalian 116024,China Corresponding author,E-mail:huizixu@hotmail.com ABSTRACT A novel process for preparation of a carbon molecular sieve(CMS)was proposed.With coconut shell char as a carbon precursor and phenol formaldehyde resin (PF)as a binder,the process consists of a series of stages,i.e.,forming,carbonization, activation with steam,and two-step chemical vapor deposition with benzene as a carbon source.The CMS has been used as an adsor- bent in pressure swing adsorption (PSA)of air for N,production.The evaluation method of CMS based on PSA was developed by in- troducing a couple of analysis items including the amount of the effluent desorption gas in PSA and the 0,concentration in it.In this way,the development of the effective volume and size of the micropores of CMS during the preparation stages could be followed and controlled on purpose.The coconut shell-based CMS prepared by this method has a superior compressive strength and a comparable PSA performance to those commercial CMSs. KEY WORDS carbon molecular sieves;pressure swing adsorption:coconut shells:air separation 炭分子筛(CMS)被广泛运用于气体分离领域四，料成本较低，但煤所含杂质量高，并且即使同一批次煤 尤其是变压吸附空分]和甲烷富集4等.对炭分子也可能由于煤质差异导致所制备的炭分子筛稳定性较 筛的基本要求是既要有较高的吸附选择性，又要有较 差，此外以煤为原料所制备的炭分子筛对气体的吸附 大的吸附容量，因而要求其具有均一、尺寸适宜的孔 容量较低0.生物质原料特别是果壳（核）类原料价 径，以及较大的有效孔容. 格低廉，来源广泛，组成稳定且具有适宜的挥发分和低 炭分子筛的制备原料广泛，包括有机高分子聚合 灰分等特点，受到研究者关注四.现阶段国内炭分 物类圆、煤及其衍生物类切和生物质类-0.有机高 子筛生产主要以酚醛树脂作为主体原料，以煤焦油为 分子基炭分子筛性能优越但是原料成本较高：煤类原 黏结剂团，生产成本高、污染大.如何以廉价、性质稳 收稿日期：201605一19工程科学学报，第 39 卷，第 3 期: 443--448，2017 年 3 月 Chinese Journal of Engineering，Vol． 39，No． 3: 443--448，March 2017 DOI: 10． 13374 /j． issn2095--9389． 2017． 03． 017; http: / /journals． ustb． edu． cn 变压吸附空分用椰壳基炭分子筛的制备 李兴伟，徐绍平，丛媛媛 大连理工大学化工与环境生命学部，大连 116024 通信作者，E-mail: huizixu@ hotmail． com 摘 要 提出以椰壳预炭化料为骨料、酚醛树脂为黏结剂制备变压吸附空分制氮用炭分子筛的新工艺路线，包括成型、炭化、 水蒸气活化、两步苯气相碳沉积调孔等主要工序; 完善了炭分子筛的变压吸附空分评价手段，即以变压吸附空分为基本手段， 结合变压吸附脱附尾气总量及其中 O2 浓度等参数分析，准确表征炭分子筛制备过程中样品的微孔孔容和孔径变化，从而实 现对炭分子筛制备工艺参数的精确控制． 所得的椰壳基炭分子筛具有较高的抗压强度，其变压吸附空分性能接近商业炭分 子筛产品． 关键词 炭分子筛; 变压吸附; 椰壳; 空气分离 分类号 TQ424. 1 Preparation of coconut shell-based carbon molecular sieves for air separation by pressure swing adsorption LI Xing-wei，XU Shao-ping ，CONG Yuan-yuan Faculty of Chemical，Environmental and Biological Science and Technology，Dalian University of Technology，Dalian 116024，China Corresponding author，E-mail: huizixu@ hotmail． com ABSTＲACT A novel process for preparation of a carbon molecular sieve ( CMS) was proposed． With coconut shell char as a carbon precursor and phenol formaldehyde resin ( PF) as a binder，the process consists of a series of stages，i． e． ，forming，carbonization， activation with steam，and two-step chemical vapor deposition with benzene as a carbon source． The CMS has been used as an adsor￾bent in pressure swing adsorption ( PSA) of air for N2 production． The evaluation method of CMS based on PSA was developed by in￾troducing a couple of analysis items including the amount of the effluent desorption gas in PSA and the O2 concentration in it． In this way，the development of the effective volume and size of the micropores of CMS during the preparation stages could be followed and controlled on purpose． The coconut shell-based CMS prepared by this method has a superior compressive strength and a comparable PSA performance to those commercial CMSs． KEY WOＲDS carbon molecular sieves; pressure swing adsorption; coconut shells; air separation 收稿日期: 2016--05--19 炭分子筛( CMS) 被广泛运用于气体分离领域［1］， 尤其是变压吸附空分［2--3］和甲烷富集［4--5］等． 对炭分子 筛的基本要求是既要有较高的吸附选择性，又要有较 大的吸附容量，因而要求其具有均一、尺寸适宜的孔 径，以及较大的有效孔容． 炭分子筛的制备原料广泛，包括有机高分子聚合 物类［6］、煤及其衍生物类［7］和生物质类［8--10］． 有机高 分子基炭分子筛性能优越但是原料成本较高; 煤类原 料成本较低，但煤所含杂质量高，并且即使同一批次煤 也可能由于煤质差异导致所制备的炭分子筛稳定性较 差，此外以煤为原料所制备的炭分子筛对气体的吸附 容量较低［11］． 生物质原料特别是果壳( 核) 类原料价 格低廉，来源广泛，组成稳定且具有适宜的挥发分和低 灰分等特点，受到研究者关注［8，12］． 现阶段国内炭分 子筛生产主要以酚醛树脂作为主体原料，以煤焦油为 黏结剂［13］，生产成本高、污染大． 如何以廉价、性质稳