CN112028085A - 含钼空心钛硅分子筛及其制备方法和应用 - Google Patents
含钼空心钛硅分子筛及其制备方法和应用 Download PDFInfo
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- CN112028085A CN112028085A CN202010510238.4A CN202010510238A CN112028085A CN 112028085 A CN112028085 A CN 112028085A CN 202010510238 A CN202010510238 A CN 202010510238A CN 112028085 A CN112028085 A CN 112028085A
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 61
- 239000011733 molybdenum Substances 0.000 title claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- 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 48
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 26
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- UVHQNHAPYJVORK-UHFFFAOYSA-N trimethoxy(3-phenylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCC1=CC=CC=C1 UVHQNHAPYJVORK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 10
- -1 amine compound Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002751 molybdenum Chemical class 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 8
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
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- 230000003647 oxidation Effects 0.000 description 4
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 239000002585 base Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
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- 239000002159 nanocrystal Substances 0.000 description 1
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- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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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
本发明提供了含钼空心钛硅分子筛及其制备方法和应用。在含水溶剂存在的条件下,将硅源和结构导向剂混合,使硅源被充分水解,再加入钼源、钛酸四丁酯和苯基丙基三甲氧基硅烷(PAPTMS),得到前驱体溶液;将所得前驱体溶液倒入晶化釜中,密封后晶化,晶化后分离出固态物质,将固态物质在500‑600℃下煅烧,得到含钼空心钛硅分子筛。该含钼空心钛硅分子筛能够作为制备环氧乙烷的催化剂。
Description
技术领域
本发明属于催化剂领域,具体涉及分子筛及其制备方法和应用。
背景技术
环氧乙烷(Ethylene Oxide,简称EO)含有环氧基,易于开环聚合,是一种重要的化工原料。环氧乙烷是一种最简单的环醚,属于杂环类化合物,化学性质活泼,有剧毒,可衍生出一些重要的精细化工中间体,被广泛应用于洗涤、制药、印染等行业。目前环氧乙烷被主要用于生产单体乙二醇、合成洗涤剂、非离子表面活性剂、抗冻剂、乳化剂等多种产品。
现有技术中,制备环氧乙烷的方法主要包括氯醇法和氧化法两种。氯醇法通过将乙烯卤醇化以后再与碱发生皂化反应制备环氧乙烷。氧化法则可分为空气法和氧气法两种,前者以空气为氧化剂,后者用浓度大于95%的氧气作为氧化剂。
氯醇法制备环氧乙烷有着悠久的历史,该法生产工艺成熟,操作负荷弹性大,选择性好,对原料烯烃的纯度要求不高,从而可提高生产的安全性;并且其固定资产建设投资少,产品成本低。
但是现有技术的氯醇法制备环氧化物主要存在以下问题:①氯气和水的反应是可逆反应,氯气通入水中反应极慢且溶解度很小,导致反应生成的次氯酸比例很小,因而致使卤醇化反应收率很低,一般只有3-4%;②反应产生盐酸,需要消耗大量的碱(以氢氧化钙为例)来中和反应生产的盐酸;③反应产生大量氯化钙,氯化钙导致产生的废水COD偏高,环境污染严重;④氯醇法水资源消耗巨大,产生大量废水和废渣,氯醇法生产1吨环氧化物会产生40-50吨含氯化物的废水、2.1吨氯化钙废渣,该废水具有温度高、pH高、氯根含量高、COD高和悬浮物含量高的“五高”特点,难以处理,严重污染环境。
如果不能有效地解决氯醇法的废水废渣问题,企业生产装置产能越大,其相对的环保包袱也就越大;产量越高,对环境的伤害就越深。所以说,环保问题已成为制约环氧化物工业发展的首要因素。
以FCC干气为原料生产环氧乙烷的工艺技术,目前普遍采用的是氯醇法工艺路线。中国石油抚顺石化分公司石油二厂建设了一套以FCC干气中稀乙烯制取环氧乙烷,进而生产乙二醇、乙醇胺、乙二醇醚等产品的工业装置,现已安全运转10多年。与纯乙烯制环氧乙烷技术相比,该技术的能耗及物耗较高,经济上还缺乏竞争力。如通过研制活性更高、选择性更好的催化剂,改进工艺技术降低生产能耗与物耗,同时随着石油资源的枯竭和乙烯价格上扬,该技术具有一定的竞争力。
发明内容
本发明的目的之一是提供一种含钼空心钛硅分子筛,它具有颗粒尺寸小、尺寸均匀、比表面积大、负载的钼活性组分稳定性好的特点,且对烯烃氧化制环氧化物反应的催化性能好。
本发明的目的之二是提供一种含钼空心钛硅分子筛的制备方法,在碱性条件下,通过多步水热法合成钼组分负载稳定的TS-1分子筛。
本发明的目的之三是提供含钼空心钛硅分子筛的应用,以含钼空心钛硅分子筛为催化剂,实现干气中乙烯的环氧化反应,制备环氧乙烷,对反应产物环氧乙烷具有较高的选择性,并能分解氯醇法工艺的废渣,解决传统氯醇法废渣难处理,污染严重的问题。
为实现上述目的,本发明所采取的技术方案为:
一种含钼空心钛硅分子筛的制备方法,包括如下步骤:
(1)在含水溶剂存在的条件下,将硅源和结构导向剂混合,使硅源被充分水解,再加入钼源、钛酸四丁酯和苯基丙基三甲氧基硅烷(PAPTMS),得到前驱体溶液;
(2)将步骤(1)所得前驱体溶液倒入晶化釜中,密封后晶化,晶化后分离出固态物质,将固态物质在500-600℃下煅烧,得到含钼空心钛硅分子筛。
进一步地,上述的含钼空心钛硅分子筛的制备方法还包括如下步骤:
(3)将步骤(2)所得含钼空心钛硅分子筛用盐酸酸化处理。
根据上述方法得到的含钼空心钛硅分子筛,具有孔径为1.2-1.8nm的超微孔和2-4nm的中孔。所述含钼空心钛硅分子筛具有优异的催化性能,能够应用于制备环氧乙烷。
根据上述方法得到的含钼空心钛硅分子筛能够作为在制备环氧乙烷过程中的催化剂。
与现有技术相比,本发明的优点与有益效果为:
(1)本发明的含钼空心钛硅分子筛,具有颗粒尺寸小、尺寸均匀、比表面积大、负载的钼组分稳定性好的特点;
(2)由于钼的良好活性和活性中心的易接近性,本发明的含钼空心钛硅分子筛催化剂在环氧化反应中的催化性能得到明显改善,对烯烃氧化制环氧化物反应的催化性大大提升;
(3)本发明的以含钼空心钛硅分子筛作为催化剂制备环氧乙烷的方法,①使用双氧水代替水,在第一步卤化反应后,没有其他副产物,原料可以完全转化为卤乙醇;由于双阳水参加反应,大大降低了中间的加成副反应,减少了有机副产品的产生;皂化过程中,碱用量大大减少,仅为原工艺的50%左右。②本发明制备的环氧乙烷浓度可以达到60%以上;本发明皂化过程能耗仅为原工艺的10%左右;本发明的水消耗不足原工艺的10%。③本发明采用双极膜电渗析技术处理含有机物的废水同时,产生的碱金属的氢氧化物和卤化氢可以重复利用。
附图说明
图1为本发明实施例1-4的含钼空心钛硅分子筛样品的XRD图谱。
图2为本发明实施例1-4的含钼空心钛硅分子筛样品N2吸附-解吸等温线。
图3为本发明实施例1-4的含钼空心钛硅分子筛SEM和TEM图像。
图4为本发明双极膜电渗析工艺图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅是本发明的一部分实例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提供了一种含钼空心钛硅分子筛的制备方法,包括如下步骤:
(1)在含水溶剂存在下,将硅源与结构导向剂混合,使硅源被充分水解,再加入钼源和钛酸四丁酯以及PAPTMS,得到前驱体溶液;
(2)将步骤(1)所得前驱体溶液倒入100ml的聚四氟乙烯内衬的高压晶化釜中,密封后晶化,将所得晶化产物过滤干燥,之后550℃煅烧6h,得到的分子筛即为HTS-y,y为前驱体溶液中的钼硅比;
(3)将步骤(2)所得分子筛用1mol/L的盐酸酸化处理,经过过滤、水洗、干燥和煅烧后,即可得到酸洗后的HTS-y。
根据本发明,本发明的硅源可以是有机硅酸酯、硅胶、白炭黑和硅溶胶中的至少一种;为了降低硅源中杂原子对晶化产物的影响,本发明中选用单一硅源,进一步优选为有机硅酸酯,进一步优化为正硅酸四乙酯。
根据本发明,所述步骤(1)中使用的结构导向剂可以为季铵碱类、季铵盐类和脂肪胺类化合物中的至少一种。其中,所述的季铵碱可以为有机季铵碱,所述的季铵盐可以为有机季铵盐类,所述的脂肪族胺可以为NH3中的至少一个氢被脂肪族烃基(如烷基)取代后形成的化合物。
优选的,步骤(1)所述的结构导向剂为四乙基氢氧化铵、四丙基氢氧化铵、四乙基氟化铵、四乙基氯化铵、四乙基溴化铵、四乙基碘化铵、二乙胺和三乙胺中的至少一种;进一步的,所述结构导向剂可以为四丙基氢氧化铵。
根据本发明,钼源是影响HTS-Mo分子筛的最重要元素,本发明中的钼盐可以为有机钼盐和无机钼盐中的至少一种。为了使合成分子筛中钼元素分布均匀,本发明中的钼源优选为可溶性钼源。为了保证生成的HTS-Mo分子筛具有相同的晶体晶型以及晶体形貌,避免多种形态的晶体产生,本发明中的钼源优选为单一钼源;进一步的,优选六钼酸铵。
根据本发明,为了促使硅源充分水解,减少前驱体溶液中的无定形杂质生成,防止前驱体溶液凝固报废,进一步的,所述步骤(1)中的优选水解条件为在50℃条件下以400r/min搅拌12h。
根据本发明,为了促使分子筛的晶化,提高晶化效率,降低晶体中的缺陷,减少无定形物质的生成,进一步的,所述步骤(2)中的晶化条件优选为在170℃下密封加热16h。
根据本发明,水热反应中,体系的压力会影响产物的晶型以及结晶速率,而反应体系的自生压力取决于反应釜中空余体积的大小;为了提高晶化反应的效率,进一步的,步骤(2)中混合溶液的总体积为所述聚四氟乙烯反应釜容量的60-75%。
以下描述几个典型的实施例。
实施例1
将20.8g正硅酸四乙酯(TEOS>99%)与16.3g四丙基氢氧化铵(TPAHO,25%wt%)混合。50℃搅拌12h,使TEOS被TPAOH水解,再加入1.36g钛酸四丁酯(>97%wt%)和0.04g的六钼酸铵,在70℃下分散6h,最后加入2.6g苯基丙基三甲氧基硅烷(PAPTMS),前驱体化学组成为:
nSi/nTi/nMo/nTPAOH/nPAPTMS/nH2O=1:0.04:0.0025:0.2:0.1:30
将所得的前驱体倒入100ml的聚四氟乙烯内衬的高压晶化釜中,密封后在170℃条件下加热16h。将所得产物过滤,水洗后110℃干燥8h,之后在550℃下煅烧6h,合成的分子筛记为HTS-0.0025。
最后,将10g HTS-0.0025与100ml 1mol/L的盐酸水溶液混合,得到的混合物在80℃加热6h。然后对样品进行过滤、水洗、干燥(110℃,6h)和煅烧(550℃,6h),所得即为酸洗后的HTS-0.0025。
实施例2
将20.8g正硅酸四乙酯(TEOS>99%)与16.3g四丙基氢氧化铵(TPAHO,25%wt%)混合。50℃搅拌12h,使TEOS被TPAOH水解,再加入1.36g钛酸四丁酯(>97%wt%)和0.08g的六钼酸铵,在70℃下分散6h,最后加入2.6g苯基丙基三甲氧基硅烷(PAPTMS),前驱体化学组成为:
nSi/nTi/nMo/nTPAOH/nPAPTMS/nH2O=1:0.04:0.005:0.2:0.1:30
将所得的前驱体倒入100ml的聚四氟乙烯内衬的高压晶化釜中,密封后在170℃条件下加热16h。将所得产物过滤,水洗后110℃干燥8h,之后在550℃下煅烧6h,合成的分子筛记为HTS-0.005。
最后,将10g HTS-0.0025与100ml 1mol/L的盐酸水溶液混合,得到的混合物在80℃加热6h。然后对样品进行过滤、水洗、干燥(110℃,6h)和煅烧(550℃,6h),所得即为酸洗后的HTS-0.005。
实施例3
将20.8g正硅酸四乙酯(TEOS>99%)与16.3g四丙基氢氧化铵(TPAHO,25%wt%)混合。50℃搅拌12h,使TEOS被TPAOH水解,再加入1.36g钛酸四丁酯(>97%wt%)和0.16g的六钼酸铵,在70℃下分散6h,最后加入2.6g苯基丙基三甲氧基硅烷(PAPTMS),前驱体化学组成为:
nSi/nTi/nMo/nTPAOH/nPAPTMS/nH2O=1:0.04:0.01:0.2:0.1:30
将所得的前驱体倒入100ml的聚四氟乙烯内衬的高压晶化釜中,密封后在170℃条件下加热16h。将所得产物过滤,水洗后110℃干燥8h,之后在550℃下煅烧6h,合成的分子筛记为HTS-0.01。
最后,将10g HTS-0.0025与100ml 1mol/L的盐酸水溶液混合,得到的混合物在80℃加热6h。然后对样品进行过滤、水洗、干燥(110℃,6h)和煅烧(550℃,6h),所得即为酸洗后的HTS-0.01。
实施例4
将20.8g正硅酸四乙酯(TEOS>99%)与16.3g四丙基氢氧化铵(TPAHO,25%wt%)混合。50℃搅拌12h,使TEOS被TPAOH水解,再加入1.36g钛酸四丁酯(>97%wt%)和0.24g的六钼酸铵,在70℃下分散6h,最后加入2.6g苯基丙基三甲氧基硅烷(PAPTMS),前驱体化学组成为:
nSi/nTi/nMo/nTPAOH/nPAPTMS/nH2O=1:0.04:0.015:0.2:0.1:30
将所得的前驱体倒入100ml的聚四氟乙烯内衬的高压晶化釜中,密封后在170℃条件下加热16h。将所得产物过滤,水洗后110℃干燥8h,之后在550℃下煅烧6h,合成的分子筛记为HTS-0.015。
最后,将10g HTS-0.0025与100ml 1mol/L的盐酸水溶液混合,得到的混合物在80℃加热6h。然后对样品进行过滤、水洗、干燥(110℃,6h)和煅烧(550℃,6h),所得即为酸洗后的HTS-0.015。
分别以实施例1-4制备的HTS-0.0025、HTS-0.005、HTS-0.01、HTS-0.015(即未酸洗的含钼空心钛硅分子筛)为催化剂,采用双极膜电渗析工艺,按照以下步骤制备环氧乙烷:
在管式反应器(其中在管内填装了固定的含钼空心钛硅分子筛催化剂床层)中加入70wt%浓度的H2O2水溶液、氯气和干气,在45℃的温度下进行氯醇化反应,其中70wt%浓度的H2O2水溶液、氯气和干气三者的流量应使得双氧水、氯气与干气的体积比大约为1.1:0.5:1;将所得到的氯乙醇与催化剂和氢氧化钙通入塔式反应器中进行皂化反应,蒸汽从塔底进入使生成的粗环氧乙烷从塔顶吹出,皂化温度控制在60-70℃。
测定的乙烯转化率和环氧乙烷的选择性结果下表。
催化剂 | 乙烯转化率% | 环氧乙烷选择性% | 环氧乙烷收率% |
HTS-0.005 | 100 | 95.26 | 93.61 |
HTS-0.05 | 100 | 95.88 | 95.01 |
HTS-0.01 | 100 | 96.69 | 96.59 |
HTS-0.015 | 100 | 98.10 | 96.71 |
钛硅分子筛(TS-1)是烯烃环氧化的重要催化剂,但对某些烯烃来说,其结晶微孔太小。虽然晶内介孔可以消除扩散限制,但考虑到烯烃的转化,催化性能还有待进一步提高。本发明通过分级合成实现了钼负载在TS-1上的烷硅化过程。虽然相对结晶度降低了,但产生了更多的约1.2-1.8nm的超微孔和2-4nm范围的中孔,导致比表面积、中空体积(VME)、和总孔体积(VT)增加。相比较而言,随着Mo含量的增加,VME和VT增加,Mo和Ti大部分被限制在晶体内。由于钼具有良好的催化活性和较为廉价易得,特别是以有机过氧化氢为氧化剂时,其催化性能明显提高。更重要的是,所负载的Mo活性组分具有更好的稳定性。
含钼空心钛硅分子筛样品的XRD图谱如图1a所示。特征衍射峰在2θ=7.9、8.8、23.1、23.9和24.4°说明,通过硅烷化过程合成的HTS为MFI拓扑结构。
然而,随着Mo含量的增加,XRD图谱中特征峰的强度降低。由于引入有机硅烷会部分抑制分子筛晶体的成核和生长过程,导致前驱体中的有机硅烷与羟基发生缩合反应,因此HTS的相对结晶度(RC)仅为48.5%。
另一方面,从图1b的RC可以看出,前驱体中钼的含量对结晶过程的影响更为严重,当nMo/nSi=0.0025时,RC降低到42%,而HTS-0.015仅为21%。此外,特征衍射峰(2θ=12.6、23.3、25.7、38.9和67.4°)[33-35]和傅里叶变换红外光谱波段(553、876和995cm-1)对应MoO3晶体的缺少,表明Mo在含钼催化剂中是高度分散的。
由N2吸附-解吸等温线得到的化学组成和结构特性(图S2)如表1所示。XRF分析表明,催化剂中硅、钛、钼(n Si/n Ti/n Mo)的摩尔比与沸石前驱物的值一致。由于有机硅烷对结晶过程的不利影响,HTS的微孔面积(SMI,222m 2/g)和微孔体积(VMI,0.096cm 3/g)均小于常规TS-1。然而,孔隙大小分布曲线(图2)说明1.76nm的超微孔和2.2-7.8nm的中孔结构的产生,以及HTS的特定区域(SBET,531m2/g),外表面积(SEA,309m2/g),总孔隙体积(VT,0.409cm3/g)。当前驱体中有钼加入时,引入了更多的超微孔结构,其直径约为1.20-1.50nm,中孔约为2-4nm,导致VT、VME、SEA(496±6m2/g)和SBET的增加。而随着钼含量的增加,VT和VME增加,HTS-0.015的超微孔增多,而HTS-0.0025、HTS-0.005、HTS-0.010的中孔较多。此外,XRF分析数据表明含钼的样品会减少晶体微孔结构,并且这种减少应该会强于当钼硅比为0.0025-0.010超微孔结构的增加,从而导致了SMI(198±4m2/g)和VMI(0.086±0.002cm3/g)的减少。另一方面,HTS-0.015中的SMI和VMI分别增加到250m 2/g和0.103cm 3/g,这应该是体积庞大的超微孔的结果。
含钼空心钛硅分子筛样品的SEM和TEM图像如图3所示。HTS沸石晶体大小约为300×400nm,由不超过20nm的纳米晶体组成,表面不光滑,晶内次生孔隙,呈海绵状结构。虽然含钼分子筛的结构性能有一定的影响,但钼分子筛的形貌和晶粒尺寸基本一致。然而,从XRD衍射图可以看出,当钼硅比=0.015时,影响非常严重,HTS-0.015的晶体并不完美(图3e)。尽管如此,TEM图像(图S3)中的晶格条纹说明了这种材料仍然是晶体状的。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围有所附权利要求而不是上述说明限定,因此只在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (11)
1.一种含钼空心钛硅分子筛的制备方法,包括如下步骤:
(1)在含水溶剂存在的条件下,将硅源和结构导向剂混合,使硅源被充分水解,再加入钼源、钛酸四丁酯和苯基丙基三甲氧基硅烷(PAPTMS),得到前驱体溶液;
(2)将步骤(1)所得前驱体溶液倒入晶化釜中,密封后晶化,晶化后分离出固态物质,将固态物质在500-600℃下煅烧,得到含钼空心钛硅分子筛。
2.根据权利要求1所述的方法,其特征在于,还包括如下步骤:
(3)将步骤(2)所得含钼空心钛硅分子筛用盐酸酸化处理。
3.根据权利要求1所述的方法,其特征在于,所述硅源是有机硅酸酯、硅胶、白炭黑和硅溶胶中的至少一种。
4.根据权利要求1所述的方法,其特征在于,所述结构导向剂为季铵碱类、季铵盐类和脂肪胺类化合物中的至少一种。
5.根据权利要求1所述的方法,其特征在于,所述钼源为有机钼盐和无机钼盐中的至少一种。
6.根据权利要求5所述的方法,其特征在于,所述钼源为六钼酸铵。
7.根据权利要求1所述的方法,其特征在于,所述步骤(2)的晶化在170℃条件下进行。
8.根据权利要求1所述的方法,其特征在于,所述步骤(2)的煅烧温度为550℃。
9.一种含钼空心钛硅分子筛,其特征在于,所述含钼空心钛硅分子筛由权利要求1-8任一权利要求所述的方法得到。
10.根据权利要求9所述的含钼空心钛硅分子筛,其特征在于,所述含钼空心钛硅分子筛具有孔径为1.2-1.8nm的超微孔和2-4nm的中孔。
11.根据权利要求9或10所述的含钼空心钛硅分子筛在制备环氧乙烷过程中作为催化剂的应用。
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