CN114797892A - 一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂 - Google Patents
一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂 Download PDFInfo
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- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000001257 hydrogen Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
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- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 4
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- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及催化技术领域,且公开了一种1,4‑丁炔二醇加氢制备1,4‑丁二醇的催化剂,包括以下步骤:步骤一、称取一定量的硝酸铜,溶解于一定量的去离子水中,得到水溶液A;步骤二、将步骤一的水溶液A置于旋转蒸发仪中,称取一定量的载体,投放入旋转蒸发仪,蒸干水分得到混合物B;步骤三、将步骤二制得的混合物B在氮气环境下进行焙烧一段时间得到改性载体C;步骤四、将一定量的聚乙烯吡咯烷酮,无水乙醇和去离子水和一定浓度的Pd盐、Ru盐、Pt盐或Au盐水溶液进行混合,得到混合溶液D;步骤五、将一定量的还原剂加入到步骤四得到的混合溶液D中,一定温度下进行反应一段时间,得到混合溶液E。
Description
技术领域
本发明涉及催化技术领域,具体为一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂。
背景技术
1,4-丁二醇(简称BDO)是一种重要的有机和精细化工原料,它被广泛应用于医药、化工、纺织、造纸、汽车和日用化工等领域。由BDO可以生产四氢呋喃(THF)、聚对苯二甲酸丁二醇酯(PBT)、γ-丁内脂(GBL)和聚氨酯树脂(PU Resin)、涂料和增塑剂等,以及作为溶剂和电镀行业的增亮剂等。
1,4-丁炔二醇是基于煤化工和甲醇工艺而生产的一种上游产品,具有较高的附加值,其加氢过程主要分为两类反应:不完全加氢反应和完全加氢反应,在加氢过程中还会发生一些副反应,例如:氢解反应和异构化反应等,加氢的目标产物选择性控制不易。
通常1,4-丁炔二醇加氢过程使用的催化剂分为非金属催化剂如Cu、Ni、 Fe、Co和贵金属催化剂如Pd、Pt、Ag、Rh、Au。非金属催化剂价格便宜易得,但反应条件较苛刻,温度,氢气压力要求较高,如工业生产中副产物多,导致催化剂稳定性差,生产成本提高;而贵金属催化剂价格较昂贵,但是其催化选择性好不会造成后续分离困难和原子经济性差的问题。
发明内容
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,具备降低了对反应设备的要求及危险性,降低了设备费用和生产成本等优点,解决了上述技术的问题。
(二)技术方案
为实现上述目的,本发明提供如下技术方案:一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,包括以下步骤:
步骤一、称取一定量的硝酸铜,溶解于一定量的去离子水中,得到水溶液A;
步骤二、将步骤一的水溶液A置于旋转蒸发仪中,称取一定量的载体,投放入旋转蒸发仪,蒸干水分得到混合物B;
步骤三、将步骤二制得的混合物B在氮气环境下进行焙烧一段时间得到改性载体C;
步骤四、将一定量的聚乙烯吡咯烷酮,无水乙醇和去离子水和一定浓度的Pd盐、Ru盐、Pt盐或Au盐水溶液进行混合,得到混合溶液D;
步骤五、将一定量的还原剂加入到步骤四得到的混合溶液D中,一定温度下进行反应一段时间,得到混合溶液E;
步骤六、将步骤三得到的改性载体C与步骤五得到的混合溶液E进行混合放置一段时间,并进行过滤洗涤、干燥过程得到催化剂前驱体F;
步骤七、将步骤六得到的催化剂前驱体F在氮气环境下进行焙烧一段时间得到催化剂G。
优选的,所述催化剂含有改性载体和负载在改性载体上的贵金属为活性组分,所述贵金属为Pd、Ru、Pt或Au中的一种或几种,所述载体为活性炭,所述三氧化二铝或硅铝分子筛的一种或几种,所述改性载体助剂为铜,所述催化剂组成中活性组分的重量比为0.05%~0.5%,所述铜组分的重量比为 2~8%,余量为载体。
通过上述技术方案,通过添加铜对载体进行改性,其原理是将活性组分直接作用于铜上,活性组分与铜协同作用提高活性组分的分散度,从而可以用含量较低的活性组分达到较好的反应效果。
优选的,所述催化剂组成中活性组分的重量比为0.05%~0.5%,所述铜组分的重量比为2%~8%,余量为载体。
优选的,所述载体为活性炭,三氧化二铝或硅铝分子筛的一种或几种。
优选的,所述的Pd盐、Ru盐、Pt盐或Au盐选自氯化钯、氯化钌、氯铂酸或氯金酸中的一种或几种。
优选的,所述的还原剂选自水合肼、硼氢化钠、硼氢化钾或甲醛中的一种或几种。
优选的,步骤三、所述的焙烧温度为300~600℃,焙烧时间为2~5h,步骤七、所述的焙烧温度为150~400℃,焙烧时间为2~5h。
优选的,一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,包括如下步骤,采用固定床反应,将一定量催化剂放在固定床反应器中,180~200℃,30Bar 条件下,1,4-丁炔二醇和氢气分别通过进料泵和流量计控制进入反应,产物得到1,4-丁二醇。
通过上述技术方案,通过1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂应用于1,4-丁炔二醇加氢制备1,4-丁二醇的反应上,反应转化率高达100%,产物丁二醇的选择性也高达96%,反应条件温和。
与现有技术相比,本发明提供了一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,具备以下有益效果:
1、该1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,通过添加铜对载体进行改性,其原理是将活性组分直接作用于铜上,活性组分与铜协同作用提高活性组分的分散度,从而可以用含量较低的活性组分达到较好的反应效果,达到了降低了对反应设备的要求及危险性的有益效果。
2、该1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,通过1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂应用于1,4-丁炔二醇加氢制备1,4-丁二醇的反应上,反应转化率高达100%,产物丁二醇的选择性也高达96%,反应条件温和,达到了大大降低了设备费用和生产成本等优点的有益效果。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
下面用实施例对本发明作更为详细的描述。这些实施例均是仅仅对本发明最优实施方案的描述,并不对本发明的范围有任何限制。
实施例1
步骤一、称取六水合硝酸铜1g,溶解于5ml去离子水中;
步骤二、将步骤一的水溶液置于旋转蒸发仪中,称取2g活性炭,投放入旋转蒸发仪,蒸干水分;
步骤三、将步骤二制得的混合物在氮气环境下400℃焙烧3小时得到改性载体;
步骤四、将0.15g聚乙烯吡咯烷酮,10ml无水乙醇和10ml去离子水和 1mlPdCl2水溶液(0.02mol/l)、混合搅拌,得到混合溶液;
步骤五、将10ml的水合肼加入到步骤四得到的混合溶液中,80℃下进行反应6小时,冷却至常温;
步骤六、将步骤三得到的改性载体与步骤五得到的混合溶液进行混合放置并搅拌12小时,并进行过滤洗涤、120℃真空干燥过程得到催化剂前驱体;
步骤七、将步骤六得到的催化剂前驱体在氮气环境下300℃进行焙烧2小时得到催化剂A。
经测定,所得催化剂的比表面积为210m2/g,孔容为0.2cm3/g,Pd元素在催化剂中的含量为0.01重量%。所得催化剂具体性质见表1。
对比例1
与实施例1方法一致,不同的是未进行步骤3),得到对比催化剂B。所得催化剂具体性质见表1。
对比例2
与实施例1方法一致,不同的是将步骤4)的PdCl2水溶液换成非贵金属硝酸铜水溶液,得到对比催化剂C。所得催化剂具体性质见表1。
对比例3
与实施例1方法一致,不同的是取消步骤1)、步骤2)和步骤3),替换为直接称取2g活性炭,最终得到对比催化剂D。所得催化剂具体性质见表1。
实施例2
步骤一、称取六水合硝酸铜1g,溶解于5ml去离子水中;
步骤二、将步骤一的水溶液置于旋转蒸发仪中,称取2g三氧化二铝,投放入旋转蒸发仪,蒸干水分;
步骤三、将步骤二制得的混合物在氮气环境下600℃焙烧2小时得到改性载体;
步骤四、将0.3g聚乙烯吡咯烷酮,30ml无水乙醇和10ml去离子水和 2mlRuCl2水溶液(0.02mol/l)、混合搅拌,得到混合溶液;
步骤五、将10ml的甲醛溶液加入到步骤四、得到的混合溶液中,85℃下进行反应2小时,冷却至常温;
步骤六、将步骤三得到的改性载体与步骤五得到的混合溶液进行混合放置并搅拌24小时,并进行过滤洗涤、100℃真空干燥过程得到催化剂前驱体;
步骤七、将步骤六得到的催化剂前驱体在氮气环境下150℃进行焙烧2小时得到催化剂E。
经测定,所得催化剂的比表面积为174m2/g,孔容为0.1cm3/g,Ru元素在催化剂中的含量为0.02重量%。所得催化剂具体性质见表1。
实施例3
步骤一、称取六水合硝酸铜2g,溶解于10ml去离子水中;
步骤二、将步骤1的水溶液置于旋转蒸发仪中,称取2g硅铝分子筛,投放入旋转蒸发仪,蒸干水分;
步骤三、将步骤2制得的混合物在氮气环境下200℃焙烧10小时得到改性载体;
步骤四、将0.1g聚乙烯吡咯烷酮,50ml无水乙醇和10ml去离子水和2ml 氯铂酸水溶液(0.01mol/l)、混合搅拌,得到混合溶液;
步骤五、将10ml的甲醛溶液加入到步骤4得到的混合溶液中,85℃下进行反应2小时,冷却至常温;
步骤六、将步骤3得到的改性载体与步骤5得到的混合溶液进行混合放置并搅拌24小时,并进行过滤洗涤、100℃真空干燥过程得到催化剂前驱体;
步骤七、将步骤6得到的催化剂前驱体在氮气环境下400℃进行焙烧5小时得到催化剂F。
经测定,所得催化剂的比表面积为343m2/g,孔容为0.5cm3/g,Pt元素在催化剂中的含量为0.015重量%。所得催化剂具体性质见表1。
表1催化剂表征测试结果
催化剂来源 | 比表面积/(m2/g) | 孔容/(cm3/g) |
实施例1 | 210 | 0.2 |
实施例2 | 174 | 0.1 |
实施例3 | 343 | 0.5 |
对比例1 | 230 | 0.6 |
对比例2 | 220 | 0.46 |
对比例3 | 105 | 0.3 |
催化剂性能测试
将实施例1-3和对比例1-2所得催化剂调整至反应工艺条件进行反应。
测试实施例1-3和对比例1-2
将制备实施例1-3和对比例1-2制备的催化剂置于微型固定床连续流动反应器中,反应器内径10mm,反应器内部装热电偶套管,催化剂装填量为2g,原料气自上而下经过催化剂床层。
1,4-丁炔二醇加氢制1,4-丁二醇的反应的操作条件如下:反应温度 200℃,反应压力3MPa,催化剂负荷(反应液时空速2.0g/g cat.H,氢气/ 丁炔二醇=40(摩尔比。反应结果如表2所示。
表2不同催化剂制备乙二醇的反应结果
反应编号 | 1,4-丁炔二醇/%(转化率) | 1,4-丁二醇/%(选择性) |
测试实施例1 | 100 | 96 |
测试实施例2 | 100 | 96 |
测试实施例3 | 100 | 96 |
测试对比例1 | 50 | 89 |
测试对比例2 | 65 | 53 |
测试对比例3 | 35 | 73 |
对比例与实施例反应结果差异性原因分析:对比例1中改性载体没有进行焙烧即立即进行活性组分的担载过程,会导致使用铜改性载体的效果变差,活性组分只有小部分与铜改性载体担载,而大部分仍然载于未改性的载体上,分散度不高,活性变差,效果不明显;对比例2中将活性组分由贵金属改为非贵金属,活性能力不够,效果变差;对比例3中取消铜的添加直接使用活性载体进行担载活性组分,活性组分的会存在叠加、分散度差而导致反应效果差。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于,包括以下步骤:
步骤一、称取一定量的硝酸铜,溶解于一定量的去离子水中,得到水溶液A;
步骤二、将步骤一的水溶液A置于旋转蒸发仪中,称取一定量的载体,投放入旋转蒸发仪,蒸干水分得到混合物B;
步骤三、将步骤二制得的混合物B在氮气环境下进行焙烧一段时间得到改性载体C;
步骤四、将一定量的聚乙烯吡咯烷酮,无水乙醇和去离子水和一定浓度的Pd盐、Ru盐、Pt盐或Au盐水溶液进行混合,得到混合溶液D;
步骤五、将一定量的还原剂加入到步骤四得到的混合溶液D中,一定温度下进行反应一段时间,得到混合溶液E;
步骤六、将步骤三得到的改性载体C与步骤五得到的混合溶液E进行混合放置一段时间,并进行过滤洗涤、干燥过程得到催化剂前驱体F;
步骤七、将步骤六得到的催化剂前驱体F在氮气环境下进行焙烧一段时间得到催化剂G。
2.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:所述催化剂含有改性载体和负载在改性载体上的贵金属为活性组分,所述贵金属为Pd、Ru、Pt或Au中的一种或几种,所述载体为活性炭,所述三氧化二铝或硅铝分子筛的一种或几种,所述改性载体助剂为铜,所述催化剂组成中活性组分的重量比为0.05%~0.5%,所述铜组分的重量比为2~8%,余量为载体。
3.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:所述催化剂组成中活性组分的重量比为0.05%~0.5%,所述铜组分的重量比为2%~8%,余量为载体。
4.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:所述载体为活性炭,三氧化二铝或硅铝分子筛的一种或几种。
5.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:所述的Pd盐、Ru盐、Pt盐或Au盐选自氯化钯、氯化钌、氯铂酸或氯金酸中的一种或几种。
6.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:所述的还原剂选自水合肼、硼氢化钠、硼氢化钾或甲醛中的一种或几种。
7.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:步骤三、所述的焙烧温度为300~600℃,焙烧时间为2~5h,步骤七、所述的焙烧温度为150~400℃,焙烧时间为2~5h。
8.根据权利要求1所述的一种1,4-丁炔二醇加氢制备1,4-丁二醇的催化剂,其特征在于:采用固定床反应,将一定量催化剂放在固定床反应器中,180~200℃,30Bar条件下,1,4-丁炔二醇和氢气分别通过进料泵和流量计控制进入反应,产物得到1,4-丁二醇。
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Publication number | Priority date | Publication date | Assignee | Title |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB832141A (en) * | 1957-08-01 | 1960-04-06 | Gen Aniline & Film Corp | Hydrogenation catalyst and its use in partial hydrogenation of 1,4-butynediol |
CN101306368A (zh) * | 2008-07-09 | 2008-11-19 | 山西大学 | 丁炔二醇两步法加氢制丁二醇二段加氢催化剂的制备方法 |
CN101786024A (zh) * | 2010-02-06 | 2010-07-28 | 山西大学 | 一种高水热稳定性氧化铝载体及其制备方法 |
CN102950002A (zh) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | 一种生产1,4-丁炔二醇的催化剂及其制备方法 |
CN108993592A (zh) * | 2018-06-13 | 2018-12-14 | 厦门大学 | 一种丁炔二醇制丁二醇的高效加氢催化剂及其制备方法与应用 |
CN113101928A (zh) * | 2021-04-23 | 2021-07-13 | 上海润颉生物医药科技有限公司 | 1,4-丁炔二醇制备1,4-丁烯二醇用催化剂及其制备方法和应用 |
-
2022
- 2022-03-10 CN CN202210228739.2A patent/CN114797892A/zh not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB832141A (en) * | 1957-08-01 | 1960-04-06 | Gen Aniline & Film Corp | Hydrogenation catalyst and its use in partial hydrogenation of 1,4-butynediol |
CN101306368A (zh) * | 2008-07-09 | 2008-11-19 | 山西大学 | 丁炔二醇两步法加氢制丁二醇二段加氢催化剂的制备方法 |
CN101786024A (zh) * | 2010-02-06 | 2010-07-28 | 山西大学 | 一种高水热稳定性氧化铝载体及其制备方法 |
CN102950002A (zh) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | 一种生产1,4-丁炔二醇的催化剂及其制备方法 |
CN108993592A (zh) * | 2018-06-13 | 2018-12-14 | 厦门大学 | 一种丁炔二醇制丁二醇的高效加氢催化剂及其制备方法与应用 |
CN113101928A (zh) * | 2021-04-23 | 2021-07-13 | 上海润颉生物医药科技有限公司 | 1,4-丁炔二醇制备1,4-丁烯二醇用催化剂及其制备方法和应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115739077A (zh) * | 2022-10-13 | 2023-03-07 | 厦门大学 | 一种高选择性钯基催化剂及其应用 |
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