CN112408414B - 一种薄层纳米片型多级孔ts-1分子筛催化剂的制备方法及其应用 - Google Patents
一种薄层纳米片型多级孔ts-1分子筛催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种高稳定性、高活性的纳米片型多级孔核壳结构TS‑1分子筛催化剂的制备方法及其应用。TS‑1催化剂核层为纳米片型多级孔TS‑1分子筛，催化剂壳层为纯硅分子筛Silicalite‑1。通过多级孔TS‑1纳米片型分子筛催化剂的构建，可消除传统颗粒型钛硅分子筛孔道存在的内扩散限制问题，通过表面构建纯硅分子筛Silicalite‑1壳层可降低常规TS‑1分子筛的表面酸性，抑制开环副产物的生成。该催化剂可应用于氯丙烯双氧水法合成环氧氯丙烷的反应，可有效提高环氧氯丙烷的选择性和催化剂的使用寿命。
Description
技术领域
本发明提供了一种高稳定性、高活性的纳米片核壳结构催化剂Silicalite-1@TS-1合成环氧氯丙烷的方法，催化剂核层为具有纳米片结构的TS-1，催化剂壳层为纯硅分子筛Silicalite-1，通过纯硅分子筛Silicalite-1的构建，可以降低分子筛表面酸性位，抑制开环副产物的产生，通过在纳米片构建多级孔，可以有效提高传质效率，进一步提高催化剂的稳定性。该催化剂可应用于卤代烯烃环氧化特别是氯丙烯双氧水法合成环氧氯丙烷的反应，可有效提高环氧氯丙烷的选择性和催化剂的使用寿命，属于精细化领域。
背景技术
环氧氯丙烷是一种重要的有机化工原料和精细化工产品，以环氧氯丙烷为原料合成的环氧树脂具有耐化学介质腐蚀强、粘结性强、化学稳定性好等特点，在胶粘剂、涂料、浇铸材料、增强材料具有广泛的应用；环氧氯丙烷还可用于合成表面活性剂、电绝缘品、硝化甘油炸药、玻璃钢、医药、农药、涂料、增塑剂、缩水甘油衍生物、氯醇橡胶等多种产品。环氧氯丙烷主流的生产方法包括丙烯高温氯化法(氯醇法)、甘油氯化法、醋酸丙烯酯法，其中丙烯高温氯化法占到全球产量的90％，合成过程主要包括丙烯高温氯化制备氯丙烯、氯丙烯次氯酸化制备二氯丙醇、二氯丙醇皂化制得环氧氯丙烷；甘油法约占全球产量的10％，该方法避免了剧毒气体氯气的使用，反应条件温和，提高了体系的安全性能，降低了装置的防腐蚀性能要求，但该工艺同样涉及到皂化废盐和废水的资源化回收及利用问题。为了有效解决环氧氯丙烷生产中间设备、环保、成本等问题，实现工艺清洁化、生产低成本，专利U.S.Pat.No.4833260提出了以具有MFI拓扑结构TS-1为催化剂H2O2为氧化剂制备烯烃环氧化产物的方法。目前，针对钛硅分子筛催化剂的构效关系研究表明，常规水热合成的钛硅分子筛TS-1颗粒粒径在100nm～300nm之间，孔道内扩散限域效应和副产高聚物引起的孔道堵塞可导致催化剂催化活性下降，通过构建空心分子筛或构建多级孔分子筛可有效调节内扩散性能，提高分子筛催化剂的稳定性和活性。专利U.S.Pat.No.4410501公开了一种以硅源、钛源、模板剂合成钛硅分子筛TS-1的合成方法，该方法合成的分子筛晶粒较大，应用于常规环氧氯丙烷反应活性下降较快。专利U.S.Pat.No.US4833260公开了一种以钛硅分子筛为催化剂，用过氧化氢生产环氧氯丙烷的方法，该专利使用水热法合成钛硅分子筛作催化剂，过氧化氢作氧化剂可高效氧化包括乙烯、丙烯、氯丙烯、环己烯等一系列烯烃化合物制备相应环氧化合物。
发明内容
针对传统TS-1分子筛内扩散限制及催化剂易失活、活性低的问题，本发明通过构建一种核壳结构多级孔薄层纳米片型Silicalite-1@TS-1催化剂，一方面可以消除内扩散限制极大增强催化剂的内扩散速率；另外，通过抑制催化剂的表面酸性，可极大延长催化剂的使用寿命，提高催化剂的稳定性。
本发明的目的在于提供一种高稳定性、高活性的核壳结构多级孔纳米片型Silicalite-1@TS-1的制备方法。TS-1纳米片合成采用正硅酸乙酯TEOS为硅源，钛酸正四丁酯TBOT为钛源，采用三乙烯二胺衍生物季胺盐和四丙基氢氧化铵作复合结构导向剂，使用分步水热法构建分子筛催化剂:
1、向玻璃反应釜中加入正硅酸乙酯(TEOS)和四丙基氢氧化铵的混合溶液剧烈搅拌30-50min至形成透明溶胶，随后于65～95℃水解1-2h形成预水解硅溶胶，滴加季胺盐得到正硅酸乙酯水解液；其中正硅酸乙酯和四丙基氢氧化铵的摩尔比范围为：1:1-5:1，正硅酸乙酯与季铵盐的摩尔比范围为4:1-10:1，季铵盐可以选择烷基二甲基羟乙基季铵盐、烷基三乙烯二胺衍生物和四丙烯基氢氧化铵季胺盐中的一种。
2、取一定量的钛酸四正丁酯(TBOT)/异丙醇溶液滴加到步骤1中的正硅酸乙酯水解液中，边搅拌边缓慢滴加，滴加完毕后升温至55～85℃后进一步水解4-6h然后转至180℃水热釜晶化48～96h，得到TS-1纳米片；其中正硅酸乙酯、钛酸四丁酯和异丙醇的摩尔比范围为：10:1：10-20:1:15；
3、对步骤2水热晶化结束后的TS-1纳米片通过离心、分离、干燥得到纳米片型TS-1分子筛晶种；
4、取TS-1分子筛晶种转移至含特定含量的20正硅酸乙酯(TEOS)：14四丙基氢氧化铵(TPAOH)：9500H2O(摩尔比)的Silicalite-1预水解液，TS-1分子筛晶种与水解液质量比控制在1～2wt.％，转至180℃晶化釜晶化24～72h；
5、经离心分离、洗涤、干燥后得钛硅分子筛；
6、将分子筛转入马弗炉以2-5℃/min的速率升温至550℃焙烧，保温时间5-7h，得Silicalite-1@TS-1分子筛；
7、将焙烧后的分子筛转入按100g Silicalite-1@TS-1分子筛：5～20g TPAOH：55mol H2O的溶液中二次晶化，其中二次晶化晶化釜水热温度控制在150～170℃下继续水热晶化12～48h后得到含多级孔的核壳结构多级孔纳米片型催化剂Silicalite-1@TS-1；
8、取10g Silicalite-1@TS-1分子筛，按摩尔比为100SiO2：25NH4HF2：3000H2O(摩尔比)混合均匀后，升温至50～100℃搅拌处理4～12h得到Silicalite-1@TS-1催化剂。
与现有技术相比，本发明的有益效果为：
(1)本发明中提供了一种超薄纳米片型核壳结构Silicalite-1@TS-1分子筛催化剂的制备方法，可有效解决常规TS-1孔道内扩散限域问题。
(2)通过对Silicalite-1@TS-1分子筛进行二次造孔，可在Silicalite-1@TS-1分子筛形成孔径为3.8nm的孔道，进一步提高内扩散性能，提高催化活性；
(3)通过对Silicalite-1@TS-1分子筛进行活化后处理可以构建出活性更高的骨架钛物种，进一步消除内扩散限制并提高催化活性。
附图说明
图1为季铵盐模板剂(Ⅰ、Ⅱ、Ⅲ)。
图2为催化剂套用结果对比。
图3为实施例1Silicalite-1@TS-1分子筛催化剂HR-TEM图像。用JEM-2010型透射电镜观测催化剂形貌，电子束电压200kV。实施例1中合成催化剂为薄层纳米片结构，薄层纳米片层厚度5～10nm。
图4为对比实施例常规TS-1催化剂HR-TEM图像。对比实施例1中合成出的常规TS-1催化剂为厚度～100nm的MFI晶体结构；
具体实施方式
1、下面通过具体实施方式来进一步说明本发明的技术方案。
实施例1：
将45.0g正硅酸乙酯(0.2mol，TEOS)与56.0g 25wt.％四丙基氢氧化铵(0.068mol，TPAOH)混合水解液搅拌30min至形成透明溶胶，于常压65℃条件下预水解1h，加入4.25g季胺盐模板剂I(0.005mol，Template-I)得到正硅酸,乙酯水解液；冷却至0℃后继续缓慢滴加18wt.％含4.4g钛酸四丁酯(0.013mol，TBOT)和19.8g异丙醇(0.33mol，IPA)溶液，滴加完毕后继续加热升温至85℃且水解4h，预水解溶胶组成为1SiO2：0.34TPAOH：1.65IPA：0.065TBT：20H2O：0.023template-I。预水解结束后转入180℃四氟水热釜水热晶化48h，得到TS-1纳米片。冷却至室温，离心分离、洗涤干燥后得到钛硅分子筛晶种，继续加入4.16g(0.02mol)TEOS与5.69g(0.007mol,25wt.％)TPAOH与85.5g H2O的预水解液，二次晶化液摩尔组成为40TEOS：14TPAOH：9500H2O，继续于180℃下晶化48h，经离心分离、洗涤、干燥后得钛硅分子筛。将分子筛转入马弗炉以5℃/min的速度程序升温至550℃焙烧5h得到Silicalite-1/TS-1分子筛。取Silicalite-1/TS-1分子筛按100g Silicalite-1/TS-1：9.90g TPAOH:55mol H2O比例混合后转入四氟反应釜，在170℃温度条件下水热晶化24h后冷却、过滤、洗涤、干燥得到含多级孔的核壳结构多级孔纳米片型催化剂Silicalite-1@TS-1。取合成的10g Silicalite-1/TS-1分子筛，加入50g 1wt.％的NH4HF2溶液搅拌均匀后升温至60℃，再滴加5ml 30wt.％的过氧化氢溶液，60℃保温4h，得到活化的Silicalite-1@TS-1分子筛催化剂1，通过ICP分析得催化剂成品Ti/Si摩尔比为0.24％。
实施例2：
将45.0g正硅酸乙酯(0.2mol，TEOS)与56.0g 25wt.％四丙基氢氧化铵(0.068mol，TPAOH)混合液剧烈搅拌30min至形成透明溶胶，于常压85℃下预水解1h，然后加入3.78g季胺盐模板剂II(0.005mol,template-II)得到正硅酸乙酯水解液；冷却至0℃后继续缓慢滴加18wt.％含4.4g钛酸四丁酯(0.013mol，TBT)和19.8g异丙醇(0.33mol，IPA)溶液，滴加完毕后继续加热升温至65℃继续水解4h，预水解溶胶组成摩尔比为1SiO2：0.34TPAOH：1.65IPA：0.065TBT：20H2O：0.023template-II。预水解结束后转入180℃四氟内水热釜水热晶化96h，得到TS-1纳米片。冷却至室温下离心分离、洗涤得到钛硅分子筛晶种，继续加入4.16g(0.02mol)TEOS与5.69g(0.007mol,25wt.％)TPAOH与85.5g H2O的预水解液，二次晶化液摩尔组成为40TEOS:14TPAOH：9500H2O，继续于180℃下晶化72h，经离心分离、洗涤、干燥后得钛硅分子筛。将分子筛以5℃/min的速度程序升温至550℃焙烧5h得到核壳结构分子筛，取Silicalite-1@TS-1分子筛按100g Silicalite-1/TS-1：9.90g TPAOH:55mol H2O比例混合后转入四氟反应釜，在170℃温度条件下水热晶化24h后冷却、过滤、洗涤、干燥得到含多级孔的核壳结构多级孔纳米片型催化剂Silicalite-1@TS-1。取合成的10gSilicalite-1@TS-1分子筛，加入100g 1wt.％的NH4HF2溶液搅拌均匀后升温至60℃，再滴加5ml 30wt.％的过氧化氢溶液，60℃保温4h，得到活化的Silicalite-1@TS-1分子筛催化剂2，通过ICP分析得催化剂成品Ti/Si摩尔比为0.20％。
实施例3：
将45.0g正硅酸乙酯(0.2mol，TEOS)与56.0g 25wt.％四丙基氢氧化铵(0.068mol，TPAOH)混合液剧烈搅拌30min至形成透明溶胶，于常压95℃条件下预水解1h，加入3.26g季胺盐模板剂III(0.005mol，Template-III)得到正硅酸乙酯水解液；冷却至0℃后继续缓慢滴加18wt.％含4.4g钛酸四丁酯(0.013mol，TBT)和19.8g异丙醇(0.33mol，IPA)溶液,升温至55℃继续水解4h,预水解溶胶组成摩尔比为1SiO2:0.325TPAOH:1.56IPA:0.06TBT:20H2O：0.023Template-III。预水解结束后转入180℃四氟内水热釜水热晶化48h，得到TS-1纳米片。冷却至室温，离心分离、洗涤得到钛硅分子筛晶种，继续加入4.16g TEOS(0.02mol)与5.69g(0.007mol,25wt.％)TPAOH与81.24g H2O的预水解液，二次晶化液摩尔组成为40TEOS:14TPAOH：9500H2O，继续于180℃下晶化72h，经离心分离、洗涤、干燥后得钛硅分子筛。将分子筛以5℃/min的速度程序升温至550℃焙烧5h得到核壳结构分子筛，取Silicalite-1@TS-1分子筛按100g Silicalite-1/TS-1：9.90g TPAOH:55mol H2O比例混合后转入四氟反应釜，在150℃温度条件下水热晶化12h后冷却、过滤、洗涤、干燥得到多级孔Silicalite-1@TS-1。取合成的10g Silicalite-1/TS-1分子筛，加入100g 1wt.％的NH4F溶液搅拌均匀后升温至60℃，再滴加5ml 30wt.％的过氧化氢溶液，60℃保温4h，得到活化的Silicalite-1@TS-1分子筛催化剂3，通过ICP分析得催化剂成品Ti/Si摩尔比为0.28％。
对比实施例1
取45.0g正硅酸四乙酯(0.2mol)与56.0g 25wt.％四丙基氢氧化铵(0.068mol)混合均匀后于常压65℃条件下预水解1h得到正硅酸乙水解液；继续滴加0.0033mol 10wt.％钛酸四丁酯的异丙醇溶液，升温至85℃继续水解4h，预水解溶胶组成摩尔比为1SiO2/0.325TPAOH/1.56IPA/0.06TBT/20H2O。预水解结束后转入180℃四氟内水热釜水热晶化2～6天，得到TS-1分子筛。冷却至室温，离心分离、洗涤后以5℃/min的速度程序升温至550℃焙烧5h，得到常规钛硅分子筛TS-1催化剂4。
催化剂评价
催化剂评价在42～45℃下进行，催化剂评价条件：n(甲醇):n(氯丙烯):n(双氧水)摩尔比为2.2:2:1，TS-1用量为4g/mol双氧水(HP)，反应温度保持在15～18℃，均匀滴加过氧化氢时间120min，并保持在15～18℃条件下继续反应1.5h，通过Agilent GC8890气相色谱分析氯丙烯的转化率、环氧氯丙烷和二氯丙醇及缩醚的选择性，色谱检测条件为：汽化温度250℃，柱箱温度为220℃，载气流量为0.8ml/min，FID温度为300℃。用乙腈作为溶剂，正丁醇作为内标分析产品组成。
催化剂的性能指标：
环氧氯丙烷的收率＝产生环氧氯丙烷摩尔量/过氧化氢转化摩尔量*100％
环氧氯丙烷的选择性％＝环氧氯丙烷的收率/(环氧氯丙烷的收率+二氯丙醇的收率+缩醚的收率)*100％
剩余双氧水用碘量法进行检测：其方法为取0.5g的反应液，加入1g的碘化钾，避光5分钟后，再加入1g钼酸铵，然后用硫代硫酸钠进行滴定。滴定至溶液的颜色发生变化的时候，加入淀粉指示剂，当溶液的颜色为透明色时候即为滴定的终点。
表1：催化剂评价结果对比
Claims (2)
1.一种催化氯丙烯制环氧氯丙烷的核壳结构多级孔纳米片型Silicalite-1@TS-1的制备方法，其特征在于，
将45.0g正硅酸乙酯与56.0g 25wt.％四丙基氢氧化铵混合水解液搅拌30mi n至形成透明溶胶，于常压65℃条件下预水解1h，加入4.25g季胺盐模板剂Template-I得到正硅酸乙酯水解液；冷却至0℃后继续缓慢滴加18wt.％含4.4g钛酸四丁酯和19.8g异丙醇溶液，滴加完毕后继续加热升温至85℃且水解4h，预水解溶胶组成摩尔比为1SiO2:0.34TPAOH:1.65IPA:0.065TBT:20H2O:0.023templa te-I；
所述Template-I的化学式为：
预水解结束后转入180℃四氟水热釜水热晶化48h，得到TS-1纳米片；
冷却至室温，离心分离、洗涤干燥后得到钛硅分子筛晶种，继续加入4.16gTEOS与5.69gTPAOH与85.5gH2O的预水解液，二次晶化液摩尔组成为40TEOS:14TPAOH:9500H2O，继续于180℃下晶化48h，经离心分离、洗涤、干燥后得钛硅分子筛；
将钛硅分子筛转入马弗炉以5℃/min的速度程序升温至550℃焙烧5h得到Silicalite-1/TS-1分子筛；
取Silicalite-1/TS-1分子筛按100g Silicalite-1/TS-1分子筛:9.90gTPAOH:55molH2O比例混合后转入四氟反应釜，在170℃温度条件下水热晶化24h后冷却、过滤、洗涤、干燥得到含多级孔的核壳结构多级孔纳米片型催化剂Silicalite-1/TS-1；
取合成的10g Silicalite-1/TS-1，加入50g 1wt.％的NH4HF2溶液搅拌均匀后升温至60℃，再滴加5ml 30wt.％的过氧化氢溶液，60℃保温4h，得到核壳结构多级孔纳米片型Silicalite-1@TS-1，通过ICP分析得催化剂成品Ti/Si摩尔比为0.24％；
所述核壳结构多级孔纳米片型Silicalite-1@TS-1用于氯丙烯双氧水法合成环氧氯丙烷。
2.一种催化氯丙烯制环氧氯丙烷的核壳结构多级孔纳米片型Silicalite-1@TS-1的制备方法，其特征在于，
将45.0g正硅酸乙酯与56.0g 25wt.％四丙基氢氧化铵混合液剧烈搅拌30min至形成透明溶胶，于常压85℃下预水解1h，然后加入3.78g季胺盐模板剂template-II得到正硅酸乙酯水解液；
所述template-II的化学式为：
冷却至0℃后继续缓慢滴加18wt.％含4.4g钛酸四丁酯和19.8g异丙醇溶液，滴加完毕后继续加热升温至65℃继续水解4h，预水解溶胶组成摩尔比为1SiO2:0.34TPAOH:1.65IPA:0.065TBT:20H2O:0.023template-II；
预水解结束后转入180℃四氟内水热釜水热晶化96h，得到TS-1纳米片；
冷却至室温下离心分离、洗涤得到钛硅分子筛晶种，继续加入4.16gTEOS与5.69gTPAOH与85.5g H2O的预水解液，二次晶化液摩尔组成为40TEOS:14TPAOH:9500H2O，继续于180℃下晶化72h，经离心分离、洗涤、干燥后得钛硅分子筛；
将钛硅分子筛以5℃/min的速度程序升温至550℃焙烧5h得到核壳结构分子筛，取Silicalite-1/TS-1分子筛按100g Silicalite-1/TS-1分子筛:9.90gTPAOH:55mol H2O比例混合后转入四氟反应釜，在170℃温度条件下水热晶化24h后冷却、过滤、洗涤、干燥得到含多级孔的核壳结构多级孔纳米片型催化剂Silicalite-1/TS-1；
取合成的10gSilicalite-1/TS-1，加入100g 1wt.％的NH4HF2溶液搅拌均匀后升温至60℃，再滴加5ml 30wt.％的过氧化氢溶液，60℃保温4h，得到核壳结构多级孔纳米片型Silicalite-1@TS-1，通过ICP分析得催化剂成品Ti/Si摩尔比为0.20％；
所述核壳结构多级孔纳米片型Silicalite-1@TS-1用于氯丙烯双氧水法合成环氧氯丙烷。
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