CN105531025B - 具有连接结构的沸石颗粒材料 - Google Patents
具有连接结构的沸石颗粒材料 Download PDFInfo
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- CN105531025B CN105531025B CN201480016330.8A CN201480016330A CN105531025B CN 105531025 B CN105531025 B CN 105531025B CN 201480016330 A CN201480016330 A CN 201480016330A CN 105531025 B CN105531025 B CN 105531025B
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- clay
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- 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 78
- 239000011236 particulate material Substances 0.000 title claims abstract description 63
- 239000010457 zeolite Substances 0.000 title claims description 76
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 67
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 17
- 238000005191 phase separation Methods 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 34
- 239000004927 clay Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- -1 nacrite Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000003738 xylenes Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001649 dickite Inorganic materials 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000177 wavelength dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
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Abstract
本发明涉及沸石颗粒材料,该材料在其整个体积上具有连接的沸石结构,在床中具有高机械耐压碎性,以及在大孔‑中孔中优化的材料传递。本发明还涉及制备所述沸石颗粒材料的方法。以及涉及其作为吸附材料在并流或对流液相分离方法中的用途,通常在模拟流动床中的用途。
Description
本发明涉及具有沸石结构的吸附剂领域,且更具体到有团聚形式沸石结构的吸附剂领域。本发明还涉及具有团聚形式的沸石结构的吸附剂领域,以及也涉及其用于分离气体或液体混合物的用途。
沸石的合成产生一般为粉末形式的晶体,其在工业规模上使用特别困难。具体而言,现在已知如何合成尺寸范围从几纳米到几微米的沸石晶体,这些尺寸是给予沸石最佳吸附能力所要求的。然而,关于这些小晶体有诸多缺点,其中可提到的缺点是在处置粉末时的困难和在其使用期间显著的压力损失。
为了克服这些缺点,因此已经建议用这些晶体的团聚形式,例如以粒、线、珠的形式或其他团聚形式。目前这种来自粉末形式的沸石晶体的团聚体的制造是众所周知的,并且科学文献和专利文献提供了许多制备沸石团聚体的例子,特别是通过本领域技术人员熟知的挤出、制粒和其他团聚技术。
这些团聚体通常的尺寸范围为大约几十微米,或甚至几百微米,或甚至几毫米,且没有粉末材料如先前定义的沸石晶体固有的缺点。
这些团聚体,无论以板、珠、挤出物或其他形式,一般由构成为活性元素(关于吸附)的沸石晶体和团聚粘结剂组成。
该团聚粘结剂旨在保证晶体在团聚的结构中互相凝结,但也必须对该团聚体提供足够的机械强度从而避免或至少减少在其工业应用中可能发生的破碎,破裂或断裂的风险,在所述工业应用期间,该团聚体受到众多应力,诸如振动,大的和/或频繁的压力变化,运动等。因此,受到这些各种应力的沸石团聚体保持凝结和不生成粉状微粒以导致上述缺点非常重要。
此外,影响吸附分离过程性能的重要因素特别包括吸附选择性,吸附容量,和定义各种化合物的吸附率和解吸率的物质转移动力学。因此,吸附剂必须具有优良的物质转移特性,以保证足够数量的理论板,从而对混合物中的物种实现有效分离,正如Ruthven在标题为Principles of Adsorption and Adsorption Processes,John Wiley&Sons,(1984),326和407页的公开物中表明的。
在团聚形式下的沸石吸附剂的情况中,总物质传递取决于结晶内扩散阻力和晶体间扩散阻力的增加(见Ruthven,同上,243页)。结晶内扩散阻力正比于晶体半径平方,且反比于待吸附分离的分子的结晶内扩散系数。晶体间扩散阻力(也被称为大孔阻力)其本身正比于团聚体半径的平方,且反比于大孔中待分离的分子的扩散系数。
因此,为了提高物质的转移,寻求沸石晶体直径的最小化和/或团聚体直径的最小化。然而这些尺寸缩小的团聚体,任选包含尺寸缩小的晶体,被证实为更加易碎,为了提高团聚体中晶体间互相的凝结,必需提高团聚粘结剂的含量。然而提高对于吸附惰性的团聚粘结剂的含量,团聚体的吸附容量也成比例降低,相对于以非团聚的粉末形式单独使用的沸石晶体。
因此,出现对产生结合有以下特点的团聚形式沸石吸附剂的需求:良好的物质转移特性,兼容于其工业规模使用的尺寸,一般在0.1mm和1mm之间,以及很大的机械强度,同时保留其使用所需的吸附特性。
现有技术提出了几种可能性,其中第一种可能性包括制备足够大的沸石单晶,其能够在工业分离过程中直接处理。大尺寸沸石单晶的制备已被文献所讨论。特别是,Qiu等人(Micropor.Mesopor.Mater.,21(4-6),(1998),245-251)表明,一个尺寸高达150μm的八面沸石单晶结构可通过使用很高纯度的试剂在成核抑制剂的存在下获得。除了这种类型的合成在工业化中可能面对的困难,合成尺寸0.1mm~1mm的沸石晶体似乎不可能,在没有重大实施困难的情况下,该尺寸通常是工业过程中所需的尺寸,特别是在液相。此外,由于这些材料中大孔和中孔几乎为零,非常可能观察到在沸石相待吸附/分离的化合物在特征距离(characteristic distance)上很差的传输,该特征距离对应于团聚体的尺寸或整块晶体形式的沸石吸附剂的尺寸。
美国专利申请US2012/0093715和US2013/0052126教导,整块沸石结构可能形成多级孔隙结构。提出的方法包括通过水解形成沸石前体的凝胶。该凝胶被加热到足够高的温度和足够长的时间将凝胶结晶和凝聚成整块沸石结构。反应介质中聚合物的加入导致产生具有多级孔隙结构的整块沸石结构。
然而,这些专利申请中描述的整块沸石结构具有大孔和中孔(用压汞测量),该大孔和中孔在不使用有机结构剂的情况下是低的。因此,如在单晶的情况下一样,在所述结构中的物质转移恐怕可能是相对中等的。在使用聚合物有机试剂的情况下,除了有机试剂的收缩步骤在实际上是必需的之外,相反地,该固体具有非常高的孔隙度。
因此,材料的机械强度恐怕可能是相对差的,且吸附剂的每单位床体积的吸附容量也是低的。
专利申请WO 2000/000287也介绍了产生无机物的宏观结构,其孔隙度通过使用有机树脂产生和控制,该树脂必须在过程结束时除去。
上述专利申请似乎都是不经济的,因为具体过程要求有机试剂的使用,涉及到额外的成本和在制造过程中额外的除去步骤。
Akhtar和(J.Am.Chem.Soc.,94(1),(2001),9298)也介绍了多级孔隙整块13X沸石的生产。作者表明通过添加聚乙二醇铸造(molding)经浓缩和稳定化的13X沸石粉末的胶状悬浮体使得可以得到称为坯体(green bodies)的材料,其在800℃“瞬间”热处理后,导致具有多级孔隙的整块沸石,所述整块沸石强度大饼接近于相应粉末(沸石晶体)的CO2吸附容量。
通过所述过程(铸造)得到的这些相对大的材料(显示特征尺寸为大于10mm)显示确实适用于气相过程,物质转移阻力的本质则是在微孔中。然而,可能会怀疑的是这些材料在液相应用中非常有效或在大孔-中孔中的物质转移还必须最优化。
因此,仍旧需要高机械强度的非粉末型沸石吸附材料,其在气相和/或在液相(优选在液相)中的吸附容量得到很大提高。
因此,本发明的第一个目标是提供一种沸石颗粒材料,其由在材料整个体积上渗入的(percolating)沸石结构构成,该材料具有高机械强度,在大孔和中孔中优化的物质转移,该材料便于工业化和具有相对低的制造成本。其它目标将在接下来的本发明的描述中呈现。
发明人成功地制备了这种沸石颗粒材料,其满足各种上述目标,并可能克服所有或至少一些现有技术已知的吸附剂的缺点和瑕疵。
因此,根据第一个方面,本发明的主题是具有高机械强度的沸石颗粒材料,其具有渗入的沸石结构,即在所述材料的整个体积上形成一个连接的集合体(assembly)。
更确切地说,本发明涉及到小尺寸沸石颗粒材料,一般为0.1mm~1mm,包括端值,该材料由此确保期望在液相或气相(优选在液相)中通过吸附分离的分子在材料的大孔和中孔中及在沸石相中的优化传递,以及具有提供很高机械强度的特殊结构。
根据本发明的沸石颗粒材料具有高的机械主体压碎强度(BCS),由适于小于1.6mm团聚体的Shell方法系列SMS1471-74测量,如本说明书之后描述。本发明沸石颗粒材料的BCS通常大于或等于1.0MPa,更通常大于或等于1.5Mpa,优选大于或等于2.0Mpa,一般大于或等于2.1Mpa。
术语“在所述材料的整个体积上连接的集合体”是指三维连接的结构,优选通过圆弧三维连接的结构,即在沸石材料中任意一对点经由路径连接,术语“路径”取自用于拓扑学的数学定义,由此提高支持整个机械应力的“力链”网络密度。
为了本发明的目的,制备多个抛光的部分,并用扫描电子显微镜(SEM)检查。在所述多个抛光部分拍摄十张图像,放大倍数5000-10000,对十张图像的每一个通过图像分析或任何其他合适的手段评估形成连接集合体的表面。当每个图像中连接表面占材料的占据表面的比例(十张图的平均值)为至少50%,优选至少70%,更优选至少80%时,认为本发明的沸石颗粒材料是“在所述材料的整个体积上连接的集合体”。
根据本发明的一个优选方面,沸石颗粒材料有开放的大孔隙。术语“开放的大孔隙”代表可以从颗粒材料外表面进入的孔隙,这种孔隙能够通过“压汞”技术表征,该“压汞”技术是本领域技术人员熟知的孔隙测量仪技术。
在本发明的描述中,术语“尺寸”代表物体的数均直径,或非球形物体的数均最大尺寸。本发明的沸石颗粒材料的尺寸通常为0.1mm~1mm,优选为0.2mm~1mm,特别是为0.3mm~0.8mm和更通常为0.4mm~0.6mm,包括端值。
本发明的沸石颗粒材料包括大孔、中孔和微孔。术语“大孔”代表孔径(aperture)大于50nm,优选50nm~400nm,更优选为50nm~300nm的孔隙。术语“中孔”代表孔径为2nm~50nm的孔隙,不包括端值。术语“微孔”代表孔径小于2nm的孔隙,通常孔径严格大于0且小于或等于2nm。
根据本发明的颗粒材料是沸石材料,表明它包含至少一种选自FAU结构沸石的沸石,特别选自沸石LSX,MSX,X,Y和沸石结构EMT,LTA或MFI。在这些沸石中,优选那些选自LSX,MSX,X的沸石,和更优选沸石X,不排除X型沸石和一种或多种上面列出的其他沸石的混合物。
作为通用规则,本发明的沸石颗粒材料包含大于94%重量的沸石,优选96%~98%重量的沸石,包括端值,相对于所述沸石颗粒材料的总重量。
根据优选实施方式,所述沸石是晶体形态的,其尺寸一般为10nm~1500nm,优选100nm~1200nm,更优选200nm~1100nm且最特别优选400nm~1000nm,包括端值。
本发明的沸石颗粒材料也由特定孔隙分布来表征,其中大孔和中孔的体积由压汞法测量和微孔的体积由氮气吸附法测量。术语“孔隙分布”表示随孔径变化的孔隙体积分布。此外,在本发明的说明书中,术语“Vma”是指大孔体积,术语“Vme”是指中孔体积,术语“Vmi”是指微孔体积。“Vg”代表颗粒材料的总体积。
根据本发明一种特别优选的实施方式,所述沸石颗粒材料的孔隙分布满足以下不等式1),2)和3):
本发明沸石颗粒材料的特定孔隙分布描述了如下材料,其微孔体积、中孔体积和大孔体积通过之前定义的比例进行调整,以便允许待吸附分离的化合物有效从所述颗粒材料的外部传递到所述沸石结构中,同时保持最佳吸附容量。
该特定孔隙分布与所述沸石结构的连接性质的组合可以一方面给予该材料很好的液体或气体分离特性,并且另一方面凭借晶体间存在的桥(或圆弧)的存在给予该材料非常好的机械强度。
特别地,据悉当提起晶体集合体,通过压缩,或者通过施加剪切力,在集合体中由此产生的力分布是很不均一的。具体而言,有些晶体几乎没有受到应力,而全部应力施加于其他晶体上。
使用通过晶体聚集制备的材料,经由同样性质的圆弧或桥连接在一起的集成的沸石晶体集合体的制造增加了承受所有应力的“力链”网络的密度,因此大大增加沸石材料的机械强度,使其具有与无孔隙材料相似的刚性。
因此,本发明的沸石颗粒材料包含大孔和中孔,其中在液相或气相循环传递待吸附分离化合物,从颗粒的外部传递到微孔,反之亦然。
这种大孔隙允许从外部到微孔表面的有效传递,反之亦然,无需循环通过较小尺寸的孔隙:即大孔是化合物来去微孔的主要孔隙。
根据另一方面,本发明涉及制备如刚定义的沸石颗粒材料的方法,该方法包括至少以下步骤:
a)混合至少一种沸石晶体和粘土粘结剂,该粘结剂包含至少80%,优选90%和更优选至少95%重量的可沸石化粘土,和任选的二氧化硅源,
b)与碱性溶液接触,所述碱性溶液典型地是氢氧化钠溶液或氢氧化钠和氢氧化钾的混合物,
c)封闭的密封容器中,在压力至少等于自生压力下,通常在所述自生压力和20巴之间,使悬浮液的温度通常至80℃~600℃,优选80℃~150℃,
d)通过与钡离子的溶液,或钡离子和钾离子的溶液接触,使在步骤c)的反应介质中所含的阳离子任选进行阳离子交换,
e)洗涤和干燥由此得到的沸石颗粒材料,和任选地在至少一个形成所需的尺寸的步骤,和
f)通过加热至通常100℃~400℃的温度,优选200℃~300℃的温度,将在步骤e)中得到的沸石颗粒材料活化。
步骤a)中沸石晶体和颗粒材料中沸石晶体的尺寸用扫描电子显微镜(SEM)通过拍摄一系列放大倍数至少5000的图像观察测量得到。然后用专用图像分析软件测量至少200个晶体的直径。精度约为3%。
本发明上下文中所用晶体的数均直径优选小于或等于1.5μm,优选严格小于1.2μm,且更好的还小于或等于1.1μm。
如前所述,优选八面结构的沸石晶体,其通过X-射线荧光化学分析测量的Si/Al原子比为1.00~1.50,优选1.05~1.50和甚至更优选1.10~1.50,包括端值。
在步骤a)中,除了沸石晶体和粘土,也可加入一种或多种添加剂,例如添加剂如二氧化硅,特别是在所用沸石是X型沸石的情况下。二氧化硅的可选源可以是本领域技术人员(为沸石合成专业人员)熟知的任意类型,例如硅胶,硅藻土,珍珠岩,煅烧灰(飞灰),沙,或任何其他形式的固体二氧化硅。
因此,步骤a)中所用沸石晶体可以从主要甚至完全包含钠离子的X型沸石晶体的合成中方便地得到,如在比如NaX沸石(或13X)的情形中,但是对于在合成NaX形式沸石和它在步骤a)中使用之间,经历一次或多次阳离子交换的晶体使用不构成背离本发明范围。
步骤a)中所用的粘土粘结剂包含至少80%,优选至少90%,更优选至少95%和更特别的至少96%重量的粘土,或来自高岭土,高岭石,珍珠陶土,地开石,埃洛石和/或偏高岭土的粘土混合物,和也可能包含其他矿物粘结剂比如膨润土,凹凸棒石,海泡石等。
所用粘土和沸石的比例通常是现有技术的比例,即5~20份重量的粘土每95~80份重量的沸石。
在任何情况下,粘土可以其原料状态使用或可预先进行一个或多个处理,选自比如,煅烧,酸处理,化学改性等。
根据一种实施方式,当所用粘土是高岭土时,为了将高岭土转换成偏高岭土,在步骤b)之前,在通常为500~600℃的温度下烘烤步骤a)中得到的混合物是有利操作。这一原理概述在D.W.Breck的Zeolite Molecular Sieves,John Wiley&Sons,New York(1973),314-315页。
步骤b)的与碱性溶液接触通常是通过将步骤a)中得到的混合物浸入碱性溶液中而实施的,该碱性溶液典型地是水溶液,例如氢氧化钠和/或氢氧化钾水溶液。通常,步骤b)中碱性溶液的浓度为0.5M~5M。
在冷或热,优选热,在高于室温的温度下,通常在室温(即约20℃)和碱性溶液的沸点之间实施步骤b)。
根据本发明过程的一个特点,为了在压力下且通常在自生压力下实施步骤c),在封闭且密封的容器中进行所述浸没。作为变型,可以设计外部加压装置,并且,在这种情况下,压力将在至少自生压力至20巴之间。
根据本领域技术人员熟知的方法,按常规方式在干燥之后实施活化,例如通常在100℃~400℃,优选200℃~300℃的温度下。活化步骤f)的目的是为预期应用将水含量和颗粒材料的燃烧损失设置在最佳水平。这通常通过热活化来实施,优选在200℃~300℃之间进行通常1到6小时,该时间根据期望的水含量和燃烧损失的变化来确定。
本发明的方法包括,在步骤e)中,任选至少一个使沸石颗粒材料形成期望尺寸的步骤,其可通过本领域技术人员熟知的任意技术来实施,例如造粒盘,研磨,压碎等,优选压碎。
本发明的方法也包括一个或多个任选的形成步骤,其可根据本领域技术人员已知的任意技术来实施,例如挤出,压实,聚集等。这些形成步骤可在步骤a),b),c),d),e)或f)中一个步骤或几个步骤之后实施。优选在步骤a),b),c),d),e)或f)之后仅实施一个形成步骤,且优选在步骤a),b),或c)之后实施。
形成步骤可以任选使用团聚粘结剂。根据本发明的优选实施方式,该粘结剂包括至少80%的粘土或粘土混合物,其可任选被沸石化,且有至多5%的添加剂和为形成团聚材料的水量。因此所述沸石颗粒材料可形成如前所示的尺寸为0.1mm~1mm的珠、挤出物等。
根据本发明的沸石颗粒材料特别适用于分离液相中的化合物的过程,特别是其中该材料受到很大机械应力的过程,例如并流或对流的液相分离过程,更具体地模拟流动床液相分离过程。根据本发明的沸石颗粒材料尤其适用于液相分离二甲苯的过程。
因此,根据另一方面,本发明涉及至少一种如刚定义的沸石颗粒材料在如下方法中作为吸附材料的用途:在并流或对流的液相分离方法中,更具体地在模拟流动床液相分离方法中,典型地在分离含有8个碳原子的芳族异构体混合物的芳族级分的方法中且更具体地在模拟流动床中液相分离二甲苯的方法中,以及最具体地在从含有8个碳原子的芳族异构体级分中回收高纯度对二甲苯的方法中。
最后,本发明还涉及分离包含具有8个碳原子的芳族异构体混合物的芳族级分的方法且更具体地在模拟流动床中液相分离二甲苯的方法,以及最具体地从含有8个碳原子的芳族异构体级分中回收高纯度对二甲苯的方法,例如专利申请WO 2009/081024所描述的,其中使用至少一种前述的沸石颗粒材料。
下述例子可以说明本发明的主题,仅作为指导给出,但不意味以任何方式限制本发明的各种实施方式。
通过X-射线衍射分析测定沸石颗粒材料中沸石组分的含量,该技术是本领域技术人员熟知的,缩写为XRD。在Brüker牌机器上进行分析,然后用来自Brüker公司的TOPAS软件评价沸石组分的含量。
通过所述沸石颗粒材料的元素化学分析,更精确地通过如标准NF ENISO 12677:2011描述的在波长色散光谱仪(WDXRF)如来自Brüker公司的Tiger S8上进行X射线荧光化学分析,就Si/Al原子比和阳离子交换程度来评价沸石颗粒材料。X射线荧光光谱具有极少依赖元素的化学结合的优势,提供既定量又定性的精确测定。在校准每一氧化物SiO2,Al2O3,还有钠,钾和钡氧化物之后,按惯例得到小于0.4%重量的测量不确定度(measuringuncertainty)。Si/Al原子比的测量不确定度为±5%。
使用传送带使样品在照相机物镜前经过,根据标准ISO 13322–2:2006的图像分析,通过对团聚样品的颗粒尺寸分布的分析进行颗粒材料尺寸的确定。通过应用标准ISO9276-2:2001,从颗粒尺寸分布计算得到物体的尺寸(数均直径)。对于本发明的沸石颗粒材料的尺寸范围,精度约为0.01mm。
在仪器操作手册(指标准ASTM D4284-83)中描述的实验方法包括放置吸附剂样品(待测量的沸石颗粒材料)(已知燃烧损失),在孔隙仪小室中提前称重,然后在预除气(至少10分钟真空压力30μmHg)之后,在给定压力(0.0036MPa)下往小室中注汞,然后施加压力逐步增加到400MPa,如此可使汞逐渐渗透到样品的孔隙网络中。
假设为圆柱孔,汞和孔壁间的接触角为140°和汞的表面张力为485dynes/cm,建立施加压力和表观孔径间的关系。记录随施加压力变化的引入的汞的累积量。压力值设定在0.2MPa,在该值及以上汞将填充所有的颗粒间孔隙,并且在该值以上汞被认为渗入到颗粒材料的孔隙。然后通过以下方法计算颗粒体积(Vg):孔隙仪小室的体积减去在所述压力(0.2Mpa)下汞的累积体积,然后将这个差值除无水等效颗粒材料质量,即该材料校正燃烧损失后的质量。
颗粒材料的大孔被定义为在压力0.2MPa~30MPa之间引入的汞的累积体积,对应于表观直径大于50nm的孔所含的体积。颗粒材料的中孔体积被定义为在压力30MPa~400MPa间引入的汞的累积体积。
因此在本文中,沸石吸附剂中大孔和中孔的体积,以cm3.g-1表达,通过压汞法测量且涉及到样品的无水等效质量,即该材料校正燃烧损失后的质量。
根据本领域技术人员熟知的任意方法确定微孔的体积,例如对气体在其液化温度下吸附等温线的测定,所述气体例如氮气,氩气,氧气等。在吸附测量前,本发明的沸石颗粒材料在300℃~450℃、在真空下(P<6.7×10-4Pa)时间除气9小时到16小时。例如,对于FAU结构沸石,在得自Micromeritics的ASAP 2010M仪器上在77K进行氮气吸附等温线的测定,在P/P0比率为0.002~1的相对压力下取至少35个测量点。通过应用标准ISO 15901-3:2007从所得的等温线,根据Dubinin-Raduskevitch等式确定微孔体积。因此,如此评价的微孔体积表示为每克吸附剂的立方厘米的吸附液体。测量不确定度为±0.003g/cm3。
测量得到的机械强度是根据Shell方法系列SMS1471-74(催化剂主体压碎强度的测定。压滤法(compression-sieve method))表征的主体压碎强度(BCS),与由VinciTechnologies公司所售的BCS测试仪有关。
该测量BCS的方法最初打算用于表征3mm~6mm的催化剂,是基于425μm筛子的使用,该筛子特别使得分离破碎过程中产生的细粒成为可能。425μm筛子的使用仍适合直径大于1.6mm颗粒,但必须根据材料期望表征的颗粒尺寸来改变。对于本发明的沸石颗粒材料,使用200μm筛子代替在Shell方法的标准SMS1471-74中提到的425μm筛子。
测量方案如下:将待分析的20cm3材料样品提前用合适的筛子(200μm)筛选并在烘箱中在250℃提前干燥至少两小时(而不是在Shell方法标准SMS1471-74中提到的300℃),然后放置在已知内截面的金属圆筒内。借助于活塞通过5cm3的钢球床在样品上逐步施加增加的压力,以便更好地分散由活塞施加到材料的力(对于直径严格小于1.6mm的球形颗粒使用2mm直径的球)。在不同压力阶段获得的细粒通过筛选分离(200μm的合适筛子)并称重。
由压力确定的BCS以兆帕(MPa)计,其中通过筛的细粒的累积量是样品重量的0.5%。通过绘制所得细粒的质量与施加于沸石材料床的压力的变化关系图并内推到0.5%的细粒累积质量而获得该值。机械主体压碎强度通常在几百KPa导几十MPa之间,且通常为0.3MPa~3.2MPa。精确度通常小于0.1兆帕。
附图是通过扫描电子显微镜(SEM)观察各种沸石颗粒材料的抛光部分所得到的图像。通过离子抛光(氩离子)制备材料的抛光表面。用于制备抛光表面的仪器是Gatan所售的仪器Ilion+TM,具有如下参数:5kV的加速电压,4小时的抛光时间,倾斜角度0°,室温,截面模式。
附图说明如下:
·图1a:对应实施例1的非连接的沸石颗粒材料,放大倍数5000;
·图1b:对应实施例1的非连接的沸石颗粒材料,放大倍数10000;
·图2a:对应实施例2的连接的沸石颗粒材料,放大倍数5000;
·图2b:对应实施例2的连接的沸石颗粒材料,放大倍数10000。
为了观察样品,在如下条件下使用场发射枪扫描电子显微镜(FEG SEM):2kV的加速电压,使用Everhart-Thornley侧面二次电子探测器的图像分析,放大参考Polaroid545。样品不经受金属化。
以下实施例可以说明本发明的主题。它们仅仅作为指南给出,并不意图以任何方式限制本发明的各种实施方式。
实施例1(比较例):
制备基于NaX的非连接的材料
基于X型沸石粉末制备沸石吸附剂,其中晶体尺寸1μm,Si/Al原子比=1.25,通过如下方式获得:均匀混合和聚集100g(表示为煅烧当量)晶体尺寸1μm和Si/Al原子比=1.25的NaX型沸石粉末与15g高岭土(表示为煅烧当量)与7.5g以商标名30(包含30%重量的SiO2和0.5%的Na2O)售出的胶体二氧化硅以及适于挤出操作的水量。
为了重新获得数均当量直径等于0.5mm的颗粒,干燥、压碎所述吸附剂,然后在550℃、在氮气气流下煅烧2小时。
在这一步中,用SEM对本发明材料的抛光部分进行观察:在十张放大倍数10000倍的图像上,观察到沸石晶体的团聚体,由此看到该晶体在所述材料整个体积上不形成连接的集合体,在图像(图1a)中连接表面为材料所占表面的约5%。
实施例2(根据本发明):
合成基于NaX的连接的沸石材料
使用实施例1中制备的沸石吸附剂。
将这些干燥和煅烧后的挤出物与碱性溶液接触,所述碱性溶液通过轻轻搅拌混合200g氢氧化钠(水中50%重量的NaOH)和300g水配制。然后将混合物转移到塑料管中,然后密封。该体系保持在自生压力下调节为120℃的温度下2小时。
回收吸附剂,然后用水洗至pH值接近于10。为了回收数均当量直径等于0.5mm的颗粒,干燥、压碎挤出物,然后在氮气流下在550℃煅烧2小时。
在本步骤中,使用SEM观察通过离子抛光制备的吸附剂的抛光部分。观察在不同抛光部分拍摄的放大倍数为10000的十张图像,显示出均匀的孔隙度和均匀的材料。SEM图像分析显示,平均十张图像,每张图像上的连接的表面约占材料所占表面的78%,对应于本发明含义中的连接材料。
而且,在所述条件下抛光的期间经由幕帘效应(在图2a或图2b中观察到的沟槽)观察到机械强度的增加,为硬物质的材料特性。在图1a或图1b代表的材料的抛光中缺少这种效应,该材料是沸石晶体的团聚体,所以该晶体不形成一个连接的集合体。
实施例3(根据本发明):
合成基于BaX的连接的沸石材料
将50g氢氧化钠(50%重量,在水中),20g(表示为无水等效物)的晶体尺寸0.8μm和Si/Al原子比=1.20的NaX沸石粉末,提前在550℃煅烧2小时的1g高岭土(表示为煅烧当量)和0.5g在商标名30下所售的胶体二氧化硅(包含30%重量的SiO2和0.5%Na2O)与25g水在容器中混合。
将由此所得的混合物转移到塑料管中,然后密封。该体系保持在自生压力下调节为120℃的温度下2小时。
回收吸附剂,然后用水洗至pH接近于10。为了回收数均当量直径等于0.5mm的颗粒,干燥、压碎挤出物,然后在氮气流下在550℃煅烧2小时。
这些吸附剂经0.5M氯化钡水溶液的作用在95℃进行四步骤阳离子交换。在每一步骤,溶液体积与固体质量的比例为20mL/g和每次交换持续4小时。在每一步交换之间,为了除去多余的盐多次洗涤该固体。然后,在80℃干燥团聚体2小时,最后在氮气气流下在250℃活化2小时。
Claims (10)
2.如权利要求1所要求的沸石颗粒材料,包括至少一种选自FAU、EMT、LTA或MFI结构沸石的沸石。
3.如权利要求1或权利要求2所要求的沸石颗粒材料,包括至少一种选自沸石LSX, 沸石MSX和沸石X的沸石。
4.如权利要求1或2所要求的沸石颗粒材料,包含超过94%重量的沸石,包括端值,相对于所述沸石颗粒材料的总重量。
5.制备如权利要求1-4任一项所要求的沸石颗粒材料的方法,包括至少以下步骤:
a)混合至少一种沸石的晶体和粘土粘结剂,所述粘结剂包含至少80%重量的可沸石化粘土,和任选的二氧化硅源,
b)与碱性溶液接触,
c)在封闭的密封容器中,在至少等于自生压力的压力下,使悬浮液的温度达到80°C~600°C,
d)通过与钡离子的溶液,或钡离子和钾离子的溶液接触,使在步骤c)的反应介质中所含的阳离子任选进行阳离子交换,
e)洗涤和干燥由此得到的沸石颗粒材料,和任选的至少一个形成所需的尺寸的步骤,以及
f)通过加热至100°C~400°C的温度,将在步骤e)中得到的沸石颗粒材料活化。
6.如权利要求5所要求的方法,其中步骤a)中所用的粘土粘结剂包含至少80%重量的来自高岭土、高岭石、珍珠陶土、地开石、埃洛石和/或偏高岭土的粘土或粘土混合物。
7.如权利要求6所要求的方法,其中步骤a)中所用的粘土粘结剂还包含其他矿物粘结剂。
8.至少一种如权利要求1-4任一项所要求的沸石颗粒材料在用于分离包括含有8个碳原子的芳族异构体混合物的芳族级分的并流或对流液相分离方法中作为吸附材料的用途。
9.一种用于分离包括含有8个碳原子的异构体混合物的芳族级分的方法,其中使用至少一种如权利要求1-4任一项所要求的沸石颗粒材料。
10.如权利要求9所要求的方法,其是在模拟流动床中分离二甲苯的液相方法。
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PCT/EP2014/075191 WO2015075140A1 (fr) | 2013-11-20 | 2014-11-20 | Matériau granulaire zéolithique à structure connexe |
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