CN114433037B - M41s介孔材料吸附剂的制备方法及m41s介孔材料吸附剂和应用 - Google Patents
M41s介孔材料吸附剂的制备方法及m41s介孔材料吸附剂和应用 Download PDFInfo
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- CN114433037B CN114433037B CN202011128338.7A CN202011128338A CN114433037B CN 114433037 B CN114433037 B CN 114433037B CN 202011128338 A CN202011128338 A CN 202011128338A CN 114433037 B CN114433037 B CN 114433037B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 101
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 title claims abstract description 44
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000003921 oil Substances 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 70
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- NMDQPQZRIKCRDU-UHFFFAOYSA-N 3-chloro-2-dodecylpyridine Chemical compound CCCCCCCCCCCCC1=NC=CC=C1Cl NMDQPQZRIKCRDU-UHFFFAOYSA-N 0.000 claims 1
- RRBZOQRGJKEVMB-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCC)C[N+](C)(C)CCCCCCCCCCCCCCCCCC Chemical compound [Br-].C(CCCCCCCCCCC)C[N+](C)(C)CCCCCCCCCCCCCCCCCC RRBZOQRGJKEVMB-UHFFFAOYSA-M 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- ZNIKJNSGUBDFLB-UHFFFAOYSA-M dimethyl-octadecyl-tridecylazanium chloride Chemical compound [Cl-].C(CCCCCCCCCCC)C[N+](C)(C)CCCCCCCCCCCCCCCCCC ZNIKJNSGUBDFLB-UHFFFAOYSA-M 0.000 claims 1
- 238000003795 desorption Methods 0.000 abstract description 30
- 239000011230 binding agent Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 230000003068 static effect Effects 0.000 description 17
- 239000002808 molecular sieve Substances 0.000 description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 12
- 239000012855 volatile organic compound Substances 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 2
- OWQGBDSLJUVLKF-UHFFFAOYSA-N 2-dodecylpyridine Chemical compound CCCCCCCCCCCCC1=CC=CC=N1 OWQGBDSLJUVLKF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YUJLIIRMIAGMCQ-CIUDSAMLSA-N Ser-Leu-Ser Chemical compound [H]N[C@@H](CO)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(O)=O YUJLIIRMIAGMCQ-CIUDSAMLSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
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- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- B01D53/00—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
- 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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Abstract
本发明涉及一种M41S介孔材料吸附剂的制备方法及M41S介孔材料吸附剂和应用。该方法包括以下步骤:a)将固体硅源、模板剂、NaOH粉碎并混合均匀;b)将液体硅源、造孔剂配成溶液,与步骤a)所得粉末采用滚球的方式成型;c)将步骤b)所得成型固体加入碱液后进行晶化,得到M41S介孔材料吸附剂。该方法所需模板剂量低,且为一次成型,不包含粘结剂,所得M41S介孔材料吸附剂具有适宜的孔径分布、较大的比表面积和较高的结晶度,用于油气回收时,具有吸附效率高、吸附容量大、易于脱附、稳定性良好等优点。
Description
技术领域
本发明属于油气回收吸附剂技术领域,具体涉及一种用于油气回收的M41S介孔材料吸附剂的制备方法。
背景技术
油气回收是指对储、运、装、卸过程中挥发出来的油气进行治理和回收的措施。由于各国对于环境保护的要求日益严格,对于油库、加油站及油箱会发出来的油气需要进行回收。DB13/2322-2016(工业企业挥发性有机物排放标准)的排放限值为100mg/m3;GB31570-2015(石油炼制工业污染物排放标准)的排放标准为120mg/m3;GB20950-2007(储油库大气污染物排放标准)、GB50759-2012(油品装载系统油气回收设施设计规范)、GB20952-2007(加油站大气污染物排放标准)均为25mg/m3。目前中国的油气回收技术有吸附法、冷凝-吸附法、膜分离方法等。其中吸附法具有装置维护方便、能耗较低、效率高的优点。冷凝-吸附法,为了降低全部冷凝的能耗,先将油气冷凝,再吸附的方式。膜分离方法的设备小、操作简单、易于维护,但是投资大、能耗高。其中,吸附法、冷凝-吸附法对于吸附剂的选择至关重要,国内目前多以活性炭作为油气回收的吸附剂。M41S系列的硅基分子筛材料虽然在吸附领域有着广泛应用,但是较少应用于油气回收技术领域中。
CN102432006A公开了一种油气回收专用活性炭及其制备方法,该方法以原煤为原料制备油气回收专用活性炭,其异丁烷吸附容量为10.5~12.2g/100mL。CN102389774A公开了一种以稻壳为原料制备油气吸附复合材料的制备方法,该方法是制备一种活性炭和二氧化硅的复合材料。CN105668565A公开了一种油气吸附用活性炭及其制备方法及碳罐,该活性炭吸附剂具有微孔-介孔-大孔复合结构,对于正丁烷的工作容量达到9.00~14.62g/100mL,并且对正丁烷有快速的吸脱附能力。但是采用活性炭作为吸附剂在实际使用过程中均存在吸附寿命短、操作存在热点、频繁开停工和异常工况等问题,并且由于其丰富的微孔结构,脱附较为困难。
CN108940188A公开了一种无粘结剂全硅MCM-41分子筛吸附剂的制备方法,该方法对已制备的MCM-41分子筛原粉通过重结晶的方式制备全硅分子筛,制备过程复杂,成本高,需多次晶化。CN106115729A公开了一种无溶剂条件下合成具有多级孔结构MCM-41和金属参杂的M-MCM-41分子筛,该方法增加了TMAOH模板剂,以固体硅源合成多级孔,但是该方法模板剂用量大,所得MCM-41的结晶度差,孔径分布主要是微孔和大孔,其中微孔不利于油气或其他VOCs气体的脱除,大孔则不利于气体的吸附,并且该方法所得MCM-41分子筛在实际应用前,还需要进一步加入粘结剂成型,从而会影响到分子筛的性能。
因此研究出一种适用于油气回收的M41S吸附剂的制备方法,对油气回收领域具有重要的现实指导意义。
发明内容
针对现有技术的不足,本发明提供一种M41S介孔材料吸附剂的制备方法及M41S介孔材料吸附剂和应用,该方法所需模板剂量低,且为一次成型,不包含粘结剂,所得M41S介孔材料吸附剂具有适宜的孔径分布、较大的比表面积和较高的结晶度,用于油气回收时,具有吸附效率高、吸附容量大、易于脱附、稳定性良好等优点。
本发明第一方面提供一种的M41S介孔材料吸附剂的制备方法,该方法包括以下步骤:
a)将固体硅源、模板剂、NaOH粉碎并混合均匀;
b)将液体硅源、造孔剂配成溶液,与步骤a)所得粉末采用滚球的方式成型;
c)将步骤b)所得成型固体加入碱液后进行晶化,得到M41S介孔材料吸附剂。
进一步地,所述固体硅源为白炭黑,具体可以为液相白炭黑和/或气相白炭黑。固体硅源引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.4:1~0.7:1。
进一步地,所述模板剂选自十二烷基至十八烷基三甲基溴化胺和/或十二烷基至十八烷基三甲基溴化胺和/或氯化胺,优选为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵或十八烷基三甲基溴化铵等中的至少一种。
进一步地,模板剂的加入量与最终体系中二氧化硅总量的摩尔比为1:10~1:50,优选为1:15~1:35;步骤a)中所述NaOH的加入量与最终体系中二氧化硅总量的摩尔比为1:4~1:15。
进一步地,所述液体硅源选自硅溶胶、水玻璃、正硅酸乙酯的一种或多种;液体硅源引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.3:1~0.6:1。
进一步地,所述造孔剂选自十二烷基硫酸钠SDC、十二烷基磺酸钠SLS、氯化十二烷基吡啶CPC、十二烷基甜菜碱DDMB、聚乙二醇PEG中的一种或多种;造孔剂的加入量与最终体系中二氧化硅总量的摩尔比为1:40~1:100。
进一步地,所述碱液为氢氧化钠、氨水或尿素中的一种或几种配成的碱性水溶液;所述碱液的质量浓度0.5%~2%,所述碱液的加入量为成型固体质量的0.1~5倍。
进一步地,所述晶化的条件包括:100℃~180℃下水热处理和100℃~120℃下常压回流处理中的一种或多种联用,优选地为水热处理;所述晶化处理的时间为24h~288h,优选为48h~96h。
进一步地,晶化后进行常规洗涤、干燥、焙烧等步骤,得到M41S介孔材料吸附剂。
所述洗涤为采用本领域的常规技术手段即可。所述干燥的温度为50~120℃,干燥的时间为4~24h;所述焙烧的温度为400℃~700℃,优选为500℃~600℃,焙烧的时间为3~6h。
本发明第二方面提供了一种采用上述方法得到的M41S介孔材料吸附剂,具有如下性质:比表面积为400m2/g~1000m2/g,孔容为0.1cm3/g~1cm3/g,平均孔径为1nm~8nm,优选为2~5nm,相对结晶度为95%~115%,机械强度为30N/cm~150N/cm;所述M41S介孔材料吸附剂的吸附容量(以环己烷计)为0.2~0.8g/g。
本发明第三方面提供一种上述M41S介孔材料吸附剂在油气回收中的应用。
将上述方法制备的M41S介孔材料吸附剂在油气回收中进行静态吸附的条件包括:将所述M41S介孔材料吸附剂研磨成大于180目的固体粉末,将粉末置于20~35℃的环己烷气氛中24~48h。静态吸附容量为新鲜吸附剂增加质量与新鲜吸附剂的质量比。
将上述方法制备的M41S介孔材料吸附剂在油气回收中进行动态吸附的条件包括:将所述M41S介孔材料吸附剂装入VOCs吸附仪器中,吸附仪器进口的VOCs浓度为300000~400000mg/m3,吸附的温度为25~35℃,吸附压力为常压,采用在线色谱对吸附仪器的出口VOCs浓度进行检测,所用的色谱为FID检测器。
将上述方法制备的M41S介孔材料吸附剂在油气回收中进行真空脱附的条件包括:将装入VOCs吸附仪器中的吸附剂,采用小于20kPa的绝对压力进行脱附,脱附的温度为40~50℃,脱附时间为20~30min。
与现有技术相比,本发明至少具有以下有益效果:
本发明的制备方法,先将白炭黑、模板剂、NaOH研磨混合,采用滚球与含液体硅源、造孔剂的溶液进行成型,再进行碱液处理、晶化等,最终得到M41S介孔材料吸附剂。该方法模板剂用量少,且在晶化前进行了一次成型,成型后的M41S分子筛不含粘结剂,结晶度高,避免了分子筛原粉因粘结剂的添加而减少吸附剂孔容和比表面积的情况。最终所得的M41S介孔材料吸附剂有适宜的孔径分布、较大的比表面积以及适宜的机械强度。
本发明所得M41S介孔材料吸附剂应用于油气回收时,其吸附量大、吸附深度高。与常规的活性炭吸附剂相比,吸附容量大,吸附热小;且多次使用后其吸脱附性能基本不变,稳定性良好,有望替代传统的活性炭应用于油气回收或其他VOCs处理过程中。
附图说明
图1为实施例1所得M41S介孔材料吸附剂的XRD衍射图。
具体实施方式
下面对本发明的具体实施方式进行详细说明,但是需要指出的是,本发明的保护范围并不受这些具体实施方式的限制,而是由权利要求书来确定。
本发明中,催化剂的比表面积、孔体积、平均孔径均为本领域公知的含义,可以采用本领域已知的方法和仪器进行测试。具体为,采用美国麦克仪器公司的ASAP2020M型物理化学吸附仪,测量前抽真空,300℃恒温处理2h,除去样品表面附着的杂质,之后在液氮低温下吸附高纯N2,取得催化剂粉末的吸附/脱附曲线。比表面积计算方法为BET法、孔径分布根据BJH法计算。
本发明中,催化剂的机械强度为本领域公知的含义,可以采用本领域已知的方法和仪器进行测试。具体为,采用大连化工研究设计院生产的DLⅢ型智能颗粒强度试验机测定催化剂强度,测量22次,去掉最大值和最小值后取平均值。
本发明中,XRD采用Bruker公司D-8Advance型X-射线衍射仪,Cu K辐射为射线源 石墨单色器,管电压40kV,管电流40mA,小角度衍射范围为1~6°。
本发明中,样品的相对结晶度%=(样品的最强衍射峰峰面积/标样的最强衍射峰峰面积)*标样的相对结晶对,本发明以常见的液相制备的MCM-41分子筛添加一定量的粘结剂成型后的产品为标样,其相对结晶度为100%。
本发明中,吸附评价中出口VOCs采用在线色谱进行测试,每隔10min自动进样,采用日本岛津搭建的FID检测器,测试条件为50℃以20℃/min的速度升温到160℃,维持2.5min。
实施例1
吸附剂的制备:
a)、按照总二氧化硅:NaOH:模板剂:造孔剂为80:16:5.3:1的摩尔比,计量所需的固体硅源液相白炭黑、液体硅源30wt%的硅溶胶、NaOH、十六烷基三甲基溴化胺、聚乙二醇。首先将白炭黑(引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.5)、NaOH和十六烷基三甲基溴化胺粉碎后混合均匀。
b)、将硅溶胶(引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.5)、造孔剂配成溶液。采用滚球成型的方式,将固体粉末与溶液滚球成型为直径0.5~3mm的成型固体小球。
c)、配制0.5wt%的NaOH碱液,按照成型固体小球与碱液2:1的质量比,将碱液加入到小球中,在110℃下水热晶化48h,晶化后用70℃热水洗涤至中性,80℃烘干24h,550℃焙烧4h,即得到具有机械强度的M41S介孔材料吸附剂,XRD衍射图见图1,吸附剂的表征结果示于表1中。
吸附剂的评价:
静态吸附:在20℃的恒温条件下,将吸附剂研磨成180目以上粉末后置于饱和的C6油气中。静态吸附量指24h后吸附剂增加质量与新鲜吸附剂的质量比,用来衡量吸附剂静态吸附性能。
动态吸附:采用自制管式固定床吸附装置。吸附的温度为20℃恒温吸附,压力为常压,用氮气携带环己烷进行鼓泡,其进口浓度在300000~400000mg/m3,测量VOCs仪器为在线色谱。动态吸附量指的是在动态吸附中,吸附剂增加质量与新鲜吸附剂的质量比,用来衡量吸附剂动态吸附性能,即吸附深度。穿透时间是指当尾气浓度大于25mg/m3时,动态吸附的时间,用来衡量吸附剂的吸附效率。
脱附:脱附采用真空脱附,将装置上方连接真空泵,用真空泵进行脱附,脱附的温度为室温,绝对压力为10kPa,脱附的温度为50℃。脱附结果表2所示。脱附率是指在相同的时间30min内,吸附剂在一定真空度下的减少的质量与饱和吸附量的质量比。用来衡量吸附剂的脱附效率。
吸附剂的静态吸附、动态吸附和脱附数据示于表2中。为了考察吸附剂的稳定性,下表中的穿透时间是吸附剂使用三次后水蒸气再生后的结果。
实施例2
与实施例1不同的是,按照总二氧化硅:NaOH:模板剂:造孔剂为80:16:3.2:1的摩尔比计量所需物质。所得M41S介孔材料吸附剂的XRD衍射图类似于图1,吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
实施例3
与实施例1不同的是,按照总二氧化硅:NaOH:模板剂:造孔剂为80:16:2.3:1的摩尔比计量所需物质。所得M41S介孔材料吸附剂的XRD衍射图类似于图1,吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
实施例4
与实施例1不同的是,按照总二氧化硅:NaOH:模板剂:造孔剂为80:8:5.3:1的摩尔比计量所需物质。所得M41S介孔材料吸附剂的XRD衍射图类似于图1,吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
实施例5
与实施例1不同的是,所采用的液体硅源为水玻璃(SiO2含量大于25wt%,Na2O含量大于8wt%)。按照总二氧化硅:NaOH:模板剂:造孔剂为80:8:5.3:1的摩尔比计量所需物质。所得M41S介孔材料吸附剂的XRD衍射图类似于图1,吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
实施例6
与实施例1不同的是,该吸附剂已反复吸脱附9次后测试的吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
对比例1
与实施例1不同的是,吸附剂评价中以进口的商用吸附专用活性炭作为吸附剂。吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
对比例2
与实施例1不同的是,吸附剂评价中以国产商用吸附专用活性炭为吸附剂。吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
对比例3
与实施例1不同的是,吸附剂为ZSM-5分子筛。吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
对比例4
与实施例1不同的是,吸附剂为商用硅球550℃焙烧后的吸附剂。吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
对比例5
与实施例1不同的是,按照常规液相制备MCM-41的方式去制备,吸附剂的制备如下:
按照CTAB、正硅酸四乙酯、NaOH、水为4:20:1:125的摩尔比将上述物质分别加入到容器中,强烈搅拌得到浆液。将上述浆液置于晶化釜中,100℃晶化48h。将晶化后的液体取出,过滤,洗涤至pH=7后,将其置于80℃烘箱中,烘干24h以上。
将烘干后粉末按照1℃/min的升温速率在马弗炉中升温至550℃焙烧4h。将已焙烧粉末采用粘结剂成型,成型后按照相同升温速率在450℃下焙烧4h。
吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中,其中吸附容量以环己烷计。
对比例6
按照专利CN106115729A的方法合成纯硅MCM-41,并将其采用一定的粘结剂成型。具体方法如下:称量90g九水硅酸钠和25g十六烷基三甲基溴化铵,将两者混合均匀,用力研磨大约十分钟,然后转移至水热反应釜中于100℃晶化24h,反应后将样品取出,在高温500℃焙烧后除去十六烷基三甲基溴化铵得到MCM-41分子筛。之后将MCM-41分子筛采用一定量的粘结剂成型。再次焙烧后得到成型的MCM-41分子筛。
吸附剂表征结果示于表1中,吸附剂的静态吸附、动态吸附和脱附数据示于表2中。
表1不同吸附剂的表征结果
表2吸附剂的吸脱附评价结果
Claims (10)
1.一种M41S介孔材料吸附剂的制备方法,其特征在于,所述方法包括以下步骤:
a) 将固体硅源、模板剂、NaOH粉碎并混合均匀;
b) 将液体硅源、造孔剂配成溶液,与步骤a)所得粉末采用滚球的方式成型;
c) 将步骤b)所得成型固体加入碱液后进行晶化,洗涤、干燥、焙烧,得到M41S介孔材料吸附剂;
所述固体硅源为白炭黑;所述晶化的条件包括:100℃~180℃下水热处理和100℃~120℃下常压回流处理中的一种或多种联用;所述晶化处理的时间为24h~288h;
所述模板剂选自十二烷基至十八烷基三甲基溴化铵和/或十二烷基至十八烷基三甲基氯化铵中的至少一种;
所述固体硅源引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.4:1~0.7:1;
所述模板剂的加入量与最终体系中二氧化硅总量的摩尔比为1:10~1:50。
2.按照权利要求1所述的方法,其特征在于,步骤a)中所述NaOH的加入量与最终体系中二氧化硅总量的摩尔比为1:4~1:15。
3.按照权利要求1所述的方法,其特征在于,模板剂的加入量与最终体系中二氧化硅总量的摩尔比为1:15~1:35。
4.按照权利要求1所述的方法,其特征在于,所述液体硅源选自硅溶胶、水玻璃、正硅酸乙酯的一种或多种;液体硅源引入的硅以二氧化硅计与最终体系中二氧化硅总量的摩尔比为0.3:1~0.6:1。
5.按照权利要求1所述的方法,其特征在于,所述造孔剂选自十二烷基硫酸钠、十二烷基磺酸钠、氯化十二烷基吡啶、十二烷基甜菜碱、聚乙二醇中的一种或多种;造孔剂的加入量与最终体系中二氧化硅总量的摩尔比为1:40~1:100。
6.按照权利要求1所述的方法,其特征在于,所述碱液为氢氧化钠、氨水或尿素中的一种或几种配成的碱性水溶液;所述碱液的质量浓度为0.5%~2%,所述碱液的加入量为成型固体质量的0.1~5倍。
7.按照权利要求1所述的方法,其特征在于,所述晶化处理的时间为48h~96h。
8.权利要求1-7任一项所述的方法制备的M41S介孔材料吸附剂,其特征在于:所述M41S介孔材料吸附剂具有如下性质:比表面积为400m2/g~1000m2/g,孔容为0.1mL/g~1mL/g,平均孔径为1nm~8nm,相对结晶度为95%~115%,机械强度为30N/cm~150N/cm;所述M41S介孔材料吸附剂的吸附容量以环己烷计为0.2~0.8g/g。
9.按照权利要求8所述的M41S介孔材料吸附剂,其特征在于,所述M41S介孔材料吸附剂的平均孔径为2nm~5nm。
10.按照权利要求1-7任一项所述方法制备的M41S介孔材料吸附剂或权利要求8-9任一所述的M41S介孔材料吸附剂在油气回收中的应用。
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