CN116328775A - 一种用于脂肪酸甲酯脱氧加氢制脂肪醇的核壳型催化剂制备方法及应用 - Google Patents
一种用于脂肪酸甲酯脱氧加氢制脂肪醇的核壳型催化剂制备方法及应用 Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明属于催化剂合成领域,提供了一种用于脂肪酸甲酯脱氧加氢制脂肪醇的核壳型催化剂制备方法及应用。采用水热原位生长法,以Al2O3微球为核,在Al2O3上原位生长的CuZnAl水滑石片层为壳,制备花状多级微米核壳结构催化剂,通过控制催化剂的形貌结构,能够同时解决应用于脂肪酸甲酯加氢制脂肪醇反应的现有催化剂生产成本高、反应条件苛刻、稳定性差、活性组分易烧结的问题,制得价格低廉、反应条件温和、高选择性、高稳定性的催化剂,应用前景广阔。
Description
技术领域
本发明属于催化剂合成领域,具体涉及一种用于脂肪酸甲酯选择性脱氧加氢制脂肪醇的核壳型催化剂的制备方法及其在脂肪酸甲酯加氢方面的用途。
背景技术
在全球经济高速发展的时代背景下,世界各国对煤炭、石油和天然气等传统一次性能源的依赖程度逐步提升,致使全球范围内的一次性资源严重匮乏,引起的环境问题也日益突出。为了实现碳中和的长期减排目标,急需要寻找经济、环保、可持续性的理想能源,而生物质是唯一的拥有可再生碳源的物质,被认为是一种很有前景的替代品。
脂肪酸甲酯(FAMEs),是生物质能源中最典型的代表,在工业上又被称为生物柴油,是一种环境友好型的清洁能源。脂肪醇作为大宗化工产品脂肪酸甲酯的下游产品,其具有高附加值的特征,应用范围较为广泛。在工业上,脂肪醇素有“工艺味精”之称,常被用于制备增塑剂、表面活性剂、洗涤剂和润滑剂等一系列精细化工产品,对国民经济的发展起着重要作用。近年来,全球脂肪醇市场需求量脂肪醇的消耗量逐步增大。
现有技术下,脂肪酸甲酯选择性加氢制脂肪醇主要使用两种类型的催化剂Cu-Cr催化剂和贵金属如Pt、Ru催化剂。但CuCr催化剂由于铬化物具有毒性,会引起强烈的环境污染;而贵金属催化剂虽然催化活性高但是贵金属价格高昂,生产成本高,因此需要提供一种催化活性优异的同时环境友好、价格低廉、稳定性高的加氢催化剂。
专利CN111701591A公开了一种加氢催化剂及其制备方法和脂肪酸酯加氢制备脂肪醇的方法,将铜源加入分散的二氧化钛溶液中,制得加氢催化剂用于脂肪酸酯加氢制备脂肪醇时,能获得较高的脂肪醇选择性,但该催化剂活性组分单一,催化活性较低。
专利CN104383921A公开了一种还原高级脂肪酸酯制脂肪醇的催化剂制备及应用方法,该催化剂以高温焙烧纳米氧化铝为载体,铜为活性组分,氧化锆为助剂。该催化剂的转化率和选择性教高,但催化剂制备过程复杂,且反应所需压力较高。
专利CN105753653B公开了一种制备脂肪醇的方法。该方法以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123或F127中的一种为金属纳米粒子稳定剂稳定Pd、Rh、Pt、Cr、Cu或Ni中的一种金属纳米粒子为催化剂,在温和条件下实现脂肪酸甲酯加氢,但该方法所用的贵金属价格昂贵,Cr可能会造成环境污染。
专利CN103664514B公开了一种脂肪酸酯加氢制备脂肪醇的方法。该方法采用氧化铝负载的铜-锌-硼催化剂,可在温和的反应条件下,获得较高的脂肪酸酯转化率和脂肪醇选择性,但由浸渍法制备出的催化剂,容易出现活性组分聚集烧结的情况,导致催化剂稳定性下降。
专利CN106622368B公开了一种脂肪酸酯加氢制备脂肪醇用的催化剂及其制法和应用。该催化剂为具有双功能催化活性位的核壳结构,以Pd或者Pt为核,以含有酸性位的多孔有机聚合物为壳。该催化剂能够高效的催化脂肪酸酯加氢制得脂肪醇,且催化剂可循环利用,但所使用的贵金属核价格昂贵,生产成本高。
专利CN 108404919B公开了一种用于酯类液相加氢合成脂肪醇的铜碳催化剂及其制备方法,以碳材料为载体,铜作为活性组分,锌作为改性助剂,在温和的反应条件下,具有良好的催化性能和稳定性。但是该方法主要用于酯类液相加氢合成脂肪醇。
虽然现有针对脂肪酸甲酯加氢反应的催化剂发明很多,但少有催化剂能同时解决成本高、反应条件苛刻、稳定性差、活性组分易烧结的问题。所以本发明采用原位生长法,控制催化剂的形貌结构,制备花状多级微米核壳结构催化剂,能够同时解决上述问题。
发明内容
本发明要解决的问题在于现有脂肪酸甲酯加氢制脂肪醇催化剂少有能够同时解决成本高、反应条件苛刻、稳定性差、活性组分易烧结的问题。
本发明的技术方案:
一种用于脂肪酸甲酯脱氧加氢制脂肪醇的核壳型催化剂制备方法,所述的核壳型催化剂以Al2O3为核,在Al2O3上原位生长的CuZnAl水滑石片层交错排列,形成花状多级微米壳层,用于脂肪酸甲酯脱氧加氢高选择性制备脂肪醇,在温和条件下达到40%-98%的转化率和90%-100%的选择性;制备步骤如下:
(1)载体制备:将Al2(SO4)3、尿素、酒石酸钾钠以10:40:1的摩尔比溶解混合,搅拌30分钟后移入水热釜内衬中,在165℃温度条件下水热2h,然后转移到空气中冷却至室温;用去离子水和乙醇交替洗涤、抽滤;在温度为80℃条件下干燥12h后,取出固体粉末,研磨后于550℃温度条件下焙烧6h,得到直径为3-5μm的Al2O3微球,作为载体备用;
(2)催化剂前驱体制备:将总浓度为0.03M的硝酸铜和硝酸锌溶液混合,并加入0.134M硝酸铵、0.018M氟化铵,充分搅拌30min,倒入装有质量比为2.5:1的尿素与Al2O3微球的水热釜内衬中,控制Cu、Zn金属离子总量与Al金属量的摩尔比为2:1,在100℃温度条件下水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃温度条件下干燥12h,研磨后得到Al2O3@CuZnAl-LDH催化剂前驱体;
(3)催化剂制备:将步骤(2)中得到的催化剂前驱体在400℃空气中焙烧4h,得到Al2O3@CuZnAl-LDO催化剂。
所述硝酸铜和硝酸锌的浓度比为3:1-1:2。
一种上述制备方法获得的核壳型催化剂用于催化加氢反应前需要进行活化还原处理,处理方法如下:在固定床反应器中原位还原,还原条件为H2压力0.1-10MPa,H2体积流速40mL/min,还原温度300℃,还原时间2h。
上述核壳型催化剂用于脂肪酸甲酯加氢脱氧反应,该反应在固定床反应器中进行;在固定床反应器中反应温度为200-300℃,氢气压力0.1-10MPa,氢油比为400,空速WHSV为0.19-1.40h-1。
上述所制备核壳型催化剂用于C8-C20的脂肪酸甲酯加氢选择性制备脂肪醇。
本发明的有益效果:本发明采用类水滑石插层组装方法制备花状多级微米核壳型催化剂,核为无定型氧化铝,壳层为CuZnAl-LDH插层,焙烧后得到Al2O3@CuZnAl-LDO用于脂肪酸甲酯加氢脱氧制脂肪醇的反应。该方法制备的催化剂在Cu作为活性中心的基础上,利用LDH层板元素可调的性质,实现催化剂助剂的均匀引入。相较于传统催化剂而言,具有更大的比表面积和发达的孔道结构,能够最大程度实现活性中心的分散和暴露,有利于反应物分子和产物分子的吸附和扩散,从而提高反应效率。并且氧化铝作为载体的同时也提供铝源,以此形成的核壳结构可以进一步提升催化剂的结构稳定性,同时催化剂采用绿色无污染非贵金属,价格低廉、环境友好,具有广阔的应用价值。
附图说明
图1为载体的SEM照片,(a)放大倍数为4万倍;(b)放大倍数为2万倍。
图2为核壳型催化剂SEM照片,(a)放大倍数为7万倍;(b)放大倍数为4万倍;(c)放大倍数为2万倍。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1
制备本发明催化剂所用载体
将0.1M的Al2(SO4)3溶液、0.4M尿素溶液与0.025M酒石酸钾钠溶液混合,搅拌30min后移入100ml水热釜内衬中,165℃条件下水热2h,然后转移到空气中冷却至室温;用去离子水和乙醇交替洗涤、抽滤;在80℃烘箱中干燥12h;取出固体粉末,研磨后转移至马弗炉中550℃焙烧6h,得到无定型Al2O3微球,直径约为3-5μm。
实施例2
制备Al2O3@Cu3Zn1Al-LDO核壳催化剂
将总浓度为0.0225M的硝酸铜和0.0075M硝酸锌溶液混合,并加入硝酸铵、氟化铵,充分搅拌30min,倒入装有0.2552g尿素和0.1gAl2O3微球的水热釜内衬中;100℃水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃烘箱中干燥12h,研磨后得到Al2O3@Cu3Zn1Al-LDH催化剂前驱体。将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到Al2O3@Cu3Zn1Al-LDO核壳催化剂。
实施例3
制备Al2O3@Cu2Zn1Al-LDO核壳催化剂
将总浓度为0.02M的硝酸铜和0.01M硝酸锌溶液混合,并加入硝酸铵、氟化铵,充分搅拌30min,倒入装有0.2552g尿素和0.1gAl2O3微球的水热釜内衬中;100℃水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃烘箱中干燥12h,研磨后得到Al2O3@Cu2Zn1Al-LDH催化剂前驱体。将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到Al2O3@Cu2Zn1Al-LDO核壳催化剂。
实施例4
制备Al2O3@Cu1Zn1Al-LDO核壳催化剂
将总浓度为0.015M的硝酸铜和0.015M硝酸锌溶液混合,并加入硝酸铵、氟化铵,充分搅拌30min,倒入装有0.2552g尿素和0.1gAl2O3微球的水热釜内衬中;100℃水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃烘箱中干燥12h,研磨后得到Al2O3@Cu1Zn1Al-LDH催化剂前驱体。将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到Al2O3@Cu1Zn1Al-LDO核壳催化剂。
实施例5
制备Al2O3@Cu1Zn2Al-LDO核壳催化剂
将总浓度为0.01M的硝酸铜和0.02M硝酸锌溶液混合,并加入硝酸铵、氟化铵,充分搅拌30min,倒入装有0.2552g尿素和0.1gAl2O3微球的水热釜内衬中;100℃水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃烘箱中干燥12h,研磨后得到Al2O3@Cu1Zn2Al-LDH催化剂前驱体。将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到Al2O3@Cu1Zn2Al-LDO核壳催化剂。
实施例6
制备浸渍负载型CuZn/Al2O3催化剂
以实施例3所述催化剂担载量为参照,使用实施例1中所制备的Al2O3微球作为载体,将3.17g硝酸铜与1.59g硝酸锌溶解在30ml去离子水中,搅拌30min后倒入装有1g的Al2O3微球的圆底烧瓶中,搅拌12h,旋蒸干燥过夜,研磨后将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到浸渍负载型CuZn/Al2O3催化剂。
实施例7
制备均匀型CuZnAl-LDO催化剂
以实施例3所述催化剂担载量为参照,将1.21g硝酸铜、0.61g硝酸锌与2.82g硝酸铝溶解在70ml去离子水中,搅拌30min后倒入水热釜内衬中,100℃水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃烘箱中干燥12h,研磨后得到CuZnAl-LDH催化剂前驱体。将催化剂前驱体放入管式炉中用空气400℃焙烧4h,得到均匀型CuZnAl-LDO催化剂。
实施例8
采用实施例2-实施例5催化剂进行加氢性能测试,考察不同金属比例对催化剂催化性能的影响。结果如下:
催化剂 | 转化率(%) | 选择性(%) |
实施例2 | 94.62 | 86.79 |
实施例3 | 97.79 | 92.88 |
实施例4 | 94.54 | 88.86 |
实施例5 | 88.46 | 87.72 |
实施例9
采用实施例3催化剂进行加氢性能测试,考察温度对催化剂催化性能的影响。
称取0.1g实施例3氧化态催化剂,置于固定床反应器的管中部,两侧用20-40目的石英砂支撑添堵。对催化剂进行氢气活化,设定反应器炉温为300℃,调节压力为4Mpa,设置氢气流量为40mL/min,还原时间为2h。活化结束后,调节反应器压力为4Mpa,空速为0.42h-1,初始炉温为200℃,待***温度、压力和气体流量稳定后向反应器输送质量分数为1%的月桂酸甲酯的环己烷溶液,反应每隔2h调整温度,取液体样品用色谱内标法进行分析测试。结果如下:
反应温度(℃) | 转化率(%) | 选择性(%) |
200 | 90.68 | 98.71 |
220 | 92.60 | 98.88 |
240 | 96.39 | 98.34 |
260 | 97.79 | 92.88 |
280 | 99.43 | 88.82 |
实施例10
采用实施例3催化剂进行加氢性能测试,考察空速对催化剂催化性能的影响。
称取0.1g实施例3氧化态催化剂,置于固定床反应器的管中部,两侧用20-40目的石英砂支撑添堵。对催化剂进行氢气活化,设定反应器炉温为300℃,调节压力为4Mpa,设置氢气流量为40mL/min,还原时间为2h。活化结束后,调节反应器压力为4Mpa,炉温为240℃,空速为0.19h-1,待***温度、压力和气体流量稳定后向反应器输送质量分数为1%的月桂酸甲酯的环己烷溶液,反应每隔2h调整进料速率,取液体样品用色谱内标法进行分析测试。反应结果如下:
实施例11
采用实施例3与实例6-7催化剂进行加氢性能测试,考察不同结构催化剂对催化性能的影响。
反应压力为4Mpa,温度为240℃,空速为0.42h-1,待***温度、压力和气体流量稳定后向反应器输送质量分数为1%的月桂酸甲酯的环己烷溶液,取液体样品用色谱内标法进行分析测试。反应结果如下:
催化剂 | 转化率(%) | 选择性(%) |
实施例3 | 97.79 | 92.88 |
实施例6 | 34.71 | 86.65 |
实施例7 | 85.72 | 79.29 |
与实施例6相比,实施例3与实施例7由于形成了水滑石结构,具有更高的催化活性。实施例3表现出最高的催化活性,归因于其特殊的核壳结构,能够更大程度提高活性中心的利用率,利于反应物分子和产物分子的吸附和扩散。
实施例12
采用实施例3进行稳定性测试。反应结果如下:
反应时间(h) | 转化率(%) | 选择性(%) |
10 | 94.02% | 93.87% |
30 | 94.71% | 92.18% |
50 | 93.96% | 94.75% |
100 | 94.88% | 95.82% |
300 | 94.41% | 93.59% |
500 | 93.18% | 92.02% |
600 | 92.66% | 91.07% |
700 | 90.08% | 91.47% |
。
Claims (5)
1.一种用于脂肪酸甲酯脱氧加氢制脂肪醇的核壳型催化剂制备方法,所述的核壳型催化剂以Al2O3为核,在Al2O3上原位生长的CuZnAl水滑石片层交错排列,形成花状多级微米壳层,用于脂肪酸甲酯脱氧加氢高选择性制备脂肪醇,在温和条件下达到40%-98%的转化率和90%-100%的选择性;其特征在于,制备步骤如下:
(1)载体制备:将Al2(SO4)3、尿素、酒石酸钾钠以10:40:1的摩尔比溶解混合,搅拌30分钟后移入水热釜内衬中,在165℃温度条件下水热2h,然后转移到空气中冷却至室温;用去离子水和乙醇交替洗涤、抽滤;在温度为80℃条件下干燥12h后,取出固体粉末,研磨后于550℃温度条件下焙烧6h,得到直径为3-5μm的Al2O3微球,作为载体备用;
(2)催化剂前驱体制备:将总浓度为0.03M的硝酸铜和硝酸锌溶液混合,并加入0.134M硝酸铵、0.018M氟化铵,充分搅拌30min,倒入装有质量比为2.5:1的尿素与Al2O3微球的水热釜内衬中,控制Cu、Zn金属离子总量与Al金属量的摩尔比为2:1,在100℃温度条件下水热12h,然后在空气中冷却至室温;将所得浆液用去离子水和乙醇反复洗涤、抽滤、在80℃温度条件下干燥12h,研磨后得到Al2O3@CuZnAl-LDH催化剂前驱体;
(3)催化剂制备:将步骤(2)中得到的催化剂前驱体在400℃空气中焙烧4h,得到Al2O3@CuZnAl-LDO催化剂。
2.根据权利要求1所述的核壳型催化剂制备方法,其特征在于,所述硝酸铜和硝酸锌的浓度比为3:1-1:2。
3.根据权利要求1或2所述的核壳型催化剂制备方法,其特征在于,所述的核壳型催化剂用于催化加氢反应前需要进行活化还原处理,处理方法如下:在固定床反应器中原位还原,还原条件为H2压力0.1-10MPa,H2体积流速40mL/min,还原温度300℃,还原时间2h。
4.权利要求1或2所述的核壳型催化剂制备方法得到的核壳型催化剂用于脂肪酸甲酯加氢脱氧反应,其特征在于,该反应在固定床反应器中进行;在固定床反应器中反应温度为200-300℃,氢气压力0.1-10MPa,氢油比为400,空速WHSV为0.19-1.40h-1。
5.根据权利要求4所述的核壳型催化剂用于脂肪酸甲酯加氢脱氧反应,其特征在于,所述的核壳型催化剂用于C8-C20的脂肪酸甲酯加氢选择性制备脂肪醇。
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