CN110548539A - 一种hppo用钛硅分子筛催化剂的改性方法 - Google Patents
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Abstract
本发明提供的一种HPPO用钛硅分子筛催化剂的改性方法,包括:将钛硅分子筛浸渍于锶盐水溶液中一段时间,过滤、洗涤、干燥,焙烧;用络合剂溶液处理,水洗,得改性钛硅分子筛。该方法可以有效减少非骨架钛含量、调节酸分布,减少环氧化反应中碱用量。
Description
技术领域
本发明属于无机化学技术领域,涉及一种HPPO用钛硅分子筛的改性方法,更具体地涉及一种金属锶盐和络合剂改性钛硅分子筛的方法。
背景技术
1983年Taramasso等将具有变价特征的过渡金属钛原子引入分子筛骨架,制备了一种具有MFI结构的含钛杂原子分子筛,它具有良好的催化氧化活性和选择性,广泛应用于烯烃环氧化、芳烃羟基化和环己酮氨肟化等反应中。2008年7月,韩国SKC公司10万吨/年双氧水法环氧丙烷(HPPO)装置投产,该装置以钛硅分子筛为催化剂、双氧水为氧化剂直接氧化丙烯为环氧丙烷,率先实现了以双氧水为氧化剂的烯烃环氧化工艺的产业化。
在钛硅分子筛的制备过程中,不可避免的因钛酯的优先水解而产生非骨架钛,引起双氧水分解增多、降低了双氧水利用率,分解产生的氧气与***内易燃易爆的丙烯共存,增加了生产装置的危险性。钛硅分子筛制备原料中往往含有的微量金属杂质(如Al3+、Fe3+)将产生强酸中心,导致副产物的形成。因此,有必要通过改性处理来提高钛硅分子筛的催化活性。大量专利披露了后处理改性钛硅分子筛和改善其催化氧化性能的方法,例如:
专利CN201611256492.6往干燥的钛硅分子筛中通入四氯化硅气体,经洗涤、过滤、干燥、焙烧等处理,调变了分子筛的酸分布,提高了双氧水转化率和环氧丙烷选择性,但过程中产生的废酸还需要中和处理,对设备的耐腐蚀性提出要求。
专利CN201410811161.9采用强酸和氢氟酸的混合溶液对钛硅分子筛进行改性处理,去除非骨架钛,使钛硅分子筛具有更好催化活性和寿命。但氟离子具有强给电子效应,五配位的SiO4/2F-基团通过氢键的方式削弱Ti活性中心的正电性,阻碍催化性能的进一步释放和提升,此外强酸和氢氟酸混合溶液的使用将对设备材质提出严苛要求。
专利CN200810115866.1将钛硅分子筛、保护剂和贵金属源加入到有机胺水溶液中混匀后加入钛的水解溶液,混匀后转入反应釜中水热处理,然后回收钛硅分子筛,提高了钛硅分子筛的氧化活性、选择性和稳定性,但该工艺中贵金属利用率低、回收难,成本高。
专利CN200910226733.6将无机铵盐、氨水、有机氨的溶液与钛硅分子筛混合,在130-190℃下水热晶化24-120h,经过滤、洗涤、干燥、焙烧等步骤,得到改性钛硅分子筛,降低非骨架钛含量,并使孔道更加通畅、晶粒更加完整,提高催化氧化性能。该改性方法在130-190℃下长时间处理,对设备耐压、耐腐蚀提出一定要求,且在改性处理前需要将钛硅分子筛原粉用30%硫酸-30%双氧水加热至80℃2h处理,容易引起双氧水大量分解,工艺安全性不足,难以工业化应用。
发明内容
本发明所要解决的问题是针对现有技术中存在的不足,提供一种高效的钛硅分子筛改性方法,该方法可以有效减少非骨架钛含量、调节酸分布,减少环氧化反应中碱用量,并可以成型后的钛硅分子筛为改性对象,使改性钛硅分子筛在丙烯环氧化反应中具有较高的催化活性和寿命。
本发明提供的一种HPPO用钛硅分子筛催化剂的改性方法,包括:
(1)将锶盐和水按照一定比例配制成锶盐水溶液,将钛硅分子筛浸渍于上述锶盐水溶液中一段时间,过滤、洗涤、干燥,所得固体在一定温度下焙烧;
(2)将上述焙烧后钛硅分子筛装填于固定床装置中,在一定温度下,络合剂溶液以一定空速通过固定床装置,随后用水洗涤至中性,得改性钛硅分子筛。
上述步骤(1)中所述的锶盐优选自硝酸锶、氢氧化锶、乙酸锶中的至少一种,所述的锶盐:水:钛硅分子筛重量比为0.01-0.5:1-3:1;
上述步骤(1)中所述的钛硅分子筛为球形钛硅分子筛、条形钛硅分子筛、片形钛硅分子筛中的至少一种;
上述步骤(1)中所述的浸渍温度为20-80℃、时间为12-72h;焙烧温度为500-600℃;
上述步骤(2)中所述的络合剂溶液为三乙醇胺、乙二胺、葡萄糖酸、1,2-二甲基-3-羟基-4-吡啶酮、草酸钠、亚氨基二琥珀酸四钠、氨基三乙酸钠、8-羟基喹啉等中的至少一种,络合剂溶液浓度为0.1-3%;
上述步骤(2)中络合剂溶液通过固定床装置的重时空速为0.1-1h-1、温度为40-90℃、时间为12-96h。
本发明与现有技术相比,具有以下优点:
(1)通过锶盐和络合剂复合改性,有效减少了非骨架钛物种,降低了双氧水分解,增强了工艺安全性;
(2)金属盐和络合剂改变了分子筛的微观结构,有效减少/屏蔽了钛硅分子筛表面的强酸中心,改变了钛硅分子筛的酸分布,可将丙烯环氧化反应中氨用量降低至零,从源头降低了废水中氨氮含量。
具体实施方式
以下对本发明技术方案的具体实施方式的详细描述,但本发明不限于以下描述内容。
实施例中使用的钛硅分子筛是按照下述方法制备而成的:按照经典文献“Thangaraj A,Eapen M J,Sivasanker S,et al.Studies on the synthesis oftitanium silicalite,TS-1[J].Zeolites,1992,12(8):943-950.”所描述的方法制备钛硅分子筛原粉:以正硅酸乙酯为硅源、钛酸四丁酯为钛源、四丙基氢氧化铵为模板剂,在150-200℃晶化12-48h,经过滤、洗涤、干燥、焙烧后得到钛硅分子筛原粉。将20g钛硅分子筛原粉与1克的田箐粉混合均匀后,加入14毫升30wt%的硅溶胶进一步混合均匀后用挤条、滚球、切片成型,将成型的样品于100℃下干燥12h后再于550℃下焙烧6h即得钛硅分子筛,标记为“对照钛硅分子筛”。
实施例1
将0.3g氢氧化锶与30g水混合制得1wt%氢氧化锶水溶液,20℃下将30g对照钛硅分子筛(片状)浸渍于上述溶液72h,过滤、洗涤、干燥,所得固体在500℃下焙烧6h。
将上述焙烧后催化剂装填于固定床装置中,在60℃下以重时空速0.1h-1泵入0.1wt%1,2-二甲基-3-羟基-4-吡啶酮水溶液72h,随后用水洗涤至中性,得改性钛硅分子筛(片状)-1。
实施例2
将5g乙酸锶与30g水混合制得14wt%乙酸锶水溶液,80℃下将30g对照钛硅分子筛(条状)浸渍于上述溶液12h,过滤、洗涤、干燥,所得固体在600℃下焙烧6h。
将上述焙烧后催化剂装填于固定床装置中,在40℃下以重时空速0.5h-1泵入3wt%三乙醇胺水溶液12h,随后用水洗涤至中性,得改性钛硅分子筛(条状)-2。
实施例3
将15g硝酸锶与90g水混合制得14wt%硝酸锶水溶液,60℃下将30g对照钛硅分子筛(球状)浸渍于上述溶液12h,过滤、洗涤、干燥,所得固体在550℃下焙烧6h。
将上述焙烧后催化剂装填于固定床装置中,50℃下以重时空速0.5h-1泵入2wt%氨基三乙酸钠水溶液48h,随后用水洗涤至中性,得改性钛硅分子筛(球状)-3。
实施例4
将0.5g氢氧化锶、5.5g硝酸锶与60g水混合制得9wt%混合锶盐水溶液,60℃下将30g对照钛硅分子筛(球状)浸渍于上述溶液48h,过滤、洗涤、干燥,所得固体在550℃下焙烧6h。
将上述焙烧后催化剂装填于固定床装置中,90℃下以重时空速1h-1泵入2wt%亚氨基二琥珀酸四钠和1wt%氨基三乙酸钠混合溶液96h,随后用水洗涤至中性,得改性钛硅分子筛(球状)-4。
实施例5
为评价改性钛硅分子筛催化剂在丙烯液相环氧化的效果,固定评价工艺为:反应压力3MPa,反应温度为40℃,催化剂装填10g,50%双氧水重时空速为0.50h-1,双氧水:丙烯:甲醇摩尔比=1:3:8,氨水预混入双氧水溶液中,随双氧水进料。反应结果的主要评价指标有:双氧水转化率XH2O2、环氧丙烷选择性SPO、双氧水利用率UH2O2,式中:n0表示反应前摩尔数、n表示反应后摩尔数,PG为1,2-丙二醇、MME为1-甲氧基-2丙醇和2-甲氧基-1丙醇。以双氧水转化率<97%判定催化剂失活,确定催化剂单程寿命。
本发明所述内容并不仅限于本发明所述实施例内容。
本文中应用了具体个例对本发明结构及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (6)
1.一种HPPO用钛硅分子筛催化剂的改性方法,包括下列步骤:
(1)将锶盐和水按照一定比例配制成锶盐水溶液,将钛硅分子筛浸渍于上述锶盐水溶液中一段时间,过滤、洗涤、干燥,所得固体在一定温度下焙烧;
(2)将上述焙烧后钛硅分子筛装填于固定床装置中,在一定温度下,络合剂溶液以一定空速通过固定床装置,随后用水洗涤至中性,得改性钛硅分子筛。
2.根据权利要求1所述的一种HPPO用钛硅分子筛催化剂的改性方法,其特征在于,上述步骤(1)中所述的锶盐选自硝酸锶、氢氧化锶、乙酸锶中的至少一种,所述的锶盐:水:钛硅分子筛重量比为0.01-0.5:1-3:1。
3.根据权利要求1所述的一种HPPO用钛硅分子筛催化剂的改性方法,其特征在于,上述步骤(1)中所述的钛硅分子筛为球形钛硅分子筛、条形钛硅分子筛、片形钛硅分子筛中的至少一种。
4.根据权利要求1所述的一种HPPO用钛硅分子筛催化剂的改性方法,其特征在于,上述步骤(1)中所述的浸渍温度为20-80℃、时间为12-72h;焙烧温度为500-600℃。
5.根据权利要求1所述的一种HPPO用钛硅分子筛催化剂的改性方法,其特征在于,上述步骤(2)中所述的络合剂溶液为三乙醇胺、乙二胺、葡萄糖酸、1,2-二甲基-3-羟基-4-吡啶酮、草酸钠、亚氨基二琥珀酸四钠、氨基三乙酸钠、8-羟基喹啉中的至少一种,络合剂溶液浓度为0.1-3%。
6.根据权利要求1所述的一种HPPO用钛硅分子筛催化剂的改性方法,其特征在于,上述步骤(2)中络合剂溶液通过固定床装置的重时空速为0.1-1h-1、温度为40-90℃、时间为12-96h。
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