CN115155550A - 一种丙酮一步法合成mibk联产dibk的催化剂及其制备方法与应用 - Google Patents
一种丙酮一步法合成mibk联产dibk的催化剂及其制备方法与应用 Download PDFInfo
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- CN115155550A CN115155550A CN202210907629.9A CN202210907629A CN115155550A CN 115155550 A CN115155550 A CN 115155550A CN 202210907629 A CN202210907629 A CN 202210907629A CN 115155550 A CN115155550 A CN 115155550A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
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- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明公开一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分、助剂组分和载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分0.05‑0.5%,助剂组分0.5‑2%,余量为载体;其中,所述活性组分为Pd,所述助剂组分为V、Nb中的一种;所述载体为AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成。同时,本发明还公开所述催化剂的制备方法及其在催化丙酮一步法合成MIBK联产DIBK中的应用。所述催化剂在催化丙酮制备MIBK时,适应的温度和压力范围宽,丙酮转化率高,产品DIBK选择性高。
Description
技术领域
本发明属于甲基异丁基酮制备技术领域,具体涉及一种丙酮一步法合成MIBK联产DIBK的催化剂及其制备方法与应用。
背景技术
甲基异丁基酮(MIBK)又名4-甲基-2-戊酮,是一种性能优良的中沸点溶剂,广泛应用于涂料、医药、燃料、选矿、炼油等行业。二异丁基酮(DIBK)具有沸点高,蒸发速度快,溶解力强,能提高涂膜流平、光泽、重涂性,对塑料底材的湿润性好,增加吸着力,可用作硝基喷漆、乙烯树脂涂料及其他合成树脂涂料的溶剂,可提高其防潮能力。也可用作制造有机气溶胶的分散剂及食品精制和某些药物、杀虫剂的中间体,还可用在稀有金属萃取和提纯中分离金属盐类。
目前,有关合成DIBK的报道不多,大多是合成MIBK或者是生产MIBK联产DIBK的方法和催化剂,并且DIBK收率较低。相应的用于丙酮一步法合成MIBK的多功能催化剂研究非常广泛。以加氢活性中心分类,主要分为 2类:一是贵金属系,主要是 Pd,其次有 Pt、Au等。该类催化剂选择性普遍较高,但是价格昂贵;二是非贵金属系,主要有 Ni、Cu、Zn 等,虽然成本低于贵金属催化剂,但是其催化性能特别是对于 MIBK 的选择性与贵金属催化剂还有着一定的差距。以载体来分,主要可分为:活性炭载体、氧化物载体、树脂类载体、金属有机物框架载体等。
目前,工业应用较多的合成MIBK和DIBK的催化剂是钯树脂催化剂,负载钯的强酸性阳离子交换树脂虽然选择性比较高,但树脂的热稳定性差,焙烧催化剂只能在 150℃下,造成加氢活性组分易流失,且不能完全被还原,导致了催化剂活性低,催化剂的再生困难。另外,该类催化剂需要在较高压力下反应,而高压操作不仅使过程繁琐,而且安全系数低。金属氧化物热稳定性好、比表面积大、酸碱度适宜,因此作为丙酮一步法合成MIBK 的催化剂载体研究较多。该类催化剂由金属氧化物载体提供丙酮缩合脱水所需的酸碱活性中心,再由负载的金属提供加氢活性中心,利用异步协同作用完成丙酮缩合、脱水和加氢过程。其中,研究最多的是Pd/Al2O3,但该类催化剂的反应结果并不是十分理想,另外,DIBK作为高附加值产品但是其选择性较低,因此,近年来人们尝试着对这种类型的催化剂进行改性,以提升催化剂的性能和DIBK的选择性。
发明内容
针对现有技术的缺陷,本发明提供一种丙酮一步法合成MIBK联产DIBK的催化剂及其制备方法与应用,所述催化剂在用于催化丙酮合成MIBK时,能联产DIBK,DIBK的选择性高,且MIBK和DIBK的总选择性保持较高水平。
一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分、助剂组分和载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分0.05-0.5%,助剂组分0.5-2%,余量为载体;其中,所述活性组分为Pd,所述助剂组分为V、Nb中的一种;所述载体为AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为5-40%,ZrO2含量为5-30%,余量为Al2O3。
所述催化剂的制备方法,包括以下步骤:
(1)制备AlZrSi复合载体:
(1-1)将氢氧化铝和锆盐加入纯水中,然后加入天然增稠剂打浆,在50-90℃、搅拌状态下加入稀硝酸溶液,保持温度加热至溶解,得铝锆溶胶;
(1-2)将(1-1)所得铝锆溶胶、硅源、扩孔剂、脱模剂、温敏材料、胶溶剂、酸改性剂混合、研磨、捏合均匀,得到胶体;
(1-3)将(1-2)所得胶体直接挤条成型,烘干,焙烧得AlZrSi复合载体;
(2)助剂组分的负载:
(2-1)将铌盐或者钒盐溶解于水中,得到助剂组分浸渍液;
(2-2)将助剂组分浸渍液在室温下超声0.3-1h,然后将所述AlZrSi复合载体加入其中,微波加热25-35min,60-100℃真空干燥,焙烧,得到接枝助剂的载体;
(3)活性组分的负载:
(3-1)将钯化合物溶解,得到钯浸渍液;
(3-2)将表面活性剂溶解在水中,得到表面活性剂溶液;
(3-3)将所得表面活性剂溶液和钯浸渍液混合,20-80℃下搅拌4-10h,超声2-5h,得到钯溶液;
(3-4)将接枝助剂的载体加入钯溶液中,室温浸渍6-18h,烘干,焙烧;
(4)还原处理。
优选地,步骤(1)中,所述氢氧化铝的质量以氧化铝计,锆盐的质量以氧化锆计,氢氧化铝和锆盐的总质量与天然增稠剂、硝酸的质量比为1:(0.001-0.03):(0.05-0.15);
所述胶溶剂、扩孔剂、脱模剂、温敏材料、酸改性剂的加入量均以占AlZrSi复合载体质量的百分比计,分别如下:胶溶剂5-30%、扩孔剂0.5-5%、脱模剂0.5-4%、温敏材料0.5-3%、酸改性剂0.5-2%。
优选地,所述锆盐为硝酸氧锆或者氧氯化锆;
所述硅源为无机硅源或者有机硅源;所述无机硅源为硅溶胶、硅胶、硅藻土或水玻璃中的一种;所述有机硅源为硅酸乙酯、卤硅烷、硅氮烷或硅氧基硅烷中的一种。
优选地,所述天然增稠剂为瓜儿豆胶、田菁胶、葡甘露聚糖、明胶、卡拉胶中的任意一种;
所述稀硝酸溶液为5-20wt%的硝酸溶液;
所述扩孔剂为炭黑、淀粉、甲基纤维素、尿素、六亚甲基四胺、碳酸氢铵、碳酸铵、乙酸铵、乙二胺中的至少一种;
所述脱模剂为脂肪酸、硬脂酸钠、石蜡、甘油、硅油、硅酯、聚乙二醇、低分子聚乙烯中的至少一种;
所述温敏材料为N-异丙基丙烯酰胺、聚甲基丙烯酸、聚甲基丙烯酸N,N-二甲氨基乙酯、聚亚苯基氧化物、聚环氧乙烷、壳聚糖-聚乙烯吡咯烷酮中的至少一种;
所述胶溶剂的浓度为1-10wt%,所述胶溶剂为硝酸溶液、盐酸溶液、甲酸溶液或醋酸溶液;
所述酸改性剂为硼酸或者磷酸。
优选地,所述铌盐为草酸铌或铌络合物,所述铌络合物为M3[NbO(C2O4)3]、M[NbO(C2O4)2]或者M[NbO2C2O4] ,所述M为钾、钠、铷、铵;
所述钒盐为偏钒酸铵、偏钒酸钠、偏钒酸钾中的一种;
所述钯化合物为氯钯酸、硝酸钯、醋酸钯、乙酰丙酮钯、二氯二氨钯、四氯钯酸铵、氯钯酸钠或硝酸四氨合钯中一种;在制备钯浸渍液时,溶解钯化合物的溶剂根据钯化合物的种类而定,只要能溶解钯化合物即可,在溶解时可以采用加热加快溶解。
优选地,所述表面活性剂为阴离子表面活性剂、阳离子表面活性剂或非离子表面活性剂,所述表面活性剂与金属Pd的摩尔比为(0.0001-0.01):1。
现有技术中的阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂均可满足本发明。
更优选地,所述阴离子表面活性剂为十二烷基磺酸钠、所述阳离子表面活性剂为十六烷基三甲基溴化铵、所述非离子表面活性剂为聚乙烯吡咯烷酮。
优选地,所述微波加热的功率为400-800W、温度为60-150℃;
所述烘干为在80-130℃下烘干9-12h;
步骤(1-3)中所述焙烧为在250-400℃下焙烧2-5h,然后在500-800℃下焙烧2-5h;
步骤(2-2)、(3-4)中所述焙烧为在350-650℃下焙烧2-5h。
优选地,步骤(4)所述还原处理具体为:在氮气气氛下,以0.5-3℃/min的升温速率升温至250-400℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3-7h,然后在氮气气氛下冷却至室温。
所述催化剂在丙酮一步法合成MIBK联产DIBK中的应用,具体如下:
(一)按照所述催化剂与惰性瓷球的体积比为2:1,将催化剂与惰性瓷球逐层交替装填于固定床反应器的反应管中,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.5-4MPa条件下,将催化剂先以1-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;
(三)将原料液丙酮和氢气分别预热至反应温度,通入固定床反应器中,进行原料丙酮缩合脱水反应,氢气与丙酮摩尔比为(0.2-2):1,反应体积空速为1-5h-1;
(四)将步骤(三)得到的产物送入气液分离器,分离精馏后得到MIBK和DIBK产品;其中,所述反应温度为100-300℃。
优选地,步骤(一)中所述惰性瓷球的粒径为1.0-1.5mm;所述固定床反应器的反应管内径为10-50mm、反应管的装填高度为1.0-6.0m。
本发明的优点:
(1)所制备的AlZrSi复合载体以AlO x ZrO y SiO z 复合氧化物混晶结构形式存在,避免单一载体结构变化,复合载体中氧化物颗粒尺寸小,载体内部为多孔网状结构,孔道多为相互连通,载体酸碱性可调范围广;而助剂金属的加入改变了载体上钯离子吸附过程中的竞争吸附状态;结合表面活性剂制备高分散稳定钯浸渍液,制备的催化剂钯金属高度分散,以上几方面的原因促使制备的催化剂在缩合脱水功能和加氢功能匹配更好,在满足DIBK选择性同时,保证MIBK和DIBK总选择性保持较高水平,在98%以上,而DIBK的选择性能达50%以上,大大提高了在合成MIBK时联产DIBK的选择性;
(2)在铝锆溶胶制备过程添加天然天然增稠剂,胶体均一性好,流动性好,与硅源研磨捏合成胶性好;胶体捏合过程添加脱模剂、扩孔剂和温敏材料,成型载体表面光滑,烘干过程温度高于温敏材料低临界溶液温度,材料由高分子链伸展的亲水状态转为疏水状态,蜷缩成团,与扩孔剂协同作用,经高温焙烧去除后,使载体内部形成许多大孔,有利于产品有效扩散;
(3)本发明催化剂适应的温度和压力范围宽,丙酮转化率高,产品DIBK选择性高。催化剂堆密相较目前工业应用较多的钯树脂催化剂小,在相同体积空速下,本发明催化剂质量空速高,单位时间产品产量大,单位产品催化成本低。
具体实施方式
实施例1
1. 一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分Pd、助剂组分Nb和AlZrSi复合载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分Pd 0.2%,助剂组分Nb 0.5%,余量为载体;其中,所述AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为30%,ZrO2含量为20%, Al2O3含量为50%;
2. 所述催化剂的制备方法,包括以下步骤:
(1)制备AlZrSi复合载体:
(1-1)氢氧化铝的量以氧化铝的质量计,硝酸氧锆的量以氧化锆的质量计,将50g氢氧化铝和20g硝酸氧锆加入纯水中,然后加入天然增稠剂田菁胶打浆均匀,在70℃、搅拌状态下加入10wt%的稀硝酸溶液,保持温度加热至溶解,得铝锆溶胶;氢氧化铝和锆盐硝酸氧锆的总质量与天然增稠剂、硝酸的质量比为1: 0.005:0.1;
(1-2)硅源的质量以氧化硅质量计,取硅溶胶作为硅源,将(1-1)所得铝锆溶胶、30g硅溶胶、扩孔剂、脱模剂、温敏材料、胶溶剂、酸改性剂混合、研磨、捏合均匀,得到胶体;所述胶溶剂为5wt%的硝酸溶液、扩孔剂为甲基纤维素、脱模剂为硬脂酸钠、温敏材料为N-异丙基丙烯酰胺、酸改性剂为磷酸;所述胶溶剂、扩孔剂、脱模剂、温敏材料、酸改性剂的加入量均以占AlZrSi复合载体质量的百分比计,分别如下:胶溶剂10%、扩孔剂2%、脱模剂2%、温敏材料2%、酸改性剂1%;
(1-3)将(1-2)所得胶体直接挤条成型,120℃烘干10h,先在250℃下焙烧5h,然后在500℃下焙烧3h焙烧得AlZrSi复合载体;
(2)助剂组分的负载:
(2-1)将草酸铌溶解于水中,得到Nb浸渍液;
(2-2)将Nb浸渍液在室温下超声0.5h,然后将步骤(1)得到的AlZrSi复合载体加入其中,在微波功率600W、温度80℃下微波加热30min,80℃真空干燥,500℃下焙烧3h,得到接枝助剂的载体;
(3)活性组分的负载:
(3-1)将硝酸钯溶解于稀硝酸中,得到钯浸渍液;
(3-2)将非离子表面活性剂聚乙烯吡咯烷酮溶解在水中,得到表面活性剂溶液;
(3-3)将所得表面活性剂溶液和钯浸渍液混合,60℃下搅拌6h,超声3h,得到钯溶液;所述表面活性剂与金属Pd的摩尔比为0.0001:1;
(3-4)将接枝助剂的载体加入钯溶液中,室温浸渍6h,在130℃下烘干9h,500℃下焙烧3h;
(4)还原处理:在氮气气氛下,以2℃/min的升温速率升温至300℃,氮气吹扫0.5h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理5h,然后在氮气气氛下冷却至室温,即可得到所述催化剂,记为S1。
实施例2
助剂组分为V,在制备时,采用的钒盐为偏钒酸钠,其他同实施例1,得到的催化剂记为S2。
实施例3
所述AlZrSi复合载体中,SiO2含量为40%,ZrO2含量为5%, Al2O3含量为55%,在制备时,氢氧化铝、硝酸氧锆、硅溶胶分别取55g、5g、40g,其他同实施例1,制备得到催化剂记为S3。
实施例4
所述AlZrSi复合载体中,SiO2含量为5%,ZrO2含量为30%, Al2O3含量为65%,在制备时,氢氧化铝、硝酸氧锆、硅溶胶分别取65g、30g、5g,其他同实施例1,制备得到催化剂记为S4。
实施例5
钯化合物采用氯钯酸,采用稀盐酸加热溶解制备钯浸渍液,其他同实施例1,制备得到的催化剂记为S5。
实施例6
钯化合物采用乙酰丙酮钯,采用乙酰丙酮溶解制备钯浸渍液,其他同实施例1,制备得到的催化剂记为S6。
实施例7
在制备AlZrSi复合载体时,所述锆盐为氧氯化锆,所述硅源为有机硅源硅酸乙酯,其他同实施例1,制备得到的催化剂记为S7。
实施例8
1. 一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分Pd、助剂组分Nb和AlZrSi复合载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分Pd 0.05%,助剂组分Nb 2%,余量为载体;其中,所述AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为20%,ZrO2含量为20%, Al2O3含量为60%;
2. 所述催化剂的制备方法,包括以下步骤:
(1)制备AlZrSi复合载体:
(1-1)氢氧化铝的量以氧化铝的质量计,硝酸氧锆的量以氧化锆的质量计,将60g氢氧化铝和20g硝酸氧锆加入纯水中,然后加入天然增稠剂瓜儿豆胶打浆均匀,在50℃、搅拌状态下加入5wt%的稀硝酸溶液,保持温度加热至溶解,得铝锆溶胶;氢氧化铝和锆盐硝酸氧锆的总质量与天然增稠剂、硝酸的质量比为1: 0.001:0.05;
(1-2)硅源的质量以氧化硅质量计,取硅藻土作为硅源,将(1-1)所得铝锆溶胶、20g硅藻土、扩孔剂、脱模剂、温敏材料、胶溶剂、酸改性剂混合、研磨、捏合均匀,得到胶体;所述胶溶剂为10wt%的甲酸溶液、扩孔剂为炭黑、脱模剂为石蜡、温敏材料为聚环氧乙烷、酸改性剂为硼酸;所述胶溶剂、扩孔剂、脱模剂、温敏材料、酸改性剂的加入量均以占AlZrSi复合载体质量的百分比计,分别如下:胶溶剂30%、扩孔剂5%、脱模剂4%、温敏材料0.5%、酸改性剂2%;
(1-3)将(1-2)所得胶体直接挤条成型,80℃烘干12h,先在400℃下焙烧2h,然后在800℃下焙烧2h焙烧得AlZrSi复合载体;
(2)助剂组分的负载:
(2-1)将K3[NbO(C2O4)3]溶解于水中,得到Nb浸渍液;
(2-2)将Nb浸渍液在室温下超声1h,然后将步骤(1)得到的AlZrSi复合载体加入其中,在微波功率800W、温度150℃下微波加热25min,100℃真空干燥,350℃下焙烧5h,得到接枝助剂的载体;
(3)活性组分的负载:
(3-1)将硝酸钯溶解于稀硝酸中,得到钯浸渍液;
(3-2)将非离子表面活性剂聚乙烯吡咯烷酮溶解在水中,得到表面活性剂溶液;
(3-3)将所得表面活性剂溶液和钯浸渍液混合,20℃下搅拌10h,超声5h,得到钯溶液;所述表面活性剂与金属Pd的摩尔比为0.01:1;
(3-4)将接枝助剂的载体加入钯溶液中,室温浸渍18h,在80℃下烘干12h,350℃下焙烧5h;
(4)还原处理:在氮气气氛下,以0.5℃/min的升温速率升温至250℃,氮气吹扫0.2h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3h,然后在氮气气氛下冷却至室温,即可得到所述催化剂,记为S8。
实施例9
1. 一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分Pd、助剂组分Nb和AlZrSi复合载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分Pd 0.5%,助剂组分Nb 1%,余量为载体;其中,所述AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为20%,ZrO2含量为20%, Al2O3含量为60%;
2. 所述催化剂的制备方法,包括以下步骤:
(1)制备AlZrSi复合载体:
(1-1)氢氧化铝的量以氧化铝的质量计,硝酸氧锆的量以氧化锆的质量计,将60g氢氧化铝和20g硝酸氧锆加入纯水中,然后加入天然增稠剂瓜儿豆胶打浆均匀,在90℃、搅拌状态下加入20wt%的稀硝酸溶液,保持温度加热至溶解,得铝锆溶胶;氢氧化铝和锆盐硝酸氧锆的总质量与天然增稠剂、硝酸的质量比为1: 0.03:0.15;
(1-2)硅源的质量以氧化硅质量计,取硅藻土作为硅源,将(1-1)所得铝锆溶胶、20g硅藻土、扩孔剂、脱模剂、温敏材料、胶溶剂、酸改性剂混合、研磨、捏合均匀,得到胶体;所述胶溶剂为1wt%的盐酸溶液、扩孔剂为六亚甲基四胺、脱模剂为甘油、温敏材料为聚甲基丙烯酸、酸改性剂为硼酸;所述胶溶剂、扩孔剂、脱模剂、温敏材料、酸改性剂的加入量均以占AlZrSi复合载体质量的百分比计,分别如下:胶溶剂5%、扩孔剂0.5%、脱模剂0.5%、温敏材料3%、酸改性剂0.5%;
(1-3)将(1-2)所得胶体直接挤条成型,100℃烘干10h,先在400℃下焙烧2h,然后在800℃下焙烧2h焙烧得AlZrSi复合载体;
(2)助剂组分的负载:
(2-1)将Na[NbO(C2O4)2]溶解于水中,得到Nb浸渍液;
(2-2)将Nb浸渍液在室温下超声0.3h,然后将步骤(1)得到的AlZrSi复合载体加入其中,在微波功率400W、温度150℃下微波加热35min,60℃真空干燥,650℃下焙烧2h,得到接枝助剂的载体;
(3)活性组分的负载:
(3-1)将硝酸钯溶解于稀硝酸中,得到钯浸渍液;
(3-2)将阴离子表面活性剂为十二烷基磺酸钠溶解在水中,得到表面活性剂溶液;
(3-3)将所得表面活性剂溶液和钯浸渍液混合,80℃下搅拌4h,超声2h,得到钯溶液;所述表面活性剂与金属Pd的摩尔比为0.05:1;
(3-4)将接枝助剂的载体加入钯溶液中,室温浸渍12h,在100℃下烘干10h,650℃下焙烧2h;
(4)还原处理:在氮气气氛下,以3℃/min的升温速率升温至400℃,氮气吹扫1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理7h,然后在氮气气氛下冷却至室温,即可得到所述催化剂,记为S9。
对比例1
不含助剂,其他同实施例1,具体如下:
1. 一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分Pd和AlZrSi复合载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分Pd0.2%,余量为载体;其中,所述AlZrSi复合载体同实施例1;
制备方法中,不进行步骤(2),在步骤(1)之后直接进行步骤(3),其他同实施例1;
制备得到的催化剂记为D1。
对比例2
AlZrSi复合载体采用现有技术中的浸渍沉淀法制备,其他同实施例1,具体如下:
1. 一种丙酮一步法合成MIBK联产DIBK的催化剂,所述催化剂由活性组分Pd、助剂组分Nb和AlZrSi复合载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分Pd 0.2%,助剂组分Nb 0.5%,余量为载体;其中,所述AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为30%,ZrO2含量为20%, Al2O3含量为50%;
制备方法中,AlZrSi复合载体的制备方法如下:
ZrOCl2·8H2O的量以ZrO2的质量计,硅溶胶的量以SiO2的质量计,称取20g的ZrOCl2·8H2O和30g硅溶胶溶于纯水中,搅拌均匀配成锆硅水溶液,将50g氧化铝粉末加入到该溶液中,剧烈搅拌下用10(v/v)%稀NH3·H2O溶液滴定至pH为9后继续搅拌30min,放置4h沉淀老化,然后用纯水洗涤至无Cl-1为止。在120℃烘干10h,先在250℃下焙烧5h,然后在500℃下焙烧3h焙烧得AlZrSi复合载体;
其他制备方法同实施例1;
制备得到的催化剂记为D2。
对比例3
不含助剂,载体同对比例2。
制备方法中,不进行步骤(2),在步骤(1)之后直接进行步骤(3),其他同对比例2;
制备得到的催化剂记为D3。
一. 催化性能检测
将本发明提供的催化剂用于丙酮一步法合成MIBK联产DIBK中,具体如下:
(一)按照所述催化剂与惰性瓷球的体积比为2:1,将催化剂与惰性瓷球逐层交替装填于固定床反应器的反应管(防止床层飞温),通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.5-4MPa条件下,将催化剂先以1-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;
(三)将原料液丙酮和氢气分别预热至反应温度,通入固定床反应器中,进行原料丙酮缩合脱水反应,氢气与丙酮摩尔比为(0.2-2):1,反应体积空速为1-5h-1;
(四)将步骤(三)得到的产物送入气液分离器,分离精馏后得到MIBK和DIBK产品;其中,所述反应温度为100-300℃;
步骤(一)中所述惰性瓷球的粒径为1.0-1.5mm;所述固定床反应器的反应管内径为10-50mm、反应管的装填高度为1.0-6.0m;
具体反应参数和反应结果见表1,其他反应条件相同。
表1 反应参数和结果
Claims (10)
1.一种丙酮一步法合成MIBK联产DIBK的催化剂,其特征在于:所述催化剂由活性组分、助剂组分和载体组成,以催化剂的总重量为100%计,各组分所占的重量比如下:活性组分0.05-0.5%,助剂组分0.5-2%,余量为载体;其中,所述活性组分为Pd,所述助剂组分为V、Nb中的一种;所述载体为AlZrSi复合载体,由SiO2、ZrO2、Al2O3组成,所述载体以其总重量为100%计,SiO2含量为5-40%,ZrO2含量为5-30%,余量为Al2O3。
2.权利要求1所述催化剂的制备方法,其特征在于:包括以下步骤:
(1)制备AlZrSi复合载体:
(1-1)将氢氧化铝和锆盐加入纯水中,然后加入天然增稠剂打浆,在50-90℃、搅拌状态下加入稀硝酸溶液,保持温度加热至溶解,得铝锆溶胶;
(1-2)将(1-1)所得铝锆溶胶、硅源、扩孔剂、脱模剂、温敏材料、胶溶剂、酸改性剂混合、研磨、捏合均匀,得到胶体;
(1-3)将(1-2)所得胶体直接挤条成型,烘干,焙烧得AlZrSi复合载体;
(2)助剂组分的负载:
(2-1)将铌盐或者钒盐溶解于水中,得到助剂组分浸渍液;
(2-2)将助剂组分浸渍液在室温下超声0.3-1h,然后将所述AlZrSi复合载体加入其中,微波加热25-35min,60-100℃真空干燥,焙烧,得到接枝助剂的载体;
(3)活性组分的负载:
(3-1)将钯化合物溶解,得到钯浸渍液;
(3-2)将表面活性剂溶解在水中,得到表面活性剂溶液;
(3-3)将所得表面活性剂溶液和钯浸渍液混合,20-80℃下搅拌4-10h,超声2-5h,得到钯溶液;
(3-4)将接枝助剂的载体加入钯溶液中,室温浸渍6-18h,烘干,焙烧;
(4)还原处理。
3.根据权利要求2所述催化剂的制备方法,其特征在于:步骤(1)中,所述氢氧化铝的质量以氧化铝计,锆盐的质量以氧化锆计,氢氧化铝和锆盐的总质量与天然增稠剂、硝酸的质量比为1:(0.001-0.03):(0.05-0.15);
所述胶溶剂、扩孔剂、脱模剂、温敏材料、酸改性剂的加入量均以占AlZrSi复合载体质量的百分比计,分别如下:胶溶剂5-30%、扩孔剂0.5-5%、脱模剂0.5-4%、温敏材料0.5-3%、酸改性剂0.5-2%。
4.根据权利要求3所述催化剂的制备方法,其特征在于:所述锆盐为硝酸氧锆或者氧氯化锆;
所述硅源为无机硅源或者有机硅源;所述无机硅源为硅溶胶、硅胶、硅藻土或水玻璃中的一种;所述有机硅源为硅酸乙酯、卤硅烷、硅氮烷或硅氧基硅烷中的一种。
5.根据权利要求4所述催化剂的制备方法,其特征在于:所述天然增稠剂为瓜儿豆胶、田菁胶、葡甘露聚糖、明胶、卡拉胶中的任意一种;
所述稀硝酸溶液为5-20wt%的硝酸溶液;
所述扩孔剂为炭黑、淀粉、甲基纤维素、尿素、六亚甲基四胺、碳酸氢铵、碳酸铵、乙酸铵、乙二胺中的至少一种;
所述脱模剂为脂肪酸、硬脂酸钠、石蜡、甘油、硅油、硅酯、聚乙二醇、低分子聚乙烯中的至少一种;
所述温敏材料为N-异丙基丙烯酰胺、聚甲基丙烯酸、聚甲基丙烯酸N,N-二甲氨基乙酯、聚亚苯基氧化物、聚环氧乙烷、壳聚糖-聚乙烯吡咯烷酮中的至少一种;
所述胶溶剂的浓度为1-10wt%,所述胶溶剂为硝酸溶液、盐酸溶液、甲酸溶液或醋酸溶液;
所述酸改性剂为硼酸或者磷酸。
6.根据权利要求2所述催化剂的制备方法,其特征在于:所述铌盐为草酸铌或铌络合物,所述铌络合物为M3[NbO(C2O4)3]、M[NbO(C2O4)2]或者M[NbO2C2O4] ,所述M为钾、钠、铷、铵;
所述钒盐为偏钒酸铵、偏钒酸钠、偏钒酸钾中的一种;
所述钯化合物为氯钯酸、硝酸钯、醋酸钯、乙酰丙酮钯、二氯二氨钯、四氯钯酸铵、氯钯酸钠或硝酸四氨合钯中一种。
7.根据权利要求2所述催化剂的制备方法,其特征在于:所述表面活性剂为阴离子表面活性剂、阳离子表面活性剂或非离子表面活性剂,所述表面活性剂与金属Pd的摩尔比为(0.0001-0.01):1。
8.根据权利要求2所述催化剂的制备方法,其特征在于:所述微波加热的功率为400-800W、温度为60-150℃;
所述烘干为在80-130℃下烘干9-12h;
步骤(1-3)中所述焙烧为在250-400℃下焙烧2-5h,然后在500-800℃下焙烧2-5h;
步骤(2-2)、(3-4)中所述焙烧为在350-650℃下焙烧2-5h。
9.根据权利要求2所述催化剂的制备方法,其特征在于:步骤(4)所述还原处理具体为:在氮气气氛下,以0.5-3℃/min的升温速率升温至250-400℃,氮气吹扫0.2-1h,然后在摩尔比为1:1的氮气和氢气的混合气体下还原处理3-7h,然后在氮气气氛下冷却至室温。
10.权利要求1所述催化剂在丙酮一步法合成MIBK联产DIBK中的应用,其特征在于:所述应用具体如下:
(一)按照所述催化剂与惰性瓷球的体积比为2:1,将催化剂与惰性瓷球逐层交替装填于固定床反应器的反应管,通入氮气排净空气;
(二)向固定床反应器中通入氢气,在气体压力0.5-4MPa条件下,将催化剂先以1-3℃/min的升温速率升温至50-100℃后保温1.5-2.5h,然后以1-2℃/min的升温速率升温至120-300℃后保温1.5-2.5h,之后自然降温或升温至设定反应温度后保持恒定;
(三)将原料液丙酮和氢气分别预热至反应温度,通入固定床反应器中,进行原料丙酮缩合脱水反应,氢气与丙酮摩尔比为(0.2-2):1,反应体积空速为1-5h-1;
(四)将步骤(三)得到的产物送入气液分离器,分离精馏后得到MIBK和DIBK产品;其中,所述反应温度为100-300℃。
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