CN106378122A - 一种硅胶负载钛催化剂及制备方法及用途 - Google Patents
一种硅胶负载钛催化剂及制备方法及用途 Download PDFInfo
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Abstract
本发明公开了一种硅胶负载钛催化剂及制备方法及用途。硅胶负载钛催化剂的制备方法为:(1)无定型硅胶粉末成型为无定型硅胶颗粒;(2)将无定型硅胶颗粒升温至200‑500℃,N2下吹扫除去水分;将液态TiCl4加热,气化后与氮气充分混合后通入化学气相沉积装置中,升温至600‑1000℃,反应;冷却,N2吹扫,降至室温;(3)焙烧得到硅胶负载钛催化剂。硅胶负载钛催化剂打破了微孔材料孔道尺寸的局限性,增加了TiO2分散度,活性组分大部分暴露于催化剂表面,Ti‑O‑Si键的形成也对锐钛矿型TiO2起到了稳定作用。催化丙烯选择性氧化一步制备环氧丙烷,提高了环氧化反应的催化活性与环氧丙烷的选择性。
Description
技术领域
本发明涉及一种硅胶负载钛催化剂及制备方法。
背景技术
Shell化学公司最早开发了TiO2-SiO2材料,所用无定型硅材料的比表面积和孔径较小,使得钛的负载量很小,作为丙烯选择性氧化为环氧丙烷反应的催化剂,影响了催化效果。
美国专利US4410501公开了TS-1分子筛的合成方法,该分子筛组分为TiO2-SiO2,其孔径大小只有0.55nm,难以催化大分子有机过氧化物参与的选择性氧化反应。
TanevPT等采用正十二胺为模板剂,钛酸异丙酯和正硅酸乙酯为原料,乙醇和异丙醇水溶液为溶剂,室温条件合成TiO2-SiO2材料。但水热方法所合成的钛主要以四配位的形式包埋于体相中,影响了催化效果。
硅胶负载钛(TiO2-SiO2)催化剂可用于催化烯烃的选择性氧化反应,还可作为光催化、酯交换以及异构化反应的催化剂。TiO2具有锐钛矿、金红石和板钛矿三种晶型结构,自身的比表面积小和孔道很少。其中锐钛矿型TiO2具有良好的活性,但在高温下不稳定,容易转化为惰性的金红石结构,失去催化活性,限制其工业化发展。研究表明,TiO2-SiO2负载氧化物间形成的Ti-O-Si键对锐钛矿型TiO2起到了稳定作用。
如上所述,由于孔道大小的限制,微孔硅催化剂并不能良好的催化大分子参与的环氧化反应。水热方法合成的介孔催化剂的活性组分又大多包埋于催化剂内部。因此,找到一种合适的制备方法,开发新型的催化剂,提高催化剂孔径和钛负载量,使活性组分大部分暴露于催化剂表面,并使锐钛矿型趋于稳定,进而提高丙烯环氧化反应的活性与选择性以及催化剂生产效率,具有非常重要的意义。
发明内容
本发明的目的是克服现有技术的不足,提供以廉价无机钛化合物为钛源,无定型硅胶为载体制备的孔径大、热稳定良好、具有较大比表面积、催化性能好的一种硅胶负载钛催化剂。
本发明的第二个目的是提供制备方法简单、易于操作,重复性高的一种硅胶负载钛催化剂的制备方法。
本明的第三个目的是提供硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷的用途。
本发明的技术方案概述如下:
一种硅胶负载钛催化剂,是载体无定型硅胶颗粒负载有TiO2。
硅胶负载钛催化剂的制备方法,包括如下步骤:
(1)无定型硅胶粉末成型为无定型硅胶颗粒;
(2)将无定型硅胶颗粒置于化学气相沉积装置中,升温至200-500℃,在50-200ml/min的N2保护下吹扫至少1h,除去水分;将液态TiCl4加热至30~100℃,气化后与氮气充分混合后通入所述化学气相沉积装置中,TiCl4蒸汽的流量为(0.05-0.5)ml/min,氮气流量为50ml/min,升温至600-1000℃,反应1~3h;将化学气相沉积装置冷却至200-500℃,50-200ml/min的N2下吹扫至少2h,降至室温;
(3)空气氛围下,以5-15℃/min的升温至400-600℃焙烧4-6h,得到硅胶负载钛催化剂。
无定型硅胶粉末成型为无定型硅胶颗粒的步骤优选的是:
将无定型胶粉末与拟薄水铝石按质量比60-90:10-40的比例于捏合机中混合得混合物,加入质量浓度为2%-10%的硝酸水溶液,所述混合物与所述硝酸水溶液的比例为10g:5-10mL,搅拌混合,挤成条状,70-110℃烘干8-12h,空气条件下,于500-550℃焙烧3-5h,研磨成颗粒,过30-40目筛,得无定型硅胶颗粒。
上述硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷(PO)的用途,包括如下步骤:在固定床中,按比例,放入0.5g硅胶负载钛催化剂,以丙烯、过氧化氢异丙苯(CHP)为原料,将过氧化氢异丙苯溶解在异丙苯中,在50-110℃,反应压力为0.1-8M Pa,空速控制在1-10h-1,反应1-12h生成环氧丙烷;所述过氧化氢异丙苯、丙烯和异丙苯的摩尔比为1:1-10:4-50,所述硅胶负载钛催化剂与过氧化氢异丙苯的质量比为1-5:10。
本发明的优点:
本发明制备的硅胶负载钛催化剂打破了微孔材料孔道尺寸的局限性,增加了TiO2分散度,活性组分大部分暴露于催化剂表面,Ti-O-Si键的形成也对锐钛矿型TiO2起到了稳定作用。硅胶负载钛催化剂催化丙烯选择性氧化一步制备环氧丙烷,提高了环氧化反应的催化活性与环氧丙烷的选择性,为加快工业化步伐提供了先决条件。
附图说明
图1为硅胶负载钛催化剂的XRD谱。
具体实施方式
下面通过具体实施例对本发明作进一步的说明。
实施例1
无定型硅胶粉末成型为无定型硅胶颗粒的方法,包括如下步骤:
将无定型硅胶粉末(商品)与拟薄水铝石按质量比80:20的比例于捏合机中混合得混合物,加入质量浓度为5%的硝酸水溶液,所述混合物与所述硝酸水溶液的比例为10g:8mL,搅拌混合,挤成条状,100℃烘干10h,空气条件下,于530℃焙烧4h,研磨成颗粒,过30-40目筛,得无定型硅胶颗粒。
实施例2
无定型硅胶粉末成型为无定型硅胶颗粒的方法,包括如下步骤:
将无定型硅胶粉末与拟薄水铝石按质量比60:40的比例于捏合机中混合得混合物,加入质量浓度为10%的硝酸水溶液,所述混合物与所述硝酸水溶液的比例为10g:10mL,搅拌混合,挤成条状,70℃烘干12h,空气条件下,于500℃焙烧5h,研磨成颗粒,过30-40目筛,得无定型硅胶颗粒。
实施例3
无定型硅胶粉末成型为无定型硅胶颗粒的方法,包括如下步骤:
将无定型硅胶粉末与拟薄水铝石按质量比90:10的比例于捏合机中混合得混合物,加入质量浓度为2%的硝酸水溶液,所述混合物与所述硝酸水溶液的比例为10g:5mL,搅拌混合,挤成条状,110℃烘干8h,空气条件下,于550℃焙烧3h,研磨成颗粒,过30-40目筛,得无定型硅胶颗粒。
实施例4
硅胶负载钛催化剂的制备方法,包括如下步骤:
(1)实施例1的方法制备无定型硅胶颗粒;
(2)将无定型硅胶颗粒置于化学气相沉积装置中,升温至350℃,在100ml/min的N2保护下吹扫1h,除去水分;将液态TiCl4加热至65℃,气化后与氮气充分混合后通入所述化学气相沉积装置中,TiCl4蒸汽的流量为0.1ml/min,氮气流量为50ml/min,升温至800℃,反应2h;将化学气相沉积装置冷却至350℃,100ml/min的N2下吹扫2h,降至室温;
在这个过程中,先使用0.1M氢氧化钠水溶液吸收未参加反应的四氯化钛气体,再用活性炭继续吸收四氯化钛气体;
(3)空气氛围下,以10℃/min的升温至500℃焙烧5h,得到硅胶负载钛催化剂。见图1。
此硅胶负载钛催化剂的比表面积为181.4m2/g,孔径为孔容为1.25cm3/g,钛的负载量为1.68%。
实施例5
硅胶负载钛催化剂的制备方法,包括如下步骤:
(1)实施例2的方法制备无定型硅胶颗粒;
(2)将无定型硅胶颗粒置于化学气相沉积装置中,升温至200℃,在200ml/min的N2保护下吹扫1.5h,除去水分;将液态TiCl4加热至30℃,气化后与氮气充分混合后通入所述化学气相沉积装置中,TiCl4蒸汽的流量为0.05ml/min,氮气流量为50ml/min,升温至600℃,反应3h;将化学气相沉积装置冷却至200℃,50ml/min的N2下吹扫2.5h,降至室温;
在这个过程中,先使用0.1M氢氧化钠水溶液吸收未参加反应的四氯化钛气体,再用活性炭继续吸收四氯化钛气体;
(3)空气氛围下,以15℃/min的升温至400℃焙烧6h,得到硅胶负载钛催化剂。
此硅胶负载钛催化剂的比表面积为153.6m2/g,孔径为孔容为1.11cm3/g,钛的负载量为1.30%。
实施例6
硅胶负载钛催化剂的制备方法,包括如下步骤:
(1)实施例3的方法制备无定型硅胶颗粒;
(2)将无定型硅胶颗粒置于化学气相沉积装置中,升温至500℃,在50ml/min的N2保护下吹扫1h,除去水分;将液态TiCl4加热至100℃,气化后与氮气充分混合后通入所述化学气相沉积装置中,TiCl4蒸汽的流量为0.5ml/min,氮气流量为50ml/min,升温至1000℃,反应1h;将化学气相沉积装置冷却至500℃,200ml/min的N2下吹扫2h,降至室温;
在这个过程中,先使用0.1M氢氧化钠水溶液吸收未参加反应的四氯化钛气体,再用活性炭继续吸收四氯化钛气体;
(3)空气氛围下,以5℃/min的升温至600℃焙烧4h,得到硅胶负载钛催化剂。
此硅胶负载钛催化剂的比表面积为123.6m2/g,孔径为孔容为0.81cm3/g,钛的负载量为1.39%。
实施例7
实施例4的硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷的用途,包括如下步骤:
在固定床中,按比例,放入0.5g硅胶负载钛催化剂,以丙烯、过氧化氢异丙苯为原料,将过氧化氢异丙苯溶解在异丙苯中,在80℃,反应压力为5MPa,空速控制在10h-1,反应6h生成环氧丙烷;所述过氧化氢异丙苯、丙烯和异丙苯的摩尔比为1:5:30,所述硅胶负载钛催化剂与过氧化氢异丙苯的质量比为3:10。副产物2-苯基-2-丙醇经过脱水、加氢、氧化成过氧化氢异丙苯后循环使用。反应结果见表1。
表1
实施例8
实施例5的硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷的用途,包括如下步骤:
在固定床中,按比例,放入0.5g硅胶负载钛催化剂,以丙烯、过氧化氢异丙苯为原料,将过氧化氢异丙苯溶解在异丙苯中,在50℃,反应压力为0.1MPa,空速控制在1h-1,反应12h生成环氧丙烷;所述过氧化氢异丙苯、丙烯和异丙苯的摩尔比为1:1:4,所述硅胶负载钛催化剂与过氧化氢异丙苯的质量比为1:10。副产物2-苯基-2-丙醇经过脱水、加氢、氧化成过氧化氢异丙苯后循环使用。反应结果见表2。
表2
实施例9
实施例6的硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷的用途,包括如下步骤:
在固定床中,按比例,放入0.5g硅胶负载钛催化剂,以丙烯、过氧化氢异丙苯为原料,将过氧化氢异丙苯溶解在异丙苯中,在110℃,反应压力为8MPa,空速控制在5h-1,反应1h生成环氧丙烷;所述过氧化氢异丙苯、丙烯和异丙苯的摩尔比为1:10:50,所述硅胶负载钛催化剂与过氧化氢异丙苯的质量比为5:10。副产物2-苯基-2-丙醇经过脱水、加氢、氧化成过氧化氢异丙苯后循环使用。反应结果见表3。
表3
Claims (5)
1.一种硅胶负载钛催化剂,其特征是载体无定型硅胶颗粒负载有TiO2。
2.权利要求1硅胶负载钛催化剂的制备方法,其特征是包括如下步骤:
(1)无定型硅胶粉末成型为无定型硅胶颗粒;
(2)将无定型硅胶颗粒置于化学气相沉积装置中,升温至200-500℃,在50-200ml/min的N2保护下吹扫至少1h,除去水分;将液态TiCl4加热至30~100℃,气化后与氮气充分混合后通入所述化学气相沉积装置中,TiCl4蒸汽的流量为(0.05-0.5)ml/min,氮气流量为50ml/min,升温至600-1000℃,反应1~3h;将化学气相沉积装置冷却至200-500℃,50-200ml/min的N2下吹扫至少2h,降至室温;
(3)空气氛围下,以5-15℃/min的升温至400-600℃焙烧4-6h,得到硅胶负载钛催化剂。
3.根据权利要求2所述的方法,其特征是无定型硅胶粉末成型为无定型硅胶颗粒的步骤是:
将无定型胶粉末与拟薄水铝石按质量比60-90:10-40的比例于捏合机中混合得混合物,加入质量浓度为2%-10%的硝酸水溶液,所述混合物与所述硝酸水溶液的比例为10g:5-10mL,搅拌混合,挤成条状,70-110℃烘干8-12h,空气条件下,于500-550℃焙烧3-5h,研磨成颗粒,过30-40目筛,得无定型硅胶颗粒。
4.权利要求1硅胶负载钛催化剂在催化丙烯选择性氧化一步制备环氧丙烷的用途。
5.根据权利要求4所述的用途,其特征是包括如下步骤:在固定床中,按比例,放入0.5g硅胶负载钛催化剂,以丙烯、过氧化氢异丙苯为原料,将过氧化氢异丙苯溶解在异丙苯中,在50-110℃,反应压力为0.1-8MPa,空速控制在1-10h-1,反应1-12h生成环氧丙烷;所述过氧化氢异丙苯、丙烯和异丙苯的摩尔比为1:1-10:4-50,所述硅胶负载钛催化剂与过氧化氢异丙苯的质量比为1-5:10。
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