CN106040255B - 一种生物质油加氢脱氧催化剂及其制备方法 - Google Patents
一种生物质油加氢脱氧催化剂及其制备方法 Download PDFInfo
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- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明属于油品精制技术领域，特别涉及一种生物质油加氢脱氧催化剂及其制备方法。该催化剂以镍钨组合物为主活性组分，稀土金属镧、铈等为助剂，二氧化硅为分散介质，同时加入元素氟对催化剂进行改性。要求催化剂中主活性组分镍钨组合物的含量为15％～60％，镍钨摩尔配比在0.8～3：1，稀土金属的含量在3％～10％，且要求镍钨组合物与稀土金属的质量比为4～10:1，氟的含量在0.5％～3％。本发明的分散介质SiO2与活性组分NiW质量比调节范围宽，且可以制备出高活性组分含量的催化剂，突破了常规的负载型催化剂活性组分含量较低的限制。该催化剂在常压及较低的反应温度下，具有很高的催化性能，应用前景广阔。
Description
技术领域
本发明属于油品精制技术领域，特别涉及一种生物质油加氢脱氧催化剂及其制备方法。
背景技术
目前，用于生物油中含氧化合物的催化加氢脱氧的催化剂有多种。对于这些HDO催化剂而言，硫化物催化剂的脱氧活性虽然较好，但在利用其进行HDO反应的过程中，由于生物油中的硫含量很低，其中的氧会破坏硫化物的硫化结构，从而导致催化剂活性下降，因此，必须靠添加少量的硫化剂来维持硫化物的催化活性，这就不可避免地给加氢后的生物油带入了新的硫污染源。同时，由于硫化物催化剂的加氢活性欠佳，导致脱氧后的生物油产物中苯和芳烃含量都较高；磷化物催化酚类化合物的HDO反应也主要是按直接脱氧的路径进行，产物达不到清洁燃油的标准；贵金属和氮化物负载型催化剂则存在着成本较高、易失活、比表面积小、孔径小或脱氧活性欠佳等不足；而非晶态合金由于热稳定性较差，严重阻碍了其工业应用。对于HDO反应，目前文献报道的酚类化合物HDO反应温度基本是在300℃以上，有些高达450℃。高温度反应能耗大，且易发生催化剂上结焦现象而降低其活性；而低温(≤250℃)条件下，这类催化剂的活性又较低，导致其对原料的脱氧率较低。
发明内容
本发明要解决的技术问题是如何克服现有技术的不足，提供一种生物质油加氢脱氧催化剂及其制备方法。
本发明为实现上述目的采用的技术方案是：一种生物质油加氢脱氧催化剂，主活性组分为镍钨组合物，稀土金属及氟为助剂，所述催化剂分散介质为SiO2,其重量比如下：镍钨组合物含量为15％～60％，镍钨摩尔配比在0.8～3：1；稀土金属的含量在3％～10％，氟的含量在0.5％～5％。
所述生物质油加氢脱氧催化剂的制备方法，采用如下工艺步骤：
a)配制一定量的尿素、镍的可溶性盐混合水溶液，向此溶液中加入一定量正硅酸乙酯，搅拌直至均一透明，加入一定量的氟化铵，搅匀，静置直至形成凝胶，将此凝胶放入密闭容器加热至60～120℃，反应1～4小时，再在80℃～140℃下分温度段干燥4～8小时，粉碎，即得到Ni/SiO2前体；
b)配制一定浓度的偏钨酸铵、稀土金属可溶性盐混合水溶液，接着向混合液中加入相当于Ni/SiO2前体质量10％～30％的扩孔剂，搅匀，再将Ni/SiO2前体加入此混合溶液中，密闭放置6～24小时；
c)上述步骤b)得到的混合体系置入晶化釜中，在90～160℃下，密闭晶化2～8小时；
d)晶化结束后，蒸发溶剂，并在100℃～140℃下干燥2～8小时，再在280～400℃焙烧2～6小时，即得NiW/SiO2催化剂。
进一步的，制备中，扩孔剂为醇类、有机胺类等。
进一步的，制备中，所述稀土金属采用镧或铈。
本发明还提供了上述生物质油加氢脱氧催化剂在油品精制领域的应用。
所述生物质油加氢脱氧催化剂使用前要进行活化，活化条件为：活化温度为300～450℃，氢气压力为常压，氢气空速为0.5～6h-1，活化时间为1～5小时。
所述生物质油加氢脱氧催化剂使用时反应条件：反应温度150～260℃，压力为常压，氢油体积比为50～800：1，体积空速0.5～6h-1。
本发明的优点在于使用一全新的镍钨组合物为主活性组分，表征结果显示此组合物为一新的结构，低温氮气吸脱附分析表明镍钨组合物本身具有介孔结构和较大的比表面积；另外，本发明催化剂采用溶胶凝胶、沉积沉淀及水热等混合方法制备，使得催化剂具有很高的比表面和孔容，进一步提高镍钨组合物的分散度，大大提高了催化剂的活性。
本发明的分散介质SiO2与活性组分镍钨组合物质量比调节范围宽，且可以制备出高活性组分含量的催化剂，突破了常规负载型催化剂活性组分含量低的限制。
附图说明
图1本发明催化剂NiW组合物与NiW/SiO2的XRD谱图。
图2本发明催化剂NiW/SiO2的Ni2p XPS谱图。
图3本发明催化剂NiW/SiO2的W4d XPS谱图。
具体实施方式
下面结合实施例详细说明本发明。
实施例1
一种生物质油加氢脱氧催化剂的制备方法如下：
a)配制含0.75mol尿素、1mol硝酸镍的混合水溶液，向此溶液中加入2.3mol正硅酸乙酯，搅拌直至均一透明，加入6克氟化铵，搅匀后，静置直至形成凝胶，将此凝胶放入密闭容器加热至90℃，反应2小时，再在80℃下干燥4小时，140℃下干燥4小时，粉碎，即得到Ni/SiO2前体；
b)配制含0.14mol偏钨酸铵、0.1mol硝酸铈混合水溶液，接着向混合液中加入30克的乙二醇，搅匀，再将Ni/SiO2前体粉末加入此混合溶液中，密闭放置12小时；
c)上述混合体系置入晶化釜中，在140℃下，密闭晶化4小时；
d)晶化结束后，蒸发溶剂，再在120℃干燥4小时，再在380℃焙烧3小时，即得NiW/SiO2催化剂。
经XRF测试，此催化剂各组分重量份数如下：镍钨组合物的含量为48.5％；氧化铈含量为4.0％，氟的含量在1.6％，SiO2含量为45.9％。
实施例2
本实施催化剂的制备方法及参数与实施例1相同，只是将镍钨摩尔配比调整为2:1。
经XRF测试，此催化剂各组分重量份数如下：镍钨组合物的含量为48.9％；氧化铈含量为3.9％，氟的含量在1.5％，SiO2含量为45.7％。
实施例3
本实施催化剂的制备方法及参数与实施例1相同，只是将镍钨组合物含量调整为30％。
经XRF测试，此催化剂各组分重量份数如下：镍钨组合物的含量为29.0％；氧化铈含量为4.1％，氟的含量在1.5％，SiO2含量为65.4％。
实施例4
本实施催化剂的制备方法及参数与实施例1相同，只是将助剂铈改为镧。
经XRF测试，此催化剂各组分重量份数如下：镍钨组合物的含量为48.6％；氧化镧含量为3.8％，氟的含量在1.6％，SiO2含量为46.0％。
实施例5
将实施例1所得到的生物质油加氢脱氧催化剂进行数据表征：
从图1中可以看到，纯态NiW催化剂的谱图中2θ在64.3°、53.8°、40.8°、38.7°、35.7°处，出现了较为强烈的衍射峰。而NiW/SiO2催化剂仅仅在2θ＝64.3°、53.8°、35.7°出现衍射峰，其它一些峰由于强度较低而未出现，且衍射峰明显宽化，根据Scherrer公式，这说明NiW/SiO2催化剂活性组分一次颗粒的尺寸越小，表面积越大，这与低温N2吸附(如表1)得到的结果相符。除此之外，两种催化剂的XRD衍射谱形非常相似的，这说明二氧化硅载体并没有改变NiW组合物的结构。
表1NiW/SiO2催化剂的BET分析结果
图2、图3为NiW/SiO2的XPS谱图。由图2、图3可以看出，Ni2p曲线经拟合后出现了两组Ni2p1/2和Ni2p3/2双峰：第一组峰出现在874.9eV(2p1/2)和856.8eV(2p3/2)，归属于Ni2+；另一组为宽化的卫星峰，分别为881.3eV(2p1/2)和862.9eV(2p3/2)。NiW组合物表面上W4d出现了两个明显的谱峰，结合能分别为257.9eV(W4d3/2)和245.2eV(W4d5/2)，对于这两个结合能还未见报道，W的不同于目前已知的化学状态。以上的分析结果表明NiW组合物为一新的化学结构，其精确结构仍需新一步研究。
实施例6
本实施例说明本发明所述催化剂的评价方法。
催化剂活性评价是在100mL固定床反应器中进行。模型化合物原料组成为：20wt％对甲基苯酚的十氢萘溶液。原料采用柱塞泵泵入，加氢产物经高压分离器(冷高分)和低压分离器(冷低分)分离出液体和气体后，液体产物流入接样罐。反应前，先通氢气对催化剂进行活化，活化条件为常压，活化温度375℃，活化时间3小时，液时空速为2.0h-1。然后降温至反应温度，开始进原料(模型化合物)，反应稳定12小时后取样，用气相色谱仪(Varian3800毛细色谱柱，FID检测器)分析。反应条件：200℃，液时空速为2.0h-1，氢油比：300/1，反应压力：常压。
参比催化剂采用工业化的负载型NiW催化剂，反应前需先硫化，将其转化为硫化态催化剂，反应条件相同。几种催化剂的反应评价结果表2所示。
表2本发明催化剂与参比催化剂加氢脱氧活性评价结果
| 催化剂 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 参比催化剂 |
| 加氢脱氧率(％) | 89 | 98 | 81 | 85 | 30 |
由表2的数据可以看出，本发明制备的催化剂催化活性远高于工业应用的负载型过渡金属硫化物催化剂；活性组分镍钨组合物的配比对催化剂的活性有着非常明显的影响，镍含量相对较高的催化剂活性较好；同时由于载体材料的含量对活性金属的担载量和利用率起着重要的作用，所以对催化剂的性能也有影响。总之，本发明提供的催化剂可以用于生物质油进行超深度加氢脱氧改质，且所适用的工艺条件非常温和，在常压及较低的反应温度下，具有很高的催化性能，显示出巨大的工业应用价值。
上述实施例只是为了说明本发明的技术构思及特点，其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所做出的等效的变化或修饰，都应涵盖在本发明的保护范围内。
Claims (4)
1.一种生物质油加氢脱氧催化剂，其特征在于：主活性组分为镍钨组合物，稀土金属及氟为助剂，所述催化剂分散介质为SiO2,其重量比如下：镍钨组合物含量为15％～60％，镍钨摩尔配比在0.8～3：1，稀土金属的含量在3％～10％，氟的含量在0.5％～5％；由以下工艺制备：
a)配制一定量的尿素、镍的可溶性盐混合水溶液，向此溶液中加入一定量正硅酸乙酯，搅拌直至均一透明，加入一定量的氟化铵，搅匀，静置直至形成凝胶，将此凝胶放入密闭容器加热至60～120℃，反应1～4小时，再在80℃～140℃下分温度段干燥4～8小时，粉碎，即得到NiF/SiO2前体；
b)配制一定浓度的偏钨酸铵、稀土金属可溶性盐混合水溶液，接着向混合液中加入相当于NiF/SiO2前体质量10％～30％的扩孔剂，搅匀，再将NiF/SiO2前体加入此混合溶液中，密闭放置6～24小时；
c)上述步骤b)得到的混合体系置入晶化釜中，在90～160℃下，密闭晶化2～8小时；
d)晶化结束后，蒸发溶剂，并在100℃～140℃下干燥2～8小时，再在280～400℃焙烧2～6小时，即得NiFW稀土/SiO2催化剂。
2.如权利要求1所述的一种生物质油加氢脱氧催化剂，其特征在于：扩孔剂是醇类或者有机胺类，所述稀土金属采用镧或铈。
3.如权利要求1所述的一种生物质油加氢脱氧催化剂在油品精制领域的应用。
4.如权利要求3所述的一种生物质油加氢脱氧催化剂在油品精制领域的应用，其特征在于：使用前进行活化，活化条件为：活化温度为300～450℃，氢气压力为常压，氢气空速为0.5～6h-1，活化时间为1～5小时；使用时反应条件：反应温度150～260℃，压力为常压，氢油体积比为50～800：1，体积空速0.5～6h-1。
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