CN111592009B - 一种沸石分子筛的制备方法及其应用 - Google Patents
一种沸石分子筛的制备方法及其应用 Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 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 16
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000003463 adsorbent Substances 0.000 abstract description 8
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- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 229910052680 mordenite Inorganic materials 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 40
- 239000012452 mother liquor Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
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- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
本发明提出了一种沸石分子筛的制备方法及其应用,涉及一种沸石吸附剂的制备方法和应用,具体涉及制备杂原子Fe取代的FM丝光沸石单块材料的制备方法及其应用,所述沸石分子筛由Fe与SiO2组成,所述Fe与SiO2的比以摩尔比计:Fe/SiO2=0.1%‑2%。本发明提供了一种高效的、低成本的、节能且环保的合成路线,制备杂原子Fe取代的FM丝光沸石单块材料,用于CO2捕获,取得了显著成效,吸附剂易于重复使用,绿色环保。
Description
技术领域
本技术涉及一种沸石吸附剂的制备方法和应用,具体涉及制备杂原子Fe取代的FM丝光沸石单块材料的制备方法及其应用。
背景技术
吸附和分离在工业上具有十分重要的应用价值,因此对它们的研究逐渐受到科学家的广泛关注。近年来,温室气体的排放逐年上升,减排压力日益增重,基于此背景,CO2在混合气中的吸附和分离变得十分迫切。在天然气净化(CO2、CH4混合气体),发电厂前燃烧(CO2、H2混合气体)和后燃烧(CO2、N2混合气体)技术方面,CO2的选择性吸附具有不可替代的地位。多年来该领域的发展进程表明,多孔固体吸附剂在CO2捕获和分离领域具有优异的应用前景,这类吸附剂包括烷基胺功能化的介孔二氧化硅、碳材料、金属有机框架、聚合物和沸石等。然而在CO2的吸附分离体系中还有面临以下几个挑战:(1)材料的制备成本高、制造难易度大;(2)材料对CO2气体捕获能力和选择性有限;(3)材料的再生性和稳定性一般。
通常,一个理想的目标吸附剂应同时具备较高的CO2吸附能力,优异的选择性,较强的化学和机械稳定性。在大规模的工业应用中,材料的制造成本也是一个不容忽视的问题。在沸石分子筛的制备中,传统的浸渍法负载铁存在的铁的状态难以控制,也难以进入骨架,不能稳定存在。
发明内容
本发明提出了一种分子筛,吸附二氧化碳效果好,用以分离二氧化碳和其他气体。
一种沸石分子筛的制备方法,包括以下步骤:
(1)将硅源、铁源和水混合,反应混合物以摩尔比计:Fe/SiO2是0.1%-2%,H2O/SiO2是30-40,加酸液以调节pH值为0.4-3;
(2)在上述混合液中加入铝源,铝源以摩尔比计:SiO2/Al2O3是10-30,加入碱液调节pH值为9-13;
(3)将上述混合液加入到高压反应釜中,在160-200℃静态晶化10-18天,洗涤、干燥,制得沸石分子筛;
其中,所述的硅源为硅溶胶、正硅酸四甲酯、正硅酸四乙酯、四甲基硅酸、硅酸或氧化硅中的一种,所述的铁源为硝酸铁、氯化铁、硫酸铁中的一种,所述的酸液为硫酸、盐酸、硝酸货高氯酸中的一种,所述的铝源为偏铝酸钠、硫酸铝、氯化铝中的一种,所述碱液是氢氧化钠溶液。
优选的,步骤(1)中反应混合物以摩尔比:Fe/SiO2是0.5%。
优选的,步骤(1)中调节pH值为0.8。
优选的,步骤(2)中调节pH值为11。
优选的,步骤(3)中所述高压反应釜为聚四氟乙烯衬里的不锈钢高压反应釜,容量为50L。
优选的,步骤(3)高压反应釜温度为180℃。
优选的,步骤(3)晶化14天。
优选的所述高压反应釜容积为50L。
沸石分子筛分离二氧化碳中和氮气或甲烷的应用。
有益效果
(1)本发明通过一步水热法将铁引入到沸石分子筛中,该目标材料中铁以两种形式存在:铁氧硅键存在于骨架中;铁氧团簇存在于孔道,在该吸附体系中,铁的存在形式是能够分离气体的关键。本发明合成的含铁沸石分子筛(FM),将其用于固定床层进行多组分的吸脱附分离,经过多轮测试仍然能保持好的分离效果。
(2)本发明提供了一种高效的、低成本的、节能且环保的合成路线,制备杂原子取代的FM沸石单块材料,用于CO2捕获,取得了显著成效,吸附剂易于重复使用,绿色环保。
附图说明
图1为FM-n系列样品和M-1的XRD图(n=2,3,4);
图2为FM-3样品的SEM图;
图3为FM-3样品的EXAFS图;
图4是M-1在吸附温度为273K的吸附等温线图;
图5是M-1在吸附温度为298K的吸附等温线图;
图6是FM-3在吸附温度为273K的吸附等温线图;
图7是FM-3在吸附温度为298K的吸附等温线图;
图8是M-1在吸附温度为273K CO2/N2、CO2/CH4吸附平衡图;
图9是M-1在吸附温度为298K CO2/N2、CO2/CH4吸附平衡图;
图10是FM-3在吸附温度为273K CO2/N2、CO2/CH4吸附平衡图;
图11是FM-3在吸附温度为298K CO2/N2、CO2/CH4吸附平衡图。
具体实施方式
实施例1
将5g硅源硅溶胶加入到含有10g H2O的烧杯中,在强烈的搅拌下,逐滴滴加0.3g浓盐酸至上述混合液中,调节pH至0.8,随后再加入0.013g的铁源Fe(NO3)3·9H2O,此时所得的混合溶液,在室温下进一步搅拌24h,记为溶液A。然后,在另一个干净的烧杯中,依次加入6gH2O、1.34g Al2(SO4)3和1.00g NaOH,调节pH至11,经搅拌得到溶液B。
将溶液A和B混合,在室温下搅拌老化24h得到均匀的母液,其母液组成摩尔比为:Fe/SiO2=0.1%,SiO2/Al2O3=15,调节pH值至11。最后,将老化后的母液转移到直径为3cm,高6.5cm的聚四氟乙烯衬里的不锈钢高压反应釜中,在180℃和水的自生压力下静态晶化14天。开釜直接得到的单块产物用去离子水洗涤数次并且在100℃的温度下进行干燥即可,无需额外的高温煅烧及其它后处理过程。最终所得的样品记为FM-2。
实施例2
将5g硅溶胶加入到含有10g H2O的烧杯中,在强烈的搅拌下,逐滴滴加0.3g浓盐酸至上述混合液中,随后再加入0.067g的Fe(NO3)3·9H2O,此时所得的混合溶液,在室温下进一步搅拌24h,记为溶液A。然后,在另一个干净的烧杯中,依次加入6g H2O、1.34g Al2(SO4)3和1.00g NaOH,经搅拌得到溶液B。
将溶液A和B混合,在室温下搅拌老化24h得到均匀的母液,其母液组成为:Fe/SiO2=0.5%,SiO2/Al2O3=15,调节pH值在11。最后,将老化后的母液转移到直径为3cm,高6.5cm的聚四氟乙烯衬里的不锈钢高压反应釜中,在180℃和水的自生压力下静态晶化14天。开釜直接得到的单块产物用去离子水洗涤数次并且在100℃的温度下进行干燥即可,无需额外的高温煅烧及其它后处理过程。最终所得的样品记为FM-3。
实施例3
将5g硅溶胶加入到含有10g H2O的烧杯中,在强烈的搅拌下,逐滴滴加0.3g浓盐酸至上述混合液中,随后再加入0.12g的Fe(NO3)3·9H2O,此时所得的混合溶液,在室温下进一步搅拌24h,记为溶液A。然后,在另一个干净的烧杯中,依次加入6g H2O、1.34g Al2(SO4)3和1.00g NaOH,经搅拌得到溶液B。
将溶液A和B混合,在室温下搅拌老化24h得到均匀的母液,其母液组成为:Fe/SiO2=1%,SiO2/Al2O3=15,调节pH值在11。最后,将老化后的母液转移到直径为3cm,高6.5cm的聚四氟乙烯衬里的不锈钢高压反应釜中,在180℃和水的自生压力下静态晶化14天。开釜直接得到的单块产物用去离子水洗涤数次并且在100℃的温度下进行干燥即可,无需额外的高温煅烧及其它后处理过程。最终所得的样品记为FM-4。
对比例1
将5g硅溶胶加入到含有10g H2O的烧杯中,在强烈的搅拌下,逐滴滴加0.3g浓盐酸至上述混合液中,此时所得的混合溶液,在室温下进一步搅拌24h,记为溶液A。然后,在另一个干净的烧杯中,依次加入6g H2O、1.34g Al2(SO4)3和1.00g NaOH,经搅拌得到溶液B。
将溶液A和B混合,在室温下搅拌老化24h得到均匀的母液,其母液组成为:SiO2/Al2O3=15,调节pH值在11。最后,将老化后的母液转移到直径为3cm,高6.5cm的聚四氟乙烯衬里的不锈钢高压反应釜中,在180℃和水的自生压力下静态晶化14天。开釜直接得到的单块产物用去离子水洗涤数次并且在100℃的温度下进行干燥即可,无需额外的高温煅烧及其它后处理过程。最终所得的样品记为M-1。
CO2和N2的吸附等温线在Micromeritics ASAP 2020自动等温吸附仪上测得。在273K,298K的温度下,测量在0.01bar,0.1bar,1bar下CO2的吸附量。分别将上述实施例中的产物置于样品槽中,样品槽浸没到液体循环恒温槽中进行吸附测量。在测量开始前,所有的样品在300℃下活化3h。选择性指在进行气体吸附时,对于二氧化碳的气体的吸附选择性。
气体选择性计算
Double-site Langmuir(DL)isotherm model(主要针对CO2气体)
为了具体地了解气体的分离效果,更精确的拟合吸附数据,选用Double-siteLangmuir模型(DL)来拟合CO2吸附等温线,其表达式为:
其中qc(mmol g-1),kc(kPa–1),qi(mmol g–1)和ki(kPa–1)是Double-site Langmuir模型的参数,P是对应的平衡压力。
Langmuir-Freundlich(LF)isotherm model(主要针对N2、CH4气体)
而N2、CH4吸附等温线选用Langmuir-Freundlich方程(LF)来拟合,其表达式为:
其中qi(mmol g–1)和ki(kPa–1)是Langmuir-Freundlich模型的参数,P是对应的平衡压力。
IAST的扩张压力π可以表达为:
为了计算单一组分的简约扩张压π*,IAST模型与Double-site Langmuir模型相结合,π*可由方程(1)和(2)组合计算得出:
π*=qcln(1+kcP)+qiln(1+kiP) (5)
当吸附平衡时,两组分的简约扩张分压相等:
π1 *=π2 * (6)
qc1 ln(1+kc1P)+qi1 ln(1+ki1P)=qc2 ln(1+kc2P)+qi2 ln(1+ki2P) (7)
下标1和2分别代表CO2和Ar(N2、CH4)。IAST最终的选择性可以表示为:
其中公式(8)里的x和y分别是吸附质在吸附相里的摩尔分数和在气相里的摩尔分数,i和j分别代表着
CO2和N2气体。按15/85CO2/N2的混合来计。
表1不同含量的Fe-MOR的吸附摩尔量及分离比
由上表可知,实施例2FM-3拥有最好的吸附效果,故此对实施例2FM-3作进一步的研究。
图1是上表中各实施例样品的XRD图,这些样品呈现出的峰完全归属于MOR沸石特有的结构峰,没有任何杂质峰,说明样品的结晶度较高,只是随着Fe含量的增加,样品的结晶度稍有下降。
图2是实施例2FM-3的SEM图,显示所得的FM-3沸石单块是由大小在50μm左右的扁平棱柱体构成。
图3是实施例2FM-3沸石的扩展x射线吸收精细结构(EXAFS)图谱。在傅立叶变换(FT)k3加权扩展x射线吸收精细结构(EXAFS)光谱中,只有一个显著的峰出现在大约1.4A处,主要是由于Fe-O的贡献。该结论与现有技术中的公开保持一致,现有技术来自于:
Baker L L,Nickerson R D,Strawn D G,et al.XAFS STUDY OF Fe-SUBSTITUTEDALLOPHANE AND IMOGOLITE[J].Clays and Clay Minerals,2014,62(1):20-34.
在无添加有机模板剂和粘结剂条件下,成功制备出杂原子Fe掺杂的FM单块型沸石分子筛材料。所得的单块沸石的机械强度可以满足直接作为成型吸附剂使用的要求,无需经过任何后处理或者进一步修饰。众所周知,CO2是一类弱酸性气体,再结合所制备的材料具有多级单块宏观形貌和超小微孔结构的优势,FM沸石单块将有利于CO2的吸附和分离。
图4-图7分别给出了M-1以及FM-3样品CO2、N2、CH4的吸附等温线图,吸附温度为273/298K,吸附压力为1bar。可以发现FM-3的CO2吸附量最大,分别为4.05、2.93mmol g-1。这与它们的动力学尺寸完全一致:CO2(0.33nm)<N2(0.364nm)<CH4(0.38nm)。而不掺Fe的M-1样品呈现出较低的CO2吸附能力,当温度为273和298K时,CO2的吸附量分别为2.26和1.77mmolg-1。这一现象则说明,这些含Fe的MOR沸石的孔口虽有所减小,但仍然相对足够大,能够允许较小的CO2气体分子进入,这一吸附特性对于拓宽从其它小分子气体中分离CO2的应用具有潜在的重大意义。
图8-图11为M-1以及FM-3样品的在分别在273K,1bar和298K,1bar条件下对下列二元混合物进行的吸附平衡预测:CO2/N2:15/85和CO2/CH4:50/50。该结果显示,在0.1~1bar的条件下,相比于M-1样品,FM-3样品具有超高的CO2/N2和CO2/CH4选择性。
Claims (9)
1.一种沸石分子筛的制备方法,包括以下步骤:
(1)将硅源、铁源和水混合,反应混合物以摩尔比计:Fe/SiO2是0.1%-2%,H2O/ SiO2是30-40,加入酸液调节pH值为0.4-3;
(2)在上述混合液中加入铝源,铝源以摩尔比计:SiO2/ Al2O3是10-30,加入碱液调节pH值为9-13;
(3)将上述混合液加入到高压反应釜中,在160-200℃静态晶化10-18天,洗涤、干燥,制得沸石分子筛;
其中,所述的硅源为硅溶胶、正硅酸四甲酯、正硅酸四乙酯、硅酸或氧化硅中的一种,所述的铁源为硝酸铁、氯化铁、硫酸铁中的一种,所述的酸液为硫酸、盐酸、硝酸或高氯酸中的一种,所述的铝源为偏铝酸钠、硫酸铝、氯化铝中的一种,所述碱液是氢氧化钠溶液。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中反应混合物以摩尔比:Fe/SiO2是0.5%。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中调节pH值为0.8。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中调节pH值为11。
5.根据权利要求1所述的制备方法,其特征在于,步骤(3)中所述高压反应釜为聚四氟乙烯衬里的不锈钢高压反应釜。
6.根据权利要求1所述的制备方法,其特征在于,步骤(3)高压反应釜温度为180℃。
7.根据权利要求1所述的制备方法,其特征在于,步骤(3)晶化14天。
8.根据权利要求5所述的制备方法,其特征在于,所述高压反应釜容积为50L。
9. 一种根据权利要求 1-8 任一项所述的制备方法制备获得的沸石分子筛在氮气或甲烷气体中分离二氧化碳的应用。
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