CN107715868A - 一种丙烯环氧化催化剂的制备方法及其用途 - Google Patents
一种丙烯环氧化催化剂的制备方法及其用途 Download PDFInfo
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- CN107715868A CN107715868A CN201711024586.5A CN201711024586A CN107715868A CN 107715868 A CN107715868 A CN 107715868A CN 201711024586 A CN201711024586 A CN 201711024586A CN 107715868 A CN107715868 A CN 107715868A
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- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明公开了一种丙烯环氧化催化剂的制备方法,先将硅源预水解,再加入钛源反应形成溶胶,将溶胶通过雾化后喷入液氨中成型,并进行扩孔,再经干燥、焙烧及硅烷化处理得到Ti‑SiO2复合氧化物催化剂。该催化剂可以应用于丙烯环氧化制备环氧丙烷化工过程中,对环氧丙烷平均选择性高达97.5%,具有工业化应用前景。
Description
技术领域:
本发明涉及一种丙烯环氧化催化剂的制备方法,具体地说是Ti-SiO2复合氧化物催化剂的制备方法及其作为催化剂催化丙烯环氧化制备环氧丙烷的用途。
背景技术:
以乙苯过氧化氢(EBHP)为氧化剂的乙苯共氧化工艺(PO/SM)和以异丙苯过氧化氢(CHP)为氧化剂的CHP工艺是生产环氧丙烷的两种重要工艺;这两种工艺克服了氯醇法的腐蚀大、污水多等缺点,具有产品成本低和环境污染较小等优点。
非均相PO/SM工艺环氧化工序所用催化剂为Ti-SiO2复合氧化物,美国公开专利US3829392、US2003166951,中国公开专利CN1894030、CN1720100公开其制备方法为:先将硅胶载体进行干燥处理,然后用N2或其它惰性气体将卤化钛蒸汽带入反应管中与硅胶发生化学反应(该步骤称为化学气相沉积),高温焙烧,最后经过水洗等步骤制备得到催化剂。钛活性物种在SiO2表面分散性不好,而且容易形成游离的TiO2,导致氧化剂无效分解,降低PO的选择性。
CHP工艺所用催化剂也为Ti-SiO2复合氧化物,美国公开专利US6211388、US5744619和中国公开专利CN7250775公开其制备方法为溶胶凝胶法:将硅源与钛源分别溶解在醇溶剂中,并加入季铵离子(如十六烷基溴化铵)作为模板剂,经水解、聚合、老化形成凝胶,再高温焙烧和硅烷化处理得到催化剂。溶胶凝胶法相比气相沉积法可以使不同组分在分子水平相互混溶,得到纳米相区甚至分子态分散的钛活性中心。但是溶胶凝胶法最大的缺点之一是在制备过程中需要加入价格昂贵的季铵盐作为模板剂,一般还需要通过高温焙烧除去模板剂,模板剂不可回收,造成催化剂成本较高。
基于现有的Ti-SiO2复合氧化物制备方法的缺陷,需要开发一种Ti活性物种在SiO2表面分散好,对PO选择性高,制造成本低的新的催化剂制备方法。
发明内容:
本发明的目的在于提供一种丙烯环氧化催化剂的制备方法,该方法的优势:Ti活性物种在SiO2表面分散好,对PO选择性高,制造成本低。
本发明还提供一种由所述方法制备的Ti-SiO2复合氧化物催化剂,可以用做丙烯环氧化制备环氧丙烷(PO)的催化剂,具有高活性和对环氧丙烷的高选择性。
为实现上述发明目的,本发明采用的技术方案如下:
本发明所述的丙烯环氧化催化剂采用溶胶法制备,优选使用Re和Zn对催化剂进行改性,在液氨中成型和扩孔、干燥、高温焙烧,最后进行硅烷化处理得到催化剂。本发明不使用模板剂,在液氨中成型和扩孔,降低催化剂制作成本;用Re和Zn对催化剂进行改性,Re、Zn和Ti协同作用能够提高催化剂的活性和对环氧丙烷的选择性。
具体地,一种丙烯环氧化催化剂的制备方法,包括以下步骤:
(1)硅源预水解:将硅酯溶解于低碳醇中,加入水解催化剂,逐滴加入一定量去离子水,一定温度下反应一定时间,记做A液;
(2)成胶:将一定量钛酯溶于低碳醇后,逐滴加入A液中;补充加入适量去离子水,反应一段时间后形成溶胶;
(3)将步骤(2)得到的溶胶通过雾化器喷入液氨中成型;
(4)将步骤(3)得到的催化剂前驱体进行扩孔处理;
(5)将步骤(4)扩孔后的催化剂前驱体干燥和高温焙烧;
(6)将步骤(5)得到的产品进行硅烷化处理得到Ti-SiO2复合氧化物催化剂。
本发明中,所述步骤(1)中硅酯可以是正硅酸乙酯、正硅酸甲酯、正硅酸丙酯、正硅酸丁酯等的一种或几种混合物,低碳醇可以是甲醇、乙醇、正丙醇、异丙醇中的一种或多种,优选异丙醇;硅酯在低碳醇中的浓度为20~30wt%;水解催化剂为甲酸、乙酸中的一种或两种的混合物,加入量为硅酯的0.8~1.5wt%;逐滴加入水量为理论上硅酯水解30~80%所需的水量;反应温度为40~70℃,反应时间为1~3h;硅酯预水解步骤为关键步骤,因为钛酯水解速率快,而硅酯水解速率慢,两者水解速率不匹配,如果不将硅酯预水解,会造成Ti活性组分分布不均匀,甚至会形成游离的TiO2,而游离TiO2会造成过氧化物的自分解反应,降低催化剂的选择性;而且,实验发现,不加水解催化剂和不将硅源进行预水解会形成沉淀,不能形成凝胶。
本发明中,所述步骤(2)中所用钛酯可以是钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯中的一种或多种,钛酯中Ti的量为步骤(1)中原料硅酯完全水解为SiO2质量的2~5%,钛酯在低碳醇中的浓度为30~50wt%,反应时间为1h~4h。
本发明中,优选地,所述步骤(2)钛酯完全加入到步骤(1)中A液后,不加水而加入一定量的NH4ReO4和锌盐混合溶液反应,形成溶胶;NH4ReO4和锌盐混合溶液浓度无特殊要求,Re与Ti的摩尔比为0.01~0.05:1,Zn与Ti的摩尔比为0.05~0.15:1,锌盐可以为ZnCl2和Zn(NO3)2中的一种或两种混合物;NH4ReO4和锌盐混合溶液所用水量为步骤(1)未水解的硅酯和步骤(2)钛酯理论上完全水解需要的水量;实验发现加入一定量的Re对催化剂进行改性(Re在催化剂中以氧化物Re2O7形式存在),Re和Ti(在催化剂中,Ti的存在形式主要为T=O四面体或者称谓四配位的骨架Ti)协同作用提高了催化剂对PO的选择性;加入一定量Zn对催化剂进行改性(Zn在催化剂中以氧化物ZnO形式存在),ZnO具有碱性,可以中和催化剂制备过程中形成的游离的TiO2的酸性,减少过氧化物的分解,提高对PO的选择性。
本发明中,所述步骤(3)雾化器为离心式雾化器,通过调整喷头大小和转速使雾化的溶胶平均粒径范围为100~850μm,优选平均粒径400~580μm;采用将溶胶通过雾化器喷入液氨中进行成型优点为:直接得到类球形颗粒,使单位体积的反应器能装填更多的催化剂;成型后颗粒强度高,平均强度达到23~26N/颗;相比油中成型工艺,没有将油从成型催化剂前驱体脱除步骤,工艺过程更简单。
本发明中,所述步骤(4)扩孔工艺条件为:扩孔剂为液氨,扩孔温度为60~140℃,扩孔时间为3~15h;扩孔的目的是使催化剂形成一定的孔道结构,使更多活性Ti物种暴露,有利于反应物接触到活性中心;扩孔得到的催化剂比表面积为180~300m2/g,孔容为0.9~1.1ml/g,平均孔径为8.5~13nm;本发明采用液氨为扩孔剂而不采用氨水或铵盐水溶液是因为:氨水或铵盐水溶液中的水会造成已经形成的骨架Ti物种变成游离的TiO2,降低催化剂对PO的选择性。
本发明中,所述步骤(5)干燥温度为80~120℃,干燥时间为2~5h;在空气或任何惰性气氛下焙烧,升温速率为没有严格限制,可以采用常用升温速率1~3℃/min,焙烧温度为450~600℃,焙烧时间为2~5h。
本发明中,所述步骤(6)中硅烷化试剂为六甲基二硅胺烷,用量为5~15wt%,以硅酯全部水解为SiO2的质量计,六甲基二硅胺烷温度为126~150℃,N2在反应管中的流速为0.5~1cm/s,硅烷化温度为200~300℃,硅烷化时间为60~180min;用N2将硅烷化试剂蒸汽带入反应管中,发生的化学反应为:
~O-Si-OH+Si(CH3)3-NH-Si(CH3)3→~O-Si-O-Si(CH3)3
目的为提高催化剂表面的疏水性,降低催化剂对过氧化物的分解能力,提高催化剂对PO的选择性。
本发明的催化剂用做丙烯环氧化制备环氧丙烷(PO)的催化剂时反应的工艺条件为:丙烯和CHP的摩尔比为5~7:1,质量空速为2~3.5hr-1;起始反应温度:50~60℃,根据CHP转化率(保证CHP转化率>99%)逐渐升高反应温度。
本发明具有以下技术效果:
(1)本发明不用模板剂,用液氨做扩孔剂即达到相关专利中用模板剂达到的技术效果,降低了催化剂成本;(2)优选的方案中通过添加NH4ReO4对催化剂进行改性,助剂Re与Ti活性中心协同作用,提高了催化剂的活性和对环氧丙烷的选择性;(3)优选的方案中添加Zn对催化剂进行改性,ZnO具有碱性,可以中和催化剂制备过程中形成的游离的TiO2的酸性,减少过氧化物氧化剂的分解,提高对PO的选择性;催化剂对PO的平均选择性高达97.5%,降低了PO产品丙烯单耗;(4)采用将溶胶通过雾化器喷入液氨中进行成型直接得到球形颗粒,不用经过一般溶胶凝胶法非常耗时的老化步骤,提高生产效率;(5)喷入液氨中进行成型,成型后颗粒强度高,平均强度达到23~26N/颗;相比油中成型工艺,没有将油从成型催化剂前驱体脱除步骤,工艺过程更简单。
具体实施方式:
为了更好理解本发明,下面结合实施例进一步阐明本发明内容,但本发明的内容不仅仅局限于下面的实施例。
本发明中实施例中比表面积及孔结构测定方法为BET法(N2物理吸附法),仪器型号为:ASP2020,美国麦克仪器公司产。
本发明中实施例中强度测定仪型号为:KC-3数显颗粒强度测定仪,姜堰市分析仪器厂产。
本发明中实施例中通过气相色谱进行分析反应液及尾气吸收液中的PO含量,通过碘量法分析CHP的转化率。色谱分析条件如表1所示。
表1色谱操作条件
通过内标法进行PO含量测定,液相浓度测定以DMF为溶剂,以DT(二氧六环)为内标物,测定PO与DT的内标标准曲线为y=0.6985x-0.0046,R2=0.999;气相吸收液PO浓度测定以甲苯为内标物,测定PO与甲苯的内标标准曲线y=2.161x+0.0002,R2=0.999。
液相PO浓度=(0.6985×(APO/ADT)-0.0046)×0.01×稀释倍数
液相PO含量=液相PO浓度×液相取样质量
气相PO浓度=(2.162×(APO/A甲苯)+0.0002)×甲苯质量
气相PO含量=气相PO浓度×吸收液总量/气相取样量
PO总生成量=气相PO含量+液相PO含量
PO的选择性=PO总生成量/理论上CHP所能氧化丙烯生成的PO量×100%
CHP转化率通过碘量法进行滴定,采用滴定仪进行测定。
CHP转化率=(CHP初始值-CHP剩余量)/EBHP初始值
CHP剩余量=(滴定终点-空白)×CNa2S2O3×0.001×0.5×142×液样总量/滴定取样量
实施例中所用硅酯为正硅酸乙酯,钛酯为钛酸四丁酯。
实施例及对比例中催化剂用于丙烯环氧化制环氧丙烷工艺条件为:氧化剂为异丙苯过氧化氢(CHP),反应管内径为24mm固定床反应器,催化剂装填量为10g;丙烯和CHP的摩尔比为7:1,质量空速为3.5hr-1;起始反应温度:50℃,根据CHP转化率(保证CHP转化率>99%)逐渐升高反应温度。
实施例1
将208g正硅酸乙酯溶解于792g异丙醇中,然后加入1.67g甲酸作为水解催化剂,逐滴加入10.8g去离子水,50℃反应1h,记做A液;称取8.5g钛酸四丁酯溶于19.8g异丙醇后,逐滴加入到A液中,搅拌均匀,记为B液;称取0.067g NH4ReO4和0.17gZnCl2溶于25.2g去离子水中,逐滴加入B液中,搅拌均匀,记为C液。C液反应4h形成溶胶,将溶胶使用离心型雾化器喷入液氨中成型,然后在80℃下扩孔处理15h。将扩孔后的催化剂前驱体在烘箱中80℃干燥2h,在马弗炉内550℃焙烧3h。将焙烧后的样品进行气相硅烷化处理:在汽化罐中加入3g六甲基二硅胺烷,汽化罐加热温度为130℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和焙烧后的样品进行反应,N2在反应管中线速度为1cm/s,硅烷化温度为200℃,硅烷化时间为180min;得到的催化剂记为TS-A1。
BET法测定TS-A1催化剂的比表面积为278.9m2/g,孔容为0.93ml/g,平均孔径为9.7nm;平均强度为26.2N/颗。对TS-A1进行评价,连续运行480hr,反应温度由最初50℃升温至65℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性最高达到96.8%,平均达到96.1%。
实施例2
将249.6g正硅酸乙酯溶解于750.4g异丙醇中,然后加入2.5g甲酸作为水解催化剂,逐滴加入21.6g去离子水,60℃反应90min,记做A液;称取17.85g钛酸四丁酯溶于26.78g异丙醇后,逐滴加入到A液中,搅拌均匀,记为B液;称取0.422g NH4ReO4和0.714gZnCl2溶于21.6g去离子水中,逐滴加入B液中,搅拌均匀,记为C液。C液反应2h形成溶胶,将溶胶使用离心型雾化器喷入液氨中成型,然后在120℃下扩孔处理6h。将扩孔后的催化剂前驱体在烘箱中100℃干燥3h,在马弗炉内450℃焙烧5h。将焙烧后的样品进行气相硅烷化处理:在汽化罐中加入7.2g六甲基二硅胺烷,汽化罐加热温度为140℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和焙烧后的样品进行反应,N2在反应管中线速度为0.5cm/s,硅烷化温度为250℃,硅烷化时间为120min;得到的催化剂记为TS-A2。
BET法测定TS-A2催化剂的比表面积为248.4m2/g,孔容为1.04ml/g,平均孔径为11nm;平均强度为27.1N/颗。对TS-A2进行评价,连续运行1000hr,反应温度由最初50℃升温至80℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性最高达到97.8%,平均达到97.5%。
实施例3
将291.2g正硅酸乙酯溶解于707.8g异丙醇中,然后加入4.36g乙酸作为水解催化剂,逐滴加入50.4g去离子水,70℃反应140min,记做A液;称取29.75g钛酸四丁酯溶于29.75g异丙醇后,逐滴加入到A液中,搅拌均匀,记为B液;称取1.172g NH4ReO4和1.785gZnCl2溶于10.08g去离子水中,逐滴加入B液中,搅拌均匀,记为C液。C液反应1h形成溶胶,将溶胶使用离心型雾化器喷入液氨中成型,然后在140℃下扩孔处理3h。将扩孔后的催化剂前驱体在烘箱中120℃干燥5h,在马弗炉内600℃焙烧2h。将焙烧后的样品进行气相硅烷化处理:在汽化罐中加入12.6g六甲基二硅胺烷,汽化罐加热温度为150℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和焙烧后的样品进行反应,N2在反应管中线速度为0.6cm/s,硅烷化时间为100min;硅烷化温度为300℃,得到的催化剂记为TS-A3。
BET法测定TS-A3催化剂的比表面积为208.6m2/g,孔容为1.2ml/g,平均孔径为12.8nm;平均强度为26.0N/颗。对TS-A3进行评价,连续运行800hr,反应温度由最初50℃升温至90℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性最高达到97.2%,平均达到96.9%。
实施例4
将249.6g正硅酸乙酯溶解于750.4g异丙醇中,然后加入2.5g甲酸作为水解催化剂,逐滴加入21.6g去离子水,60℃反应90min,记做A液;称取17.85g钛酸四丁酯溶于26.78g异丙醇后,逐滴加入到A液中,搅拌均匀,记为B液;将21.6g去离子水中,逐滴加入B液中。B液反应3h形成溶胶。将溶胶使用离心型雾化器喷入液氨中成型,然后在120℃下扩孔处理6h。将扩孔后的催化剂前驱体在烘箱中100℃干燥3h,在马弗炉内450℃焙烧5h。将焙烧后的样品进行气相硅烷化处理:在汽化罐中加入7.2g六甲基二硅胺烷,汽化罐加热温度为140℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和焙烧后的样品进行反应,N2在反应管中线速度为0.5cm/s,硅烷化温度为250℃,硅烷化时间为120min;得到的催化剂记为TS-A4。
BET法测定TS-N1催化剂的比表面积为248.2m2/g,孔容为1.04ml/g,平均孔径为11nm;平均强度为26.6N/颗。对TS-A2进行评价,连续运行600hr,反应温度由最初60℃升温至90℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性最高达到93.8%,平均达到92.7%。
对比例1
将249.6g正硅酸乙酯溶解于750.4g异丙醇中,然后加入2.5g甲酸作为水解催化剂,逐滴加入21.6g去离子水,60℃反应90min,记做A液;称取17.85g钛酸四丁酯溶于26.78g异丙醇后,逐滴加入到A液中,搅拌均匀,记为B液;将21.6g去离子水中,逐滴加入B液中,搅拌均匀,记为C液。C液反应1h形成溶胶,将溶胶经过12h老化形成凝胶。然后将凝胶在烘箱中100℃干燥3h,破碎,筛分0.4~1.2mm颗粒,在马弗炉内450℃焙烧5h。将焙烧后的样品进行气相硅烷化处理:在汽化罐中加入7.2g六甲基二硅胺烷,汽化罐加热温度为140℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和焙烧后的样品进行反应,N2在反应管中线速度为0.5cm/s,硅烷化温度为250℃,硅烷化时间为120min;得到的催化剂记为TS-A5。
BET法测定TS-A5催化剂的比表面积为17.6m2/g,孔容为12.3ml/g,平均孔径为1.2nm;单颗粒平均强度为14.2N/颗。对TS-A4进行评价,连续运行10hr,反应温度80℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性为7.4%。
对比例2
参考专利CN1894030进行催化剂制备:称取30g硅胶载体装填入反应管中,在N2气氛下,240℃下干燥240min,N2在反应管中线速度为2cm/s;在TiCl4汽化罐中加入4.17gTiCl4,TiCl4汽化罐加热温度为145℃,用N2将TiCl4蒸汽带入反应管中和硅胶进行反应,N2在反应管中线速度为0.8cm/s,沉积时间为200min;以2℃/min升温速率升至600℃,N2在反应管中线速度为2cm/s,焙烧200min;在水和硅烷化试剂汽化罐中加入33.5g蒸馏水,水和硅烷化试剂汽化罐加热温度为160℃,用N2将水蒸汽带入反应管中进行水洗,N2在反应管中线速度为2cm/s,水洗时间为200min;在水和硅烷化试剂汽化罐中加入2.4g六甲基二硅胺烷,水和硅烷化试剂汽化罐加热温度为140℃,用N2将六甲基二硅胺烷蒸汽带入反应管中和硅胶进行反应,N2在反应管中线速度为0.5cm/s,硅烷化温度为250℃,硅烷化时间为120min;得到的催化剂记为TS-A6。
对TS-A6进行评价,连续运行200hr,反应温度由最初50℃升温至90℃,取样进行气相色谱分析,CHP转化率>99.9%,对PO的选择性最高达到92.8%,平均达到91.7%。
Claims (10)
1.一种丙烯环氧化催化剂的制备方法,包括以下步骤:
(1)硅源预水解:将硅酯溶解于低碳醇中,加入水解催化剂和水反应后得到A液;
(2)成胶:将钛酯溶于低碳醇后加入到A液中;加入水反应后得到溶胶;
(3)将步骤(2)得到的溶胶雾化后喷入液氨中进行成型,得到催化剂前驱体;
(4)将步骤(3)得到的催化剂前驱体进行扩孔处理;
(5)将步骤(4)扩孔后的催化剂前驱体干燥和焙烧;
(6)将步骤(5)得到的产物进行硅烷化处理得到Ti-SiO2复合氧化物催化剂。
2.根据权利要求1所述的方法,其特征在于,所述步骤(1)中硅酯选自正硅酸乙酯、正硅酸甲酯、正硅酸丙酯、正硅酸丁酯中的一种或多种,硅酯在低碳醇中的浓度为20~30wt%。
3.根据权利要求1或2所述的方法,其特征在于,所述步骤(1)中水解催化剂为乙酸、甲酸中的一种或两种的混合物,加入量为硅酯的0.8~1.5wt%;加入的水量为理论上硅酯水解30~80%所需的水量;反应温度为40~70℃,反应时间为1~3h。
4.根据权利要求1所述的方法,其特征在于,所述步骤(2)中所用钛酯选自钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯中的一种或多种,钛酯中Ti的量为步骤(1)中原料硅酯完全水解为SiO2质量的2~5%,钛酯在低碳醇中的浓度为30~50wt%,反应时间为1~4h。
5.根据权利要求1-4中任一项所述的方法,其特征在于,所述步骤(2)中加入钛酯后,不加水而加入一定量的NH4ReO4和锌盐混合溶液反应得到溶胶,Re与Ti的摩尔比为0.01~0.05:1,Zn与Ti的摩尔比为0.05~0.15:1。
6.根据权利要求1-5中任一项所述的方法,其特征在于,所述步骤(3)中使用离心式雾化器雾化溶胶,雾化器喷出的溶胶平均粒径范围为100~850μm,优选平均粒径为400~580μm。
7.根据权利要求1-6中任一项所述的方法,其特征在于,所述步骤(4)扩孔工艺条件为:扩孔剂为液氨,扩孔温度为60~140℃,扩孔时间为3~15h。
8.根据权利要求1-7中任一项所述的方法,其特征在于,所述步骤(5)干燥温度为80~120℃,干燥时间为2~5h;焙烧温度为450~600℃,焙烧时间为2~5h。
9.根据权利要求1所述的方法,其特征在于,所述步骤(6)中硅烷化试剂为六甲基二硅胺烷,用量为5~15wt%,以原料硅酯全部水解为SiO2的质量计,六甲基二硅胺烷温度为126~150℃,硅烷化处理的温度为200~300℃,硅烷化处理的时间为60~180min。
10.一种根据权利要求1-9中任一项所述的方法制备的Ti-SiO2复合氧化物催化剂作为丙烯环氧化制备环氧丙烷催化剂的用途。
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CN113181961B (zh) * | 2020-01-14 | 2022-09-20 | 万华化学集团股份有限公司 | 一种丙烯环氧化催化剂的制备方法及其用途 |
US11918987B2 (en) | 2020-01-14 | 2024-03-05 | Wanhua Chemical Group Co., Ltd. | Preparation method for propylene epoxidation catalyst and use thereof |
CN114618536A (zh) * | 2020-12-14 | 2022-06-14 | 万华化学集团股份有限公司 | 一种用于制备新己烯的催化剂组合物及制备新己烯的方法 |
CN114618536B (zh) * | 2020-12-14 | 2023-10-20 | 万华化学集团股份有限公司 | 一种用于制备新己烯的催化剂组合物及制备新己烯的方法 |
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US11291985B2 (en) | 2022-04-05 |
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CN107715868B (zh) | 2019-07-23 |
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