CN110743540A - 一种选择性氢化制备环十二烯的催化剂及其制备方法与应用 - Google Patents

一种选择性氢化制备环十二烯的催化剂及其制备方法与应用 Download PDF

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CN110743540A
CN110743540A CN201911078182.3A CN201911078182A CN110743540A CN 110743540 A CN110743540 A CN 110743540A CN 201911078182 A CN201911078182 A CN 201911078182A CN 110743540 A CN110743540 A CN 110743540A
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rhodium
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metal
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冯传密
吴昊
史文涛
王聪
刘新伟
杨克俭
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China Tianchen Engineering Corp
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Abstract

本发明提供了一种选择性氢化制备环十二烯的催化剂及其制备方法与应用，该催化剂包括载体，载体上附着的主金属铑以及助金属；主金属铑与载体的重量比为0.03％～5.0％；主金属与助金属的重量比为(0.001～1)：1，优选比例为(0.05～0.1)：1。所述载体为γ‑氧化铝，活性炭，二氧化硅、碳酸钙、全硅分子筛，钛硅分子筛TS‑1，ZSM‑5分子筛，β‑分子筛，水滑石，高岭土中的一种；所述助金属为钌、金、银、铂、铱、铁、铋、铅、锡、铈、镍、铜、锌、镉中的一种或两种以上。使用本发明所述的催化剂，制备环十二烯的工艺路线间接，以1,5,9‑环十二碳三烯为原料一步选择加氢反应即可完成，选择性可达到99.3～99.6％，转化率99.8～100％。

Description

一种选择性氢化制备环十二烯的催化剂及其制备方法与应用
技术领域
本发明属于氢化催化剂技术领域，尤其是涉及一种选择性氢化制备环十二烯的催化剂及其制备方法与应用。
背景技术
环十二烯是制备环十二醇的关键中间体，环十二醇作为大环麝香酮、长碳链特种尼龙的核心原料，环十二烯下游具体产品为3-甲基环十五酮、消旋麝香酮、环十五酮内酯、5-环十六烯酮、环十五酮、12-甲基-14-羰基双环[9，3，1]十五烷、十二烷二酸、十二烷二胺、尼龙12、尼龙1212、尼龙612、尼龙12T和尼龙1012等。
环十二醇第一种工业化路线采用均相催化环十二三烯制备环十二烯。US5180870专利报道中提到使用钌配合物进行选择性氢化，为了提高反应的转化率和选择性向均相反应液中添加位阻胺和游离的三芳基膦，通过助剂的加入使得催化剂部分中毒，反应结果最高转化率为93.9％。该工艺存在比较大的问题是胺与产物的分离十分困难。US5177278、US3804914、US5210349、US5128296和US6194624专利报道中同样使用均相钌催化剂，反应体系中彻底分离产物避免其他溶剂或助剂的干扰也非常困难。
环十二醇第二种工业化路线采用非均相催化环十二三烯制备环十二烯。US3400164、US3400166和GB19680712专利报道中提到使用金属钯载体催化剂可以实现选择性氢化，反应选择性为94％。过氢产物环十二烷、环十二烯、环十二二烯和环十二三烯的同时存在，专利中也提及反应中伴随芳族副产物，由于混合液体系中各种物料沸点较为接近，必然导致分离能耗较高，同时分离收率也相对较低。Chem.Res.(1996),35(12),4412-4416中报道使用微反评价可以得到96％的转化率，反应的选择性仅为88％。Catl.Today 1995，24(1-2),95-101中报道微反评价转化率为85％，选择性仅为70％。
提高原子经济性，需要实现环十二三烯选择性氢化的高选择性与高转化率，利用非均相催化剂选择性加氢方案是最具有前景的工艺，不仅可以降低生产设备投资，同时可以有效避免副产物的生成，实现工业化绿色环保运行，因此亟需提供一种新的催化剂以及工艺方法可以满足上述需求。
发明内容
有鉴于此，本发明旨在提出一种选择性氢化制备环十二烯的催化剂及其制备方法与应用，以克服现有技术的不足，实现高选择性高转化率制备环十二烯。
为达到上述目的，本发明的技术方案是这样实现的：
一种选择性氢化制备环十二烯的催化剂，包括载体，载体上附着的主金属铑以及助金属；主金属铑与载体的重量比为0.03％～5.0％；催化剂中助金属的重量比为(0.001～1)：1，优选比例为(0.05～0.1)：1。
优选的，所述载体为γ-氧化铝，活性炭，二氧化硅、碳酸钙、全硅分子筛，钛硅分子筛TS-1，ZSM-5分子筛，β-分子筛，水滑石，高岭土中的一种，优选γ-氧化铝；所述助金属为钌、金、银、铂、铱、铁、铋、铅、锡、铈、镍、铜、锌、镉中的一种或两种以上；助金属优选铋、铈中的一种或两者的混合。
本命同时提供一种制备如上所述的选择性氢化制备环十二烯的催化剂的方法，包括以下制备步骤，
1)将金属铑盐溶解于水中，升温至30～100℃；
2)维持步骤1)温度不变，将载体加入铑金属盐溶液中，浸渍吸附0.5～24小时；
3)洗涤后，在35～700℃灼烧0.5～24小时；洗涤用纯净水洗涤即可，洗涤至无杂质，优选为洗涤3次。
4)将助金属溶解于水中，升温至30～100℃；
5)维持步骤4)温度不变，将步骤3)灼烧后的载体加入步骤4)的溶液中，浸渍吸附0.5～24小时；
6)洗涤，在35～700℃灼烧0.5～24小时；洗涤用纯净水洗涤即可，洗涤至无杂质，优选为洗涤3次。
7)在氢气氛围下，35～300℃还原0.5～24小时。
优选的，步骤1)中，金属铑盐为三氯化铑、硝酸铑、醋酸铑中的一种或两种以上；升温至35～75℃。
优选的，步骤2)中，溶液中，金属铑元素与载体的重量比为(0.001～0.05)：1，优选比例为(0.003～0.03)：1；浸渍吸附的温度是35～75℃，时间为1～3小时。
优选的，步骤3)中，温度为350～450℃，灼烧的时间为1～3小时；步骤4)中，升温至35～75℃；步骤5)中，助金属总量与主金属铑重量比为(0.001～1)：1，优选比例为(0.05～0.1)：1，浸渍吸附的温度是35～75℃，时间为1～3小时。
优选的，步骤6)中，在300～450℃下灼烧1～3小时；步骤7)中，还原温度是80～150℃，时间为4～8小时。
如上所述的催化剂，或者如上所述的制备方法制备的催化剂在选择性氢化1,5,9-环十二碳三烯制备环十二烯中的应用。
一种选择性氢化1,5,9-环十二碳三烯制备环十二烯的方法，使用如上所述的催化剂，或者如上所述的制备方法制备的催化剂，反应温度为35～200℃，氢气压力为0.01～4.0Mpa；优选的，温度为50～120℃，氢气压力为0.02～0.8Mpa。
如上所述的应用，或者如上所述的方法，催化反应在间歇反应釜或固定床反应器中进行。
相对于现有技术，本发明所述的一种选择性氢化制备环十二烯的催化剂及其制备方法与应用，具有以下优势：
(1)本发明所述的催化剂，可实现高选择性高转化率制备环十二烯。
(2)使用本发明所述的催化剂，制备环十二烯的工艺路线间接，以1,5,9-环十二碳三烯为原料一步选择加氢反应即可完成；
(3)使用本发明所述的催化剂，制备环十二烯的加氢反应，选择性可达到99.3～99.6％，转化率99.8～100％。
具体实施方式
除有定义外，以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。
下面结合实施例来详细说明本发明。
实施例1
1g三氯化铑(铑含量为0.50g)溶于100mL水中，升温至100℃，90gγ-氧化铝(10-30目)加入其中载体浸渍吸附0.5小时，纯净水洗涤3次后，于400℃条件下灼烧3小时。助金属0.45g硝酸铋(铋含量为0.20g)溶于100mL水中，升温至100℃，浸渍吸附0.5小时，纯净水洗涤3次后，于400℃条件下灼烧3小时。在氢气氛围下，于100℃下还原0.5小时，催化剂CAT-01(0.5％Rh-0.20％Bi/γ-氧化铝)制备完毕。
在500mL高压釜中，催化剂CAT-01加入1.0g，加入环十二三烯200g，设定反应釜温为120℃，通入氢气维持压力至0.5MPa，反应3小时结束，环十二烯的转化率为99.9％，选择性为99.5％。
与实施例1工序相同，制备其他不同含量催化剂并选择性加氢评价：表1为催化剂制备及反应评价，详细数据见附表。
表1
Figure BDA0002263141670000051
表1续
Figure BDA0002263141670000052
其中表1中，铑含量指的是催化剂载体中铑含量；助金属的含量指的是催化剂载体中的含量；第一次浸渍以及第二次浸渍中的温度指的是浸渍的过程中始终维持的温度。
加氢反应评价中，Con/％指的是转化率，Sec/％指的是选择性。
实施例2
选用CAT-15催化剂20g，压片成型，然后破碎，使用20-40目筛网。选取10g加入到管径为10mm和管长度为800mm的固定床反应器中。控制反应温度为110～120℃，反应体系背压至0.02MPa。调节1,5,9-环十二碳三烯进料量为0.36ml/min，氢气速度为120ml/min。连续运转100小时，收集反应物料，检测反应结果：转化率为99.8％，选择性为99.3％。
对比例1
在500mL高压釜中，催化剂1％Rh/γ-氧化铝加入1.0g，加入1,5,9-环十二碳三烯100g，设定反应釜温为120℃，通入氢气维持压力至0.5MPa，反应3小时结束，环十二烯的转化率为99.9％，选择性为39％。
对比例2
在500mL高压釜中，催化剂1％Pd/γ-氧化铝加入1.0g，加入1,5,9-环十二碳三烯100g，设定反应釜温为120℃，通入氢气维持压力至0.5MPa，反应3小时结束，环十二烯的转化率为100％，选择性为15％。
对比例3
在500mL高压釜中，催化剂1％Ru/C加入1.0g，加入1,5,9-环十二碳三烯100g，设定反应釜温为120℃，通入氢气维持压力至0.5MPa，反应3小时结束，环十二烯的转化率为12％，选择性为5％。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种选择性氢化制备环十二烯的催化剂，其特征在于：包括载体，载体上附着的主金属铑以及助金属；催化剂主金属铑与载体的重量比为0.03％～5.0％；催化剂中主金属与助金属的重量比为(0.001～1)：1，优选比例为(0.05～0.1)：1。
2.根据权利要求1所述的选择性氢化制备环十二烯的催化剂，其特征在于：所述载体为γ-氧化铝，活性炭，二氧化硅、碳酸钙、全硅分子筛，钛硅分子筛TS-1，ZSM-5分子筛，β-分子筛，水滑石，高岭土中的一种，优选γ-氧化铝；所述助金属为钌、金、银、铂、铱、铁、铋、铅、锡、铈、镍、铜、锌、镉中的一种或两种以上；助金属优选铋、铈中的一种或两者的混合。
3.一种制备如权利要求1或2所述的选择性氢化制备环十二烯的催化剂的方法，其特征在于：包括以下制备步骤，
1)将金属铑盐溶解于水中，升温至30～100℃；
2)维持步骤1)温度不变，将载体加入铑金属盐溶液中，浸渍吸附0.5～24小时；
3)洗涤后，在35～700℃灼烧0.5～24小时；
4)将助金属溶解于水中，升温至30～100℃；
5)维持步骤4)温度不变，将步骤3)中灼烧后的载体加入步骤4)的溶液中，浸渍吸附0.5～24小时；
6)洗涤，在35～700℃灼烧0.5～24小时；
7)在氢气氛围下，35～300℃还原0.5～24小时。
4.根据权利要求3所述的制备方法，其特征在于：步骤1)中，金属铑盐为三氯化铑、硝酸铑、醋酸铑中的一种或两种以上；升温至35～75℃。
5.根据权利要求3所述的制备方法，其特征在于：步骤2)中，溶液中，金属铑元素与载体的重量比为(0.001～0.05)：1，优选比例为(0.003～0.03)：1；浸渍吸附的温度是35～75℃，时间为1～3小时。
6.根据权利要求3所述的制备方法，其特征在于：步骤3)中，温度为350～450℃，灼烧的时间为1～3小时；步骤4)中，升温至35～75℃；步骤5)中，助金属总量与主金属铑重量比为(0.001～1)：1，优选比例为(0.05～0.1)：1，浸渍吸附的温度是35～75℃，时间为1～3小时。
7.根据权利要求3所述的制备方法，其特征在于：步骤6)中，在300～450℃下灼烧1～3小时；步骤7)中，还原温度是80～150℃，时间为4～8小时。
8.根据权利要求1或2所述的催化剂，或者权利要求3～7任一项所述的制备方法制备的催化剂在选择性氢化1,5,9-环十二碳三烯制备环十二烯中的应用。
9.一种选择性氢化1,5,9-环十二碳三烯制备环十二烯的方法，其特征在于：使用权利要求1或2所述的催化剂，或者权利要求3～7任一项所述的制备方法制备的催化剂，反应温度为35～200℃，氢气压力为0.01～4.0Mpa；优选的，温度为50～120℃，氢气压力为0.02～0.8Mpa。
10.如权利要求8所述的应用，或者权利要求9所述的方法，催化反应在间歇反应釜或固定床反应器中进行。
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