CN1311757A - 制备分子筛的方法 - Google Patents
制备分子筛的方法 Download PDFInfo
- Publication number
- CN1311757A CN1311757A CN99809151A CN99809151A CN1311757A CN 1311757 A CN1311757 A CN 1311757A CN 99809151 A CN99809151 A CN 99809151A CN 99809151 A CN99809151 A CN 99809151A CN 1311757 A CN1311757 A CN 1311757A
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- Prior art keywords
- molecular sieve
- desired method
- seed
- sapo
- structure type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 50
- 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 50
- 238000000034 method Methods 0.000 title claims description 46
- 230000008569 process Effects 0.000 title description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 67
- 239000002245 particle Substances 0.000 claims description 32
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- 239000000725 suspension Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 6
- 229910052676 chabazite Inorganic materials 0.000 claims description 6
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
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- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- 238000006317 isomerization reaction Methods 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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Abstract
将胶体结晶分子筛种子用于生产含磷结晶分子筛。某些产物在含氧物转化中具有较高的应用价值。
Description
本发明涉及分子筛及其制备方法。更具体地说,它涉及其中对合成混合物进行引种以控制工艺条件和产物特性的方法。本发明主要涉及含磷分子筛的制备方法。
人们熟知,向分子筛合成混合物引种往往产生有益效果,例如控制产物的粒径,避免需要有机模板剂(template),加速合成,并提高期望结构类型产物的比例。
美国专利4440871描述了许多含磷分子筛的制备工艺,按照其所述,结晶过程可通过对合成混合物的搅拌、或其它温和搅动、或通过用待生产的分子筛晶体或具有几何形态类似结构的分子筛晶体对合成混合物进行引种而促进。
该专利特别描述了制备包括SAPO-34的许多结晶微孔硅铝磷酸盐(SAPO)的方法,其中采用了硅源(如,硅胶)、铝源(如,水合氧化铝)、和磷源(如,正磷酸)、以及有机模板剂,例如四乙基氢氧化铵(TEAOH)、异丙胺(iPrNH2)或二正丙胺(DPA)。该专利(其内容在此作为参考并入本发明)给出了SAPO的X-射线衍射图,并描述了它们在催化和吸收方面的用途。
现已发现,在制备含磷分子筛时使用胶体种子是有利的。
因此,本发明的第一方面提供了一种制备在其骨架中含磷的结晶分子筛的方法,该方法包括,在适合形成所需分子筛的时间和温度下,对包含形成所述含磷分子筛所需的元素和胶体结晶分子筛种子的合成混合物进行处理。
还已惊人地发现,该种子晶体可具有不同于所需分子筛的结构类型。这种引种可看作“异结构的”,而用相同结构类型的种子进行引种则称作“同结构的”,而无论该种子是否具有与所要制备的结晶分子筛相同的组成(即,包含相同比例的相同元素)。
在种子的结构类型不同于所需的分子筛的情形,该种子和所需分子筛有利地在拓扑结构上类似,例如,为ABC-6组材料的组元,例如描述于沸石和相关材料的拓扑化学。J.V.Smith,Chem.Rev.1988,88,149-167,在此将该回顾论文的内容作为参考并入本发明。ABC-6组包括,尤其是钾沸石、菱沸石、和插晶菱沸石结构。
本说明书所用的术语“结构类型”按照结构类型图集,沸石17,(1996)所述的含义使用。
因此,本发明的第二方面提供了一种制备在其骨架中含磷的结晶分子筛的方法,该方法包括,在对于形成第一结构类型分子筛的充分的时间和适宜的温度下,对包含形成第一结构类型含磷分子筛所需的元素和第二的不同结构类型的胶体分子筛种子晶体的合成混合物进行处理。
另一方面,本发明提供了胶体种子晶体在合成含磷结晶分子筛中的应用,以便控制产物的粒径,或加速形成产物,或同时控制粒径并加速形成产物。
作为通过本发明方法制备的含磷分子筛,可以更尤其提及铝磷酸盐和硅铝磷酸盐。作为所产生的结构类型的例子,可以更尤其提及具有结构类型CHA和LEV的分子筛。作为种子,可以使用例如具有结构类型LEV、OFF、和CHA的晶体。作为可以使用的具体材料,可以提及插晶菱沸石、ZSM-45、菱沸石、钾沸石、和SAPO-34。
用于本发明的种子可通过本文描述或本领域已知的或在文献中描述的方法而得到。
OFF-结构类型种子晶体,尤其是胶体钾沸石种子可例如按照国际专利申请WO97/03020所述来生产,而适用于生产LEV-和CHA-结构类型晶体具体的工艺步骤,包括合成混合物和水热处理的细节则描述于EP-A-91048、91049、107370、143642和美国专利4495303(对于LEV)和GB-A-868846和2061500以及美国专利3030181和4544538(对于CHA),在此将其作为参考并入本发明。CHA-和LEV-结构类型种子晶体的生产有利地按照以下实施例所述来进行。
除了存在种子,用于本发明的合成混合物通常是本领域已知的或在文献中描述为适用于生产有关的分子筛的那些。对于处理条件也如此,只是种子的存在使得减少反应时间成为可能,或可避免搅拌,如果搅拌否则是必需的。
一般来说,对合成混合物生成所需含磷结晶分子筛的处理通常称作水热处理,但严格地说该术语应仅用于其中存在蒸气相水的处理,这种处理有利地在自生压力下,例如在高压釜如不锈钢高压釜(如果需要,衬以聚四氟乙烯)中进行。该处理例如,可在从50(有利地90,尤其是120)-250℃的温度下进行,这取决于所制的分子筛。该处理可例如,在20-200小时,优选最高100小时的时间内进行,这同样取决于所形成的分子筛。工艺步骤可包括熟化期,可以在室温下或优选在中等高温下,在更高温度下水热处理之前。后者可包括温度逐渐或逐步变化的过程。
对于某些应用场合,处理是在搅拌下或在将容器围绕水平轴旋转(滚动)的同时进行的。对于其它应用场合,优选静态水热处理。如果需要,可在加热阶段的起始部分过程中搅拌或滚动该合成混合物,例如从室温至升高的(例如,最终处理)温度,其余为静态处理。搅拌一般得到一种比起静态水热处理具有较小粒径和较窄粒径分布的产物。
种子一般在合成混合物中的浓度最高为10000,有利地最高3000,更有利地最高1500,优选最高1000,更优选最高500,最优选最高350ppm,以合成混合物的总重为基。最低引种量一般为1ppb(0.001ppm),有利地至少0.1,更有利地至少1,优选至少10ppm,以合成混合物的总重为基。有利的比例范围为1-2000,优选100-1500,最优选100-250ppm。
有利的是,胶体种子以悬浮液的形式加入合成混合物中,有利地在含水介质,优选水、或合成混合物的另一液体组分中。它们不太优选以干的、但未煅烧的形式加入。据信煅烧明显降低微小晶用作种子的活性;类似地,应该避免降低材料引种活性的任何其它处理。本文所用的术语“胶体”在用于悬浮液时是指,一种包含分散在连续液相中的离散细分颗粒的悬浮液,优选是指一种在预期使用的足够期间内,在环境温度(23℃)下有利地至少10,更有利地至少20,优选至少100,更优选至少500小时内稳定的悬浮液,即,没有发生可见的分离或形成沉淀物。
悬浮液保持稳定(胶溶的)的最大粒径在某种程度上取决于它们的形状、该连续介质的性质和pH值、以及该悬浮液必须保持稳定的期限。一般来说,最大粒径可以是1μm,有利地为500,更有利地400,优选300,更优选200,最优选100纳米。颗粒可以是球状、柱状、杆、棺材、片、或针状。如果颗粒是片状或针状,那么所指尺寸是它们的最小尺寸。
最低尺寸是指使得这些颗粒不会溶解或再溶解于介质中,而且对于结晶度,它们必须包含至少少量多个,有利地至少两个,优选四个晶体单元晶胞。最低粒径一般为5,有利地为10,优选为20纳米。平均粒径一般为5-1000,有利地10-300,更有利地10-200,优选20-100纳米。有利地至少50%,更有利地至少80%,更优选至少95%数目的颗粒大于给定的最小值、小于给定的最大值、或在给定的粒径范围内。粒径的测量可通过电子显微镜,例如使用Philips SEM 515装置来进行。
如果要求产物为小粒径形式,最好采用较大数目的尺寸较小的种子。种子的粒径越小,有效的重量百分数越低。有利地将晶体在足够时间内搅拌到合成混合物中以得到一种均匀的分散体,该时间主要取决于合成混合物的粘度、以及设备的规模和种类,但范围一般为30秒至10分钟。
更具体地说,本发明提供了其中将胶体LEV结构类型种子用于生产含磷结晶分子筛的方法和用途。
LEV胶体悬浮液可这样得到:通过水热处理合适的合成混合物来合成出LEV结构类型分子筛,将产物从合成混合物中分离,洗涤产物,然后回收所得洗涤液体。
LEV结构类型的例子包括插晶菱沸石、NU-3、ZK-20、ZSM-45和SAPO-35。
胶体LEV种子特别适用于得到具有CHA结构类型的结晶分子筛。这种CHA材料的例子为SAPO-、ALPO-、MeAPO-、MeAPSO-、ElAPSO-和ElAPO-47,尤其是相应的-34材料。在这些结构式中,El表示镁、锌、铁、钴、镍、锰、铬或任何两种或多种这些元素的混合物。CHA结构类型种子也可用于合成这些材料。LEV和CHA结构类型种子可用于合成具有LEV结构类型的SAPO-、ALPO-、MeAPO-、MeAPSO-、ElAPSO-和ElAPO-材料,如-35材料。如果一种材料称作例如SAPO材料,那么该术语包括其它元素以在骨架中或其它方式存在的可能性,例如在以下讨论Ni-SAPO时的情形。
在这些材料中,已发现SAPO-34明显可用于将甲醇催化转化成轻质烯烃,主要是具有2-4个碳原子的那些(参见,例如美国专利5126308,也在此并入本发明))。能够增加乙烯在产物中的比例是有价值的。
因此,本发明还提供了一种通过其中所述合成混合物包含胶体结晶分子筛晶体的工艺来制备SAPO-34的方法,其中Broensted酸位对IR光谱中总OH面积的百分面积贡献至少为30%,有利地至少为50%,优选至少60%。在某些实施方案中,百分面积贡献最高为95%。
更具体地说,本发明还提供了一种生产SAPO-34的方法,包括,在足以形成SAPO-34的时间和温度下,对具有适合形成SAPO-34的摩尔组成且还包含有利地具有最高400纳米平均粒径的胶体OFF类型、CHA类型、或LEV类型种子晶体的合成混合物进行处理。
本发明方法还能够提供其中粒径最高为0.75μm,有利地最高为0.5μm的SAPO-34。有利地,粒径分布使得80%(数目)的颗粒在平均值的±10%以内。
另一方面,本发明提供了一种将含氧物,尤其是甲醇转化成烯烃的方法,包括,将该含氧物与催化剂在转化条件下接触,所述催化剂包含按照本发明生产的SAPO-34。
所得烯烃有利地为轻质烯烃,可以理解为其中至少50%重量包含2-4个碳原子的一种烯烃混合物。
现更尤其考虑到本发明的Broensted酸位,据信(但本发明不受任何理论考虑的局限)Broensted酸性对于分子筛的催化活性是重要的,尤其是在含氧物转化成烯烃时,而且其中在晶体中高比例羟基为桥接羟基的分子筛时具有高活性。本发明高活性产物的红外分析(在以下实施例中更详细描述了测量方法)表明,在SAPO-34的OH区,4000至3000厘米-1的两个峰(在~3620和~3595厘米-1)是主要特征,而较不活性的样品则在3750至3620厘米-1范围内表现出许多带,归属于外表面上或内缺陷上的Al-OH、Si-OH、和P-OH基团。
与催化活性有关的其它IR光谱特性是在T-O非对称伸缩区中(在1050-1150厘米-1)的高峰值强度,强度由高度和锐度两者来表示,即高度的内部结晶度。因此,高内部结晶度或晶体完整性与Broensted OH基团对该材料总OH含量的高贡献率之间据信存在关联。
此外,与许多其它的分子筛一样,一般而言,粒径越小,SAPO-34的催化活性和活性稳定性越大。
按照本发明,除了胶体种子,用于生产SAPO-34的合成混合物有利地包括具有以下范围内的摩尔组成:
P2O5∶Al2O3 0.9-1.2∶1
SiO2∶Al2O3 0.05-0.4∶1
H2O∶Al2O3 10-100∶1
以及有机模板剂,有利地为四乙基氢氧化铵(TEAOH)、二丙胺(DPA)、异丙胺或吗啉、或两种或多种这些模板剂的混合物,其比例适合生成SAPO-34。优选的模板剂混合物包含TEAOH和DPA。
在本发明的一个特别有利的实施方案中,该合成混合物有利地包含金属元素源,尤其是第Ⅷ族金属,更尤其是镍。金属的常规源为水溶性盐,例如硝酸盐。该金属相对Al2O3的摩尔比例(以氧化物计)有利地为0.001-0.05,优选0.005-0.01。镍的存在可增强至少在含氧物转化时的催化活性。其它的合适族Ⅷ金属包括Fe和Co,而其它的合适金属包括Mn、Cr、Cu、Zn、Mg、Ti和Zr。
材料源可以是任何的商业用途的那些或描述于文献,可在制备合成混合物时使用。
本发明还提供了本发明早先方面所述方法的产物和应用。如果需要,该产物可在阳离子交换和/或煅烧之后用作催化剂前体、催化剂、以及分离和吸收介质。它们尤其适用于多种烃转化、分离和吸收。它们可单独或与其它分子筛结合,以颗粒形式(承载或未承载的)、或以承载层的形式,例如以膜的形式来使用,例如描述于国际专利申请WO94/25151。烃转化包括,例如裂解、重整、加氢精制、芳构化、低聚化、异构化、脱蜡、和加氢裂化(如,石脑油至轻质烯烃、高分子量至低分子量烃,烷基化、烷基转移反应、芳香物质的歧化或异构化)。其它的转化包括醇类与烯烃的反应、以及含氧物转化成烃。
含氧物的转化可将含氧物例如甲醇在液体或优选在蒸气相中,以分批或优选连续方式来进行。如果以连续方式来进行,可方便地采用,有利地为1-1000,优选1-100/小时的基于含氧物重量小时空间速度(WHSV)。一般需要高温来获得经济的转化率,如300-600℃,优选400-500℃,更优选约450℃。催化剂可以在固定床,或动态如流化床或移动床中。
可将含氧物原料与在反应条件下惰性的稀释剂,如氩气、氮气、二氧化碳、氢气或水蒸气进行混合。甲醇在原料中的浓度可变化较大,例如为原料的5-90%摩尔。压力可在较宽范围内变化,例如为大气压至500kPa。
以下实施例用于说明本发明,除非另有所指,其中份数都是以重量计的。除非另有所指,起始原料的来源和纯度都是首次给出的。
实施例1
该实施例说明LEV型沸石的制备工艺,该沸石的粒径在生产尤其是含磷结晶分子筛时适用作种子。
在第一步中,将15.95份铝酸钠(Dynamit Nobel,53%Al2O3、41%Na2O、6%H2O)、19.95份氢氧化钠(Baker,98.6%)和5.58份氢氧化钾(Baker,87.4%)溶解在151.06份水中,然后加热至沸腾,得到一种澄清的溶液。冷却至室温之后,补偿水损失以形成溶液A。将270.60份胶体硅石(Ludox HS40,40%SiO2)与106.12份胆碱盐酸盐(R,Fluka)混合形成一种粘稠的物质,然后在搅拌下加入溶液A随着以递增速率搅拌粘度下降,以及190份漂洗水,然后继续混合5分钟。摩尔组成为:
1.95Na2O∶0.24K2O∶0.46Al2O3∶10SiO2∶4.187R∶155H2O。
向290份该混合物中,加入0.49份常规LEV沸石种子,然后将样品转移到高压釜中,在此将其在120℃炉中加热144小时。洗涤产物,离心处理回收,然后在120℃下干燥过夜。该产物包含2-2.5μm的球状聚集体,由约100纳米颗粒组成,X-射线衍射图(XRD)为ZSM-45,一种LEV型结构沸石,例如描述于EP-A-107370(Mobil)。
将该产物用作下一步的种子,其中将8.38份铝酸钠、10.53份氢氧化钠、2.96份氢氧化钾、和78.95份水按照上述进行处理,得到溶液A。然后按照上述,将该溶液A连同100.00份漂洗水加入142.42份胶体硅石和55.5份胆碱盐酸盐的混合物中并混合,同时加入0.68份第一步种子。将该反应混合物在120℃下在高压釜中加热174小时,通过洗涤、离心处理和干燥而回收的产物具有类似于第一步产物的XRD。洗涤工艺的第二上层清液并不澄清,且pH值为10.3。结果发现,它是一种固体含量2.3%的分散体。扫描电子显微镜(SEM)和XRD分析表明是具有ZSM-45结构(LEV结构类型)的约100纳米未聚集晶体。
实施例2
该实施例说明菱沸石分散体的制备过程,后者又适合在制备SAPO-34时用于引种。种子制备如下:
按照实施例1的第一部分所述制备出合成混合物,只不同的是使用来自实施例1第二部分的第二上层清液的胶态溶胶作为种子,引种量为0.15%重量(固体物质)。将引种的合成混合物在120℃下在不锈钢高压釜中加热96小时,其中加热升温(heat-up)时间为3小时。离心处理并干燥而回收的产物具有对应于ZSM-45的XRD图。第一上层清液并不澄清,在11000rpm下离心处理并进一步洗涤之后,得到一种粒径约100纳米的晶体的固体含量4.6%的分散体,XRD表明该产物为ZSM-45,一种LEV结构类型沸石。
使用以下组分,按照以下比例,如实施例1所述制备出溶液A:
NaOH 61.66
KOH 28.73
Al(OH)3(Alcoa,99.3%) 15.73
H2O 190.30
将300.23份胶体硅石和168.89份水倒入混合器中,然后将溶液A与12.65份漂洗水一起加入。混合5分钟之后,加入16份的4.6%固体含量LEV浆液。该合成混合物的摩尔组成为:
3.8Na2O∶1.12K2O∶0.5Al2O3∶10SiO2∶161H2O,其中有927ppm种子。
将合成混合物经2小时在高压釜中加热至100℃,然后在该温度下保持96小时。冷却之后,用软化水5次洗涤该高压釜的内容物,一种乳状悬浮液,然后在9000rpm下离心处理。在为XRD和SEM取样之后,将剩余物再分散,形成一种在几天内稳定且固体含量为6.4%的胶体溶液。该产物的XRD表明,它是一种具有均匀粒径100×400纳米的菱沸石。
实施例3
该实施例说明具有小粒径和均匀粒径分布的SAPO-34的生产工艺。
由以下组分,按照所示比例制备出合成混合物。溶液 组分 比例A Al2O3(Pural SB Condea 75%) 68.18
H2O 100.02B H3PO4(Acros,85%) 115.52
H2O 80.27C 胶体硅石(Ludox AS40) 22.73
H2O,漂洗 10.20D TEAOH(Eastern Chemical,40%) 182.85E DPA(Fluka) 80.23F 种子,4.6%重量LEV 31.95
在混合器中制备出浆液A,然后加入溶液B,得到一种粘稠的溶液。将该溶液放置2分钟之后,加26.84份漂洗水。混合该膏体6分钟之后,加入C,然后在加入溶液D之前混合2分钟。在与70.72份漂洗水一起加入E时,形成了两相。另外混合3分钟之后,得到一种视觉均匀的溶液,然后在另外混合10分钟之后,加入种子F。摩尔组成如下:
Al2O3∶P2O5∶0.3SiO2∶TEAOH∶1.6DPA∶56H2O.
+1860ppm(重量)LEV种子。
将引种后的凝胶在175℃下,在不锈钢高压釜中加热60小时。固体产物通过离心处理而回收,水洗11次至导电率为约18μs/cm,然后在120℃下干燥。XRD和SEM表明为一种晶体为0.2-1.3μm,且少数晶体为2-3μm的纯SAPO-34产物。化学分析表明一种具有以下摩尔组成的产物:
Al2O3∶0.99P2O5∶0.36SiO2。
按照类似方式,由以下组分,以所示比例制备出合成混合物。溶液 组分 比例A Al2O3(Pural SB Condea 75%) 68.06
H2O 100.15B H3PO4(Acros,85%) 115.74
H2O,包括漂洗水 104.92C 胶体硅石(Ludox AS40) 22.50
H2O,漂洗 10.20D TEAOH(Eastern Chemical,40%) 183.31
H2O,漂洗 43.17E DPA(Fluka) 80.79
H2O,漂洗 26.27
在混合器中制备出浆液A,然后加入溶液B,得到一种粘稠的混合物。混合6分钟之后,加入溶液C并混合2分钟,然后加入溶液D并混合5分钟。在加入E时,形成了两相。另外混合15分钟之后,得到一种视觉均匀的混合物。摩尔组成如下:
Al2O3∶P2O5∶0.3SiO2∶TEAOH∶1.6DPA∶52H2O。
将合成溶液分开,然后向一个样品中加入按照实施例2所述制备的CHA沸石的6.4%浆液,得到410ppm的引种量,另一样品保持未引种。
将未引种样品在175℃下在不锈钢高压釜中加热60小时。将引种样品分开,一部分在175℃下在聚四氟乙烯内衬的高压釜中在没有搅拌下加热60小时,而另一部分则在175℃下在不锈钢高压釜中在滚动下加热60小时。
将样品冷却,然后将产物洗涤并在120℃下干燥而回收。在所有情况下,得到纯的SAPO-34产物,其摩尔化学组成和晶体尺寸如下:
未引种:Al2O3∶0.91P2O5∶0.33SiO2,1-10μm
引种,
静态: Al2O3∶0.89P2O5∶0.31SiO2,0.2-1.5μm
引种,
滚动:Al2O3∶0.91P2O5∶0.35SiO2,~0.5μm。
用胶体菱沸石种子引种来降低晶体尺寸和尺寸分布的益处是显然的,尤其是在结合滚动操作时。
实施例4
该实施例说明胶体钾沸石种子在制备SAPO-34中的应用。胶体钾沸石按照WO97/03020实施例2所述来制备。按照实施例3所述制备出合成混合物,其摩尔组成如下:
Al2O3∶P2O5∶0.3SiO2∶TEAOH∶1.6DPA∶51H2O。
向其中加入一部分5.36%固体含量的胶体钾沸石浆液(晶体尺寸低于100纳米),得到203ppm的引种量。按照实施例3所述进行水热处理和产物回收。所得产物为纯的SAPO-34,晶体的粒径主要为0.2-1.3μm,少量晶体为2-3μm。
对比例A
该实施例说明被某些钾沸石污染的粉状LEV在制备SAPO-34中的应用。向为实施例4制备的相同合成混合物中加入LEV粉末,得到217ppm的引种量。通过在聚丙烯瓶中振动凝胶2分钟而将粉末混入合成混合物的凝胶中。按照实施例4所述进行水热处理和产物回收。所得产物为纯的SAPO-34,大部分晶体的尺寸为0.5-2.5μm。该对比例与实施例4的比较表明,胶体种子在大约相同的重量比率下产生较小的晶体。
实施例5
在该实施例中,检查在Ni-SAPO-34生产中进行引种的作用。按照实施例3来制备合成混合物,只不同的是将足够的硝酸镍(Ni(NO3)26H2O,Fluka)加入溶液A中,得到具有如下摩尔组成的合成混合物:
Al2O3∶P2O5∶0.3SiO2∶0.0075NiO∶TEAOH∶1.6DPA∶50H2O。
将该混合物分成两部分,一部分用CHA浆液(6.4%固体含量)引种至409ppm引种量。将引种和未引种样品都在不锈钢高压釜中在175℃下加热60小时。冷却之后,将产物回收,洗涤并在120℃下干燥。在两种情况下,回收得到纯SAPO-34相,其摩尔化学组成和晶体尺寸如下:
未引种:Al2O3∶0.88P2O5∶0.36SiO2∶0.0040NiO,1-10μm
引种: Al2O3∶0.84P2O5∶0.31SiO2∶0.0042NiO,0.2-1.5μm
同样,在生产较小晶体时引种的益处是显然的。
将按照上述制备的两个样品通过漫反射FTIR来检查以确定它们的晶体质量和Broensted酸性。使用KBr稀释样品(约4%样品,在无水KBr中)得到在常规高温DRIFT池中的IR光谱。样品在测试之前在200-300℃下真空脱水。使用Gaussian-Lorentzian峰来分析在4厘米-1分辨率下使用64扫描得到的该光谱,确定位置和相对面积和形状。
在1400-1000厘米-1波数之间的区域,检查该实施例的引种和未引种产物的光谱,然后测定可归属于骨架T-O伸缩的主峰。下表给出了该区域三个主带的中心位置、峰高度和峰宽度(C,H,W)。
C,H,W C,H,W C,H,W
经引种的 1106/8.7/51 1135/12.3/54.7 1179/6.7/65.5
未经引种的 1082/1.4/90 1129/2.1/71 1190/0.9/90.6
从该表显然看出,引种样品具有明显最高和最尖锐的峰,因此具有最高的内部结晶度。
附图中的唯一图给出了在波数3800-3450厘米-1之间的区域。
现在参照该图,给出了这些样品中归属于桥接羟基的主峰的位置、高度和宽度。在≈3620处的带归属于8-元环中未扰动Broensted OH基团,而在≈3595处的带则归属于与骨架氧相互作用的OH基团或位于6-元环中的OH基团。这些带对OH区总面积的贡献(以面积计)的测量给出了下表中的结果:
样品 %面积贡献率
经引种 62
未经引种 21
显然,引种样品具有来自Broensted酸位的较高百分面积贡献率,尽管该样品具有较小的粒径,因此表面/体积比较大。由此暂定推断,3800-3620厘米-1区域中的剩余峰与内缺陷而不是与表面羟基有关,因此可以假定,Broensted酸OH基团对总OH面积具有高百分面积贡献率的产物是具有高度内部结晶完整性的物质。
实施例6
该实施例说明CHA种子在制备具有不同于实施例3的硅含量的SAPO-34中的应用。按照实施例3所述制备出合成溶液,只是组分的比例使得摩尔组成如下:
Al2O3∶P2O5∶0.1SiO2∶TEAOH∶1.6DPA∶52H2O。
加入CHA种子的浆液(6.4%固体含量),得到397ppm的种子含量。
按照实施例3所述将该混合物进行水热处理,然后以相同方式回收产物。它是纯的SAPO-34,大多数晶体为0.2-1.5μm,也存在少量尺寸为2-4μm的晶体。产物分析为:
Al2O3∶0.79P2O5∶0.21SiO2。
实施例7
重复实施例6,只不同的是改变硅石含量,得到摩尔组成如下的合成混合物:
Al2O3∶P2O5∶0.45SiO2∶TEAOH∶1.6DPA∶52H2O,以及397ppm的CHA种子。
按照实施例3所述进行水热处理,产物是粒径为0.2-1.5μm的纯SAPO-34。化学分析为:
Al2O3∶0.92P2O5∶0.42SiO2。
实施例6和7、以及实施例3第二部分的静态引种部分的产率如下,它们的合成混合物主要在硅含量上不同:
实施例6,0.1SiO2;产率7.8%
实施例3,0.3SiO2;产率12.5%
实施例7,0.45SiO2;产率12.7%。
对比例B
在实施例5-7中,在静态高压釜中进行水热处理。在该实施例和以下实施例中,检查搅拌和滚动对SAPO-34性能的影响,该实施例采用一种摩尔组成类似于实施例3第二部分的未引种合成混合物,但具有51摩尔的H2O而不是52。将合成混合物在不锈钢高压釜中在6小时内由室温加热至175℃以进行水热处理,其中在120rpm下搅拌,然后在继续搅拌下在175℃下保持60小时。按照实施例3所述进行回收。产物为SAPO-34、SAPO-18、以及一些SAPO-5的混合物,晶体为0.2-1μm。
实施例8
该实施例说明在水热处理过程中搅拌对钾沸石引种的合成混合物的作用。由5.36%固体含量钾沸石浆液加入胶体(小于100nm)钾沸石种子,所得引种混合物的摩尔组成如下:
Al2O3∶P2O5∶0.3SiO2∶TEAOH∶1.6DPA∶54H2O,加上0.19%重量的种子。
将合成混合物分成两部分。一部分(A)放在配有120rpm搅拌器的不锈钢高压釜中,然后在6小时内由室温加热至175℃,然后在继续搅拌下在175℃保持60小时。第二部分(B)则在没有搅拌下在2小时内在搅拌下由室温加热至175℃,然后在175℃下保持48小时,样品(C)是在24小时时取样。回收和干燥之后,将产物进行SEM和XRD分析。
样品A:SAPO-34,被SAPO-18和某些SAPO-5污染,晶体为0.2-1.0μm。
样品B:纯SAPO-34,晶体尺寸为0.5-2μm。
样品C:具有一些无定形物质的SAPO-34,晶体为0.2-1.5μm。
实施例9
该实施例说明在水热处理的加热升温过程中搅拌对Ni-SAPO-34生产的影响,随后则进行静态均热处理。按照实施例4所述的步骤,制备出含镍的合成混合物,得到一种摩尔组成如下的混合物:
Al2O3∶P2O5∶0.3SiO2∶0.0076NiO∶TEAOH∶1.6DPA∶52H2O。
将该混合物分成两部分,一部分(样品A)使用在实施例5中所用CHA引种浆液进行引种,得到202ppm的种子含量,而另一部分(样品B)则保持未引种。将两个样品都转移到不锈钢高压釜中,放在炉中并安装在一个于60rpm旋转的水平轴上。将高压釜在加热至175℃的2小时时间内进行滚动,然后停止滚动并将温度在175℃下保持60小时。
冷却之后,将产物通过离心处理回收、洗涤和在120℃下干燥。XRD表明,两种产物都是纯的Ni-SAPO-34。样品A包含粒径约1μm的具有受损表面的晶体。样品B包含粒径最高10μm的晶体,其中许多晶体呈破碎状。
该实施例表明,即使使用了起始滚动,也需要进行引种以将粒径降至所需水平。
实施例10
该实施例说明SAPO-34种子浆液在SAPO-34生产中的应用。
向具有在实施例3第二部分给出的摩尔组成的合成混合物中,加入在滚动条件下按照实施例3第二部分所述制备的10%SAPO-34浆液,得到0.1%(1000ppm)的引种量。将引种混合物在175℃下在不锈钢高压釜中加热48小时。将该混合物冷却,然后回收产物并确定为晶体尺寸0.5-4μm的纯SAPO-34。该实施例说明,尽管胶体SAPO-34晶体在生产SAPO-34时是有效的,但它们不如CHA或LEV结构类型沸石种子那些有效。
实施例11
在该实施例中,测定在实施例5中制备和讨论的产物在将甲醇催化转化成烯烃时的效果。在保持于450℃的台架规模固定床反应器中,将用氮气(总压力为大气压,甲醇分压为0.12)稀释的甲醇以1小时-1的WHSV(基于甲醇)和约5500小时-1的GHSV(基于甲醇和氮气)经过催化剂。在100%甲醇转化率下运转(on stream)1小时之后,结果如表所示。产率,% 实施例5,引种 实施例5,未引种C2= 50.1 47.9C3= 28.0 33.4C2=+C3=+C4=85.6 91.4C1-C4饱和 11.0 6.1
比起未引种产物,更理想乙烯的产率通过使用引种得到的产物而提高约5%。
Claims (24)
1.一种制备在其骨架中含磷的结晶分子筛的方法,该方法包括,在适合形成所需分子筛的时间和温度下,对包含形成所述含磷分子筛所需的元素和胶体结晶分子筛种子的合成混合物进行处理。
2.根据权利要求1所要求的方法,其中所述含磷分子筛是铝磷酸盐或硅石-铝磷酸盐,任选地包含其它元素。
3.根据权利要求1或权利要求2所要求的方法,其中所述含磷分子筛具有CHA或LEV结构类型。
4.根据权利要求1或权利要求2所要求的方法,其中所述含磷分子筛为SAPO-34。
5.根据权利要求4所要求的方法,其中Broensted酸位对IR光谱中总OH面积的百分面积贡献率至少为30%。
6.根据权利要求5所要求的方法,其中所述贡献率至少为50%。
7.根据权利要求4-6中任何一项所要求的方法,其中所述SAPO-34为Ni-SAPO-34。
8.根据权利要求1-7中任何一项所要求的方法,其中所述种子具有结构类型LEV、OFF、或CHA。
9.根据权利要求1-7中任何一项所要求的方法,其中所述种子为插晶菱沸石、ZSM-45、菱沸石、钾沸石、或SAPO-34。
10.根据权利要求1-9中任何一项所要求的方法,其中所述种子的存在比例为基于所述合成混合物总重的1-2000ppm。
11.根据权利要求10所要求的方法,其中所述比例为100-1500ppm。
12.根据权利要求10所要求的方法,其中所述比例为100-250ppm。
13.根据权利要求1-12中任何一项所要求的方法,其中所述种子以悬浮液的形式加入合成混合物中。
14.根据权利要求1-13中任何一项所要求的方法,其中所述种子的粒径为5-1000纳米。
15.根据权利要求14所要求的方法,其中所述粒径为10-300纳米。
16.根据权利要求14所要求的方法,其中所述粒径为20-100纳米。
17.根据权利要求1-16中任何一项所要求的方法,其中所述含磷分子筛具有第一结构类型且所述种子具有第二结构类型。
18.根据权利要求17所要求的方法,其中所述第一结构类型为CHA且所述二结构类型为LEV。
19.一种通过根据权利要求1-18中任何一项所要求的方法制成的分子筛。
20.可通过根据权利要求1-18中任何一项所要求的方法制成的SAPO-34,其中Broensted酸位对IR光谱中总OH面积的百分面积贡献率至少为30%。
21.根据权利要求19或权利要求20所要求的分子筛,为微粒或层的形式。
22.一种将含氧物转化成烯烃的方法,包括,在催化转化条件下,将该含氧物与权利要求19-21中任何一项的分子筛进行接触。
23.根据权利要求19-21中任何一项所要求的分子筛的应用,该分子筛如果需要在洗涤、阳离子交换或煅烧之后,用于烃转化、吸附或分离中。
24.胶体结晶分子筛种子晶体在含磷结晶分子筛合成中的应用,以便控制产物的粒径,或加速形成产物,或同时控制所述粒径和加速形成产物。
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- 1999-07-28 ID IDW20010495A patent/ID28170A/id unknown
- 1999-07-28 AT AT99936791T patent/ATE236080T1/de not_active IP Right Cessation
- 1999-07-28 CA CA002337505A patent/CA2337505A1/en not_active Abandoned
- 1999-07-28 JP JP2000562305A patent/JP2002521303A/ja active Pending
- 1999-07-28 AU AU51782/99A patent/AU750576B2/en not_active Ceased
- 1999-07-28 EP EP99936803A patent/EP1105347B1/en not_active Expired - Lifetime
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- 1999-07-28 EP EP99936791A patent/EP1105348B1/en not_active Expired - Lifetime
- 1999-07-28 WO PCT/GB1999/002480 patent/WO2000006493A1/en not_active Application Discontinuation
- 1999-07-28 JP JP2000562306A patent/JP4693239B2/ja not_active Expired - Fee Related
- 1999-07-28 CN CNB998091502A patent/CN1214976C/zh not_active Expired - Fee Related
- 1999-07-28 WO PCT/GB1999/002468 patent/WO2000006494A1/en active IP Right Grant
- 1999-07-28 KR KR20017001219A patent/KR100624246B1/ko not_active IP Right Cessation
- 1999-07-28 CN CN99809151A patent/CN1311757A/zh active Pending
- 1999-07-28 US US09/744,697 patent/US6974889B1/en not_active Expired - Lifetime
- 1999-07-28 KR KR1020017001238A patent/KR20010079583A/ko not_active Application Discontinuation
- 1999-07-28 ES ES99936791T patent/ES2194490T3/es not_active Expired - Lifetime
- 1999-07-28 DE DE69906545T patent/DE69906545T2/de not_active Expired - Lifetime
- 1999-07-28 CA CA002337628A patent/CA2337628A1/en not_active Abandoned
- 1999-07-28 BR BR9912472-6A patent/BR9912472A/pt not_active IP Right Cessation
- 1999-07-28 RU RU2001104888/12A patent/RU2001104888A/ru not_active Application Discontinuation
- 1999-07-28 DK DK99936791T patent/DK1105348T3/da active
- 1999-07-28 AU AU51773/99A patent/AU5177399A/en not_active Abandoned
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CN1890178B (zh) * | 2003-12-23 | 2011-04-13 | 埃克森美孚化学专利公司 | 菱沸石型分子筛、其合成及其在含氧化合物转化成烯烃中的应用 |
CN100569646C (zh) * | 2004-10-28 | 2009-12-16 | 中国石油化工股份有限公司 | 一种ael结构分子筛的合成方法 |
CN101213016B (zh) * | 2005-06-30 | 2013-01-09 | 环球油品公司 | 分子筛性能的增强 |
CN103124694B (zh) * | 2010-06-18 | 2016-03-16 | 巴斯夫欧洲公司 | Lev型结构的沸石材料及其制备方法 |
CN103124694A (zh) * | 2010-06-18 | 2013-05-29 | 巴斯夫欧洲公司 | Lev型结构的沸石材料及其制备方法 |
CN102838131B (zh) * | 2012-09-17 | 2015-02-18 | 神华集团有限责任公司 | Sapo-34分子筛及其制备方法 |
CN102838131A (zh) * | 2012-09-17 | 2012-12-26 | 神华集团有限责任公司 | Sapo-34分子筛及其制备方法 |
CN105692643A (zh) * | 2016-01-21 | 2016-06-22 | 嘉兴学院 | 利用zsm-57沸石晶种的模板效应合成其它结构沸石晶体的方法 |
CN105692643B (zh) * | 2016-01-21 | 2018-02-27 | 嘉兴学院 | 利用zsm‑57沸石晶种的模板效应合成其它结构沸石晶体的方法 |
CN108083292A (zh) * | 2018-01-31 | 2018-05-29 | 吉林大学 | 一种磷掺杂cha分子筛、制备方法及其应用 |
CN108083292B (zh) * | 2018-01-31 | 2020-12-29 | 吉林大学 | 一种磷掺杂cha分子筛、制备方法及其应用 |
CN113979443A (zh) * | 2021-12-01 | 2022-01-28 | 郑州大学 | 一种纳米sapo-34分子筛的制备方法 |
CN113979443B (zh) * | 2021-12-01 | 2023-11-24 | 郑州大学 | 一种纳米sapo-34分子筛的制备方法 |
Also Published As
Publication number | Publication date |
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BR9912472A (pt) | 2001-04-17 |
DE69906545D1 (de) | 2003-05-08 |
DE69906545T2 (de) | 2004-03-04 |
RU2001104888A (ru) | 2003-01-27 |
AU5177399A (en) | 2000-02-21 |
JP2002521304A (ja) | 2002-07-16 |
WO2000006494A1 (en) | 2000-02-10 |
US6974889B1 (en) | 2005-12-13 |
AU5178299A (en) | 2000-02-21 |
ES2194490T3 (es) | 2003-11-16 |
ID28170A (id) | 2001-05-10 |
KR100624246B1 (ko) | 2006-09-13 |
EP1105348B1 (en) | 2003-04-02 |
EP1105347A1 (en) | 2001-06-13 |
WO2000006493A1 (en) | 2000-02-10 |
US7264789B1 (en) | 2007-09-04 |
KR20010079583A (ko) | 2001-08-22 |
CA2337628A1 (en) | 2000-02-10 |
DK1105348T3 (da) | 2003-07-28 |
JP2002521303A (ja) | 2002-07-16 |
ATE236080T1 (de) | 2003-04-15 |
EP1105348A1 (en) | 2001-06-13 |
CA2337505A1 (en) | 2000-02-10 |
CN1311758A (zh) | 2001-09-05 |
JP4693239B2 (ja) | 2011-06-01 |
KR20010079581A (ko) | 2001-08-22 |
CN1214976C (zh) | 2005-08-17 |
AU750576B2 (en) | 2002-07-25 |
EP1105347B1 (en) | 2012-11-28 |
NO20010463L (no) | 2001-03-28 |
NO20010463D0 (no) | 2001-01-26 |
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