CN112892471A - 一种超高疏水性能VOCs吸附剂分子筛的制备方法 - Google Patents
一种超高疏水性能VOCs吸附剂分子筛的制备方法 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 18
- 239000003463 adsorbent Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 42
- 239000010703 silicon Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000499 gel Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 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 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000002444 silanisation Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 24
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008710 crystal-8 Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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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Abstract
本发明公开了一种超高疏水性能VOCs吸附剂分子筛的制备方法,本发明通过一步法对分子筛产品进行表面硅烷化处理得到超高疏水性能的HZSM5分子筛,并将其应用于VOCs尾气吸附降解方面,产品具有疏水性更强、VOCs竞争吸附选择性高、水热稳定性更高等特点,相对于分步处理工艺,更加容易实现工业化、操作简便,且克服了传统硅烷化表面不均匀的缺点。
Description
技术领域
本发明属于分子筛制备的技术领域,具体涉及一种超高疏水性能VOCs吸附剂分子筛的制备方法。
背景技术
挥发性机物(VOCs)是指在标准状况下饱和蒸气压大于0.13kPa的有机化合物,包括烃、醛、酮、醇、醚、酯、杂原子取代烃等300多种有机物。大气中VOCs具有种类繁多、来源广泛、毒性大、浓度相对较低但污染物总量大等特点。吸附法是主要的VOCs净化方法之一,与其它方法相比,吸附法具有工艺成熟、操作简单、能耗低、净化效率高等优点,适用于低浓度、高风量的VOCs净化,但也存在着高温度下吸附效率低、高湿度下VOCs的吸附被抑制等缺点。
沸石分子筛是优良的吸附剂之一,广泛用于基本有机化工、石油化工的生产上,在有害气体的治理上,也常用于SO2、NOx、CO、CO2,NH3,CCl4、水蒸气和气态碳氢化合物废气的净化。主要是由于它具有以下特点:1、分子筛吸附选择性强。这是由于分子筛的孔径大小整齐均一,又是一种离子型吸附剂,因此,它能根据分子的大小及极性的不同进行选择性吸附;2、分子筛吸附能力强。即使气体的组成浓度很低,仍然具有较大的吸附能力。3、在较高的温度下仍有较大的吸附能力,而其他吸附剂却受温度的影响很大,因而在相同温度条件下,分子筛的吸附容量大。
随着研究的不断深入,目前沸石转轮浓缩技术是针对低浓度VOCs治理而发展起来的一种新技术,与化学法进行组合,形成了沸石转轮浓缩+焚烧技术。整个沸石转轮吸附浓缩技术中,用于吸附浓缩的疏水形沸石分子筛是其技术的核心,沸石分子筛作为疏水性吸附材料的优势越来越明显,目前国内外已有多项专利涉及了以沸石分子筛作为吸附剂用于处理VOCs的报道,主要有US6281406B1、US4705909、CN1781885A、CN11055906A、CN1280977A、CN1749226A、CN201710375783等,上述专利中所合成的分子筛作为吸附剂时,存在着以下主要缺陷:一、分子筛作为吸附剂时需要添加一些无机或者有机材料作为粘结剂使用,这就造成了产品合成步骤繁琐、且过程中还需掺加有毒有害物质,不利于工业生产;二、分子筛疏水性能及水热稳定性均需要有待进一步提高,因为VOCs属于低浓度高含水量的有机废气,疏水性能的高低直接影响其吸收效率。因此,如何提高分子筛产品的疏水性能成为目前急需解决的关键性技术。
分子筛的改性主要有两种方法,脱铝改性和接枝改性,脱铝改性包括高温水热法、酸碱改性法等;接枝改性即硅烷化反应,通过硅烷化试剂与分子筛表面的硅羟基作用从而在表面接枝有机官能团,主要通过硅羟基Si-OH与有机硅的共价结构实现。本发明一改传统的硅烷化技术,将硅烷化反应通过一步法直接引入到分子筛合成中来,取得了优良的使用效果。
发明内容
本发明的目的在于针对现有技术中的缺陷与缺点,提出一种成本低、能耗小,可实现工业化生产的超高疏水性VOCs吸附剂——HZSM5沸石分子筛制备方法。
为了实现上述发明的目的,本发明采用以下方案来实现:
一种超高疏水性能VOCs吸附剂分子筛的制备方法,其特征在于:包括以下步骤:
(1)将硅源、碱源、模板剂、ZSM-5分子筛晶种与水混合,形成凝胶;
(2)将步骤(1)中所述凝胶置于反应釜中进行水热晶化,反应结束后,进行急冷降温,得到产物A;
(3)将步骤(2)中产物温度降至室温后,向反应釜中按一定比例补加有机醇溶剂和有机硅烷类试剂,搅拌均匀后在100-180℃条件下继续晶化6-12小时;
(4)将步骤(3)所得产物进行固液分离、洗涤、干燥、焙烧得到分子筛原粉;
(5)将步骤(4)所得分子筛原粉置入稀酸溶液中进行离子交换,然后干燥焙烧得到HZSM-5分子筛。
进一步地,所述步骤(1)中的水、碱源、模板剂、硅源以其氧化物计,所述混合物中各组分摩尔比为(2-10):(0.03-0.20):(0.03-0.50):1,所述步骤(1)中的晶种添加量为SiO2质量的0.05-10%。
进一步地,所述步骤(1)中的硅源选用固体硅胶、九水合硅酸钠、硅粉、白炭黑、硅藻土、硅酸盐和正硅酸乙酯中的任意一种或多种的混合;所述碱源选用氢氧化钠、氢氧化钾中的任意一种或多种的混合;所述模板剂选用甲胺、二乙胺、四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、四丙基氢氧化铵、1,6己二胺、正丁胺、十六烷基三甲基溴化铵中的任意一种或多种的混合。
进一步地,所述步骤(1)中的晶种选用市售或自制ZSM5分子筛晶种。
进一步地,所述步骤(2)中水热晶化温度为150-180℃,水热时间为18-48h。
进一步地,所述步骤(3)中所述有机醇溶剂选用甲醇、乙醇、环己醇、异丁醇、乙二醇中的任意一种或多种的混合;所述有机硅烷类试剂选用三甲基氯硅烷、六甲基硅烷、六甲基二氮硅烷的任意一种或多种的混合。
进一步地,所述步骤(3)中,产物A、有机醇溶剂、有机硅烷类试剂的质量比为1:0.5:5。
进一步地,所述步骤(4)中干燥温度为120℃,干燥时间12h,焙烧温度为500-550℃,焙烧时间6-12小时。
进一步地,所述步骤(5)中离子交换条件为:将原料置于0.5~2mol·L-1的稀酸溶液中搅拌1~4h,其中交换溶液与分子筛原粉的液固质量比10-20:1,交换温度为60~95℃,并重复离子交换过程1~3次。
进一步地,所述稀酸溶液选用硫酸、盐酸或硝酸溶液中的任意一种或多种的混合。
所述合成方法制备得到的HZSM5分子筛应用于VOCs吸附降解中。
与现有技术相比,本发明合成超高疏水性能的HZSM5沸石分子筛的方法有以下优点:
1)合成工艺简单可行,所用原料价格低廉,制备过程无任何有毒物质加入,产品成本低,环保压力小。
2)本发明所得到的HZSM5分子筛具有更强的疏水性能,超高水热稳定性及强大的VOCs吸附性能。
3)本发明在分子筛硅烷化处理工艺精简为一步法硅烷化处理,使其更好实现,更加具备工业化价值。
附图说明
图1为实施例1-5和对比样的XRD图谱。
图2a为实施例1硅烷化处理的样品的SEM图谱;
图2b为对比样的未硅烷化处理的样品的SEM图谱。
其中:图1中横坐标表示XRD衍射仪扫描的2θ角度范围,纵坐标表示衍射峰轻度。图1中A、B、C、D、E、F分别表示实施例1-5和对比样的XRD图谱,A-E为硅烷化处理的样品,F为未进行硅烷化处理的样品。从图中可以看出在保持良好疏水性能的同时,硅烷化处理前后样品很好的保持了晶体结构。
图2中十小格表示1μm。图2a为硅烷化处理的样品,图2b为未硅烷化处理的样品。从图2a和图2b中可以看出,在保持良好疏水性能的同时,硅烷化处理前后样品的形貌没有明显变化,很好的保持了晶体的形貌。
具体实施方式
下面结合具体实例对本发明进行进一步说明,但本发明不局限于下述实例。
实施例中所用原料介绍如下:
ZSM-5分子筛晶种,合成方法如下:将3.0g氢氧化钠、70g硅胶、溶于120g去离子水中,11gTPAOH,搅拌均匀后将凝胶装入晶化釜中,160℃下晶化24h。晶化后的产物洗涤至pH=8,100℃干燥12h;实施例1
将硅源(硅粉),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPAOH∶800H2O的比例混合制备成凝胶,置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,向其中加入5g甲醇和15g六甲基硅烷溶剂,混合均匀后,放置于150℃条件下反应6h,经洗涤、干燥、焙烧后,经交换得到高硅ZSM-5分子筛(样品1)。
实施例2
将硅源(固体硅胶),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPABr∶3000H2O的比例混合制备成凝胶,添加市售ZSM5晶种1%(以SiO2质量计)。置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,向其中加入5g甲醇和15g甲基硅烷溶剂,混合均匀后,放置于150℃条件下反应10h,洗涤、干燥、焙烧后经交换得到高硅的ZSM-5分子筛(样品2)。
实施例3
将硅源(固体硅胶),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPABr∶3000H2O的比例混合制备成凝胶,添加市售ZSM5晶种3%(以SiO2质量计)。置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,向其中加入5g甲醇和15g甲基硅烷溶剂,混合均匀后,放置于150℃条件下反应12h,洗涤、干燥、焙烧后经交换得到高硅的ZSM-5分子筛(样品3)。
实施例4
将硅源(固体硅胶),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPABr∶3000H2O的比例混合制备成凝胶,添加市售ZSM5晶种5%(以SiO2质量计)。置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,洗涤、干燥、焙烧后经交换得到高硅的ZSM-5分子筛(样品4)。
实施例5
将硅源(固体硅胶),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPABr∶3000H2O的比例混合制备成凝胶,添加市售ZSM5晶种8%(以SiO2质量计)。置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,向其中加入5g甲醇和15g甲基硅烷溶剂,混合均匀后,放置于150℃条件下反应12h,洗涤、干燥、焙烧后经交换得到高硅的ZSM-5分子筛(样品5)。
对比样
将硅源(硅粉),碱源(NaOH),模板剂(四丙基氢氧化铵),按照200SiO2∶25NaOH:10TPABr∶800H2O的比例混合制备成凝胶,添加市售ZSM5晶种8%(以SiO2质量计),置于晶化釜中,在160℃下晶化48h,晶化完成后水冷,经洗涤、干燥、焙烧后,经交换得到高硅ZSM-5分子筛(样品6)。
分子筛吸附性能测试
参照国家标准GB6287-1986《分子筛静态水吸附测定方法》分别测试实施例1-5的分子筛样品和对比样的疏水性能,同时选取几种常见的有机物作为VOCs来源样品进行测试。实验结果见表1:
吸附物种 | 样品1 | 样品2 | 样品3 | 样品4 | 样品5 | 对比样 |
水 | 1.5 | 1.4 | 1.3 | 0.9 | 0.76 | 1.66 |
甲苯 | 11.31 | 11.48 | 11.57 | 12.09 | 12.45 | 11.38 |
乙酸乙酯 | 12.72 | 13.26 | 12.98 | 13.11 | 13.29 | 13.01 |
正己烷 | 12.34 | 13.18 | 12.79 | 13.21 | 13.54 | 12.16 |
甲醇 | 13.18 | 12.99 | 12.91 | 13.67 | 13.55 | 12.55 |
丙酮 | 13.16 | 13.06 | 13.49 | 13.65 | 14.07 | 13.07 |
正丁胺 | 12.67 | 13.26 | 12.91 | 13.29 | 13.77 | 12.77 |
环己烯 | 8.15 | 8.07 | 7.99 | 8.19 | 8.28 | 8.03 |
由表1的数据可知:(1)与对比样(未硅烷化处理)相比,本发明的合成方法制备的高硅ZSM-5对水的吸附作用弱于对比样,说明本发明的合成方法制备的沸石分子筛具有较强的疏水性;(2)本发明的合成方法制备的沸石分子筛对各种VOCs分子的吸附量高于对比样。
Claims (10)
1.一种超高疏水性能VOCs吸附剂分子筛的制备方法,其特征在于:包括以下步骤:
(1)将硅源、碱源、模板剂、ZSM-5分子筛晶种与水混合,形成凝胶;
(2)将步骤(1)中所述凝胶置于反应釜中进行水热晶化,反应结束后,进行急冷降温,得到产物A;
(3)将步骤(2)中产物温度降至室温后,向反应釜中按一定比例补加有机醇溶剂和有机硅烷类试剂,搅拌均匀后在100-180℃条件下继续晶化6-12小时;
(4)将步骤(3)所得产物进行固液分离、洗涤、干燥、焙烧得到分子筛原粉;
(5)将步骤(4)所得分子筛原粉置入稀酸溶液中进行离子交换,然后干燥焙烧得到HZSM-5分子筛。
2.根据权利要求1所述的方法,其特征在于:所述步骤(1)中的水、碱源、模板剂、硅源以其氧化物计,所述混合物中各组分摩尔比为(2-10):(0.03-0.20):(0.03-0.50):1,所述步骤(1)中的晶种添加量为SiO2质量的0.05-10%。
3.根据权利要求1所述的方法,其特征在于:所述步骤(1)中的硅源选用固体硅胶、九水合硅酸钠、硅粉、白炭黑、硅藻土、硅酸盐和正硅酸乙酯中的任意一种或多种的混合;所述碱源选用氢氧化钠、氢氧化钾中的任意一种或多种的混合;所述模板剂选用甲胺、二乙胺、四乙基溴化铵、四乙基氢氧化铵、四丙基溴化铵、四丙基氢氧化铵、1,6己二胺、正丁胺、十六烷基三甲基溴化铵中的任意一种或多种的混合。
4.根据权利要求1所述的方法,其特征在于:所述步骤(1)中的晶种选用市售或自制ZSM5分子筛晶种。
5.根据权利要求1所述的方法,其特征在于:所述步骤(2)中水热晶化温度为150-180℃,水热时间为18-48h。
6.根据权利要求1所述的方法,其特征在于:所述步骤(3)中所述有机醇溶剂选用甲醇、乙醇、环己醇、异丁醇、乙二醇中的任意一种或多种的混合;所述有机硅烷类试剂选用三甲基氯硅烷、六甲基硅烷、六甲基二氮硅烷的任意一种或多种的混合。
7.根据权利要求1所述的方法,其特征在于:所述步骤(3)中,产物A、有机醇溶剂、有机硅烷类试剂的质量比为1:0.5:5。
8.根据权利要求1所述的方法,其特征在于:所述步骤(4)中干燥温度为120℃,干燥时间12h,焙烧温度为500-550℃,焙烧时间6-12小时。
9.根据权利要求1所述的方法,其特征在于:所述步骤(5)中离子交换条件为:将原料置于0.5~2mol·L-1的稀酸溶液中搅拌1~4h,其中交换溶液与分子筛原粉的液固质量比10-20:1,交换温度为60~95℃,并重复离子交换过程1~3次。
10.根据权利要求9所述的方法,其特征在于:所述稀酸溶液选用硫酸、盐酸或硝酸溶液中的任意一种或多种的混合。
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