CN115920897A - Metal catalyst and its preparation method and application - Google Patents
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Translated fromChinese技术领域technical field
本发明涉及纳米催化剂领域，具体地，涉及一种金属催化剂及其制备方法和应用。The invention relates to the field of nano catalysts, in particular to a metal catalyst and its preparation method and application.
背景技术Background technique
2-甲基呋喃是一种重要的化工原料，应用前景广阔，可用于有机溶剂、有机合成中间体，在化工、医药、农药、能源领域均有重要的应用。工业上，通常利用铬、铜催化剂来催化糠醛转化制备2-甲基呋喃。由于铬在反应处理过程中对环境污染严重，如果未经处理排放，则会对土壤和地下水导致铬超标，被人体吸收就会产生不可逆的伤害。同时，铜基催化剂在糠醛催化加氢制备2-甲基呋喃的催化反应中也存在诸多不足，如2-甲基呋喃的收率及选择性均较低，且Cu颗粒容易在反应过程中流失，并能引起较多的副反应发生，催化剂的重复循环效果较差。2-Methylfuran is an important chemical raw material with broad application prospects. It can be used as an organic solvent and an intermediate in organic synthesis, and has important applications in the fields of chemical industry, medicine, pesticide and energy. In industry, chromium and copper catalysts are usually used to catalyze the conversion of furfural to prepare 2-methylfuran. Because chromium pollutes the environment seriously during the reaction treatment process, if it is discharged without treatment, it will cause excessive chromium to the soil and groundwater, and irreversible damage will occur if it is absorbed by the human body. At the same time, copper-based catalysts also have many shortcomings in the catalytic reaction of furfural catalytic hydrogenation to 2-methylfuran, such as the yield and selectivity of 2-methylfuran are low, and Cu particles are easily lost during the reaction process. , and can cause more side reactions to occur, and the repeated cycle effect of the catalyst is poor.
文献(Applied Catalysis B:Environmental,2021,282，119576)中研究了Cu物种在催化糠醛制备2-甲基呋喃中的影响，验证了Cu对该反应的有效性。Cu/SiO2催化剂多用于糠醛加氢反应，但由于SiO2是中性物质，与活性组分之间的相互作用不够紧密，使得在催化糠醛性能方面仍有待提高。文献(Catalysis Today,2021,365:291-300)中向Cu-SiO2催化剂体系中添加了贵金属Pd，使得2-甲呋喃的收率有所提高。然而，催化剂在反应过程中同样会出现活性组分的不稳定，导致催化剂性能下降。这使得研究催化剂的制备工艺及调控活性组分与载体之间的作用来提高催化剂性能至关重要。In the literature (Applied Catalysis B: Environmental, 2021, 282, 119576), the influence of Cu species on the catalysis of furfural to 2-methylfuran was studied, and the effectiveness of Cu for this reaction was verified. Cu/SiO2 catalyst is mostly used in furfural hydrogenation reaction, but because SiO2 is a neutral substance, the interaction with active components is not close enough, so the catalytic performance of furfural still needs to be improved. In the literature (Catalysis Today, 2021, 365:291-300), the noble metal Pd was added to the Cu-SiO2 catalyst system to increase the yield of 2-methylfuran. However, the instability of the active components of the catalyst will also occur during the reaction process, resulting in a decrease in the performance of the catalyst. This makes it very important to study the preparation process of the catalyst and adjust the interaction between the active component and the support to improve the performance of the catalyst.
发明内容Contents of the invention
本发明的目的是提供一种金属催化剂及其制备方法和应用，该金属催化剂具有优异的糠醛液相加氢性能，在糠醛液相加氢制取2-甲基呋喃的反应中，糠醛转化率高达100％，2-甲基呋喃收率高达99％，且该催化剂的制备方法只需在氢化试剂下低温还原，制备工艺简单绿色环保。The purpose of the present invention is to provide a metal catalyst and its preparation method and application. The metal catalyst has excellent furfural liquid-phase hydrogenation performance. In the reaction of furfural liquid-phase hydrogenation to produce 2-methylfuran, the furfural conversion rate As high as 100%, the yield of 2-methylfuran is as high as 99%, and the preparation method of the catalyst only needs low-temperature reduction under a hydrogenation reagent, and the preparation process is simple and green.
为了实现上述目的，本发明提供了一种金属催化剂，该金属催化剂的载体为Al2O3，活性组分为Co和/或Ni；In order to achieve the above object, the present invention provides a metal catalyst, the carrier of the metal catalyst is Al2 O3 , and the active component is Co and/or Ni;
其中，所述Al2O3经过有机酸酸化处理进行改性。Wherein, the Al2 O3 is modified by an acidification treatment with an organic acid.
本发明还提供了一种所述金属催化剂的制备方法，该制备方法包括：The present invention also provides a kind of preparation method of described metal catalyst, and this preparation method comprises:
1)将Al2O3酸化处理，第一过滤，第一洗涤，第一干燥后得到载体Al2O3；1) acidifying Al2 O3 , first filtering, first washing, and first drying to obtain the carrier Al2 O3 ;
2)将金属盐溶解于溶剂中，加入载体Al2O3，再加入还原剂，得到混合溶液进行反应，第二过滤，第二洗涤，第二干燥，获得金属催化剂；2) dissolving the metal salt in a solvent, adding carrier Al2 O3 , and then adding a reducing agent to obtain a mixed solution for reaction, second filtering, second washing, and second drying to obtain a metal catalyst;
其中，所述金属盐为Co盐和/或Ni盐。Wherein, the metal salt is Co salt and/or Ni salt.
本发明进一步提供了一种所述的金属催化剂在糠醛液相加氢制取2-甲基呋喃反应中的应用。The present invention further provides an application of the metal catalyst in the reaction of furfural liquid-phase hydrogenation to prepare 2-methylfuran.
本发明进一步提供了一种糠醛加氢制取2-甲基呋喃的方法，该方法包括：在氢气环境中，金属催化剂催化糠醛在微型浆态床反应装置上进行液相加氢反应，使其转化为2-甲基呋喃；The present invention further provides a method for preparing 2-methylfuran by hydrogenating furfural, the method comprising: in a hydrogen environment, a metal catalyst catalyzes furfural in a micro-slurry bed reaction device to carry out a liquid-phase hydrogenation reaction to make it Converted to 2-methylfuran;
其中，所述金属催化剂为权利要求1或2所述的金属催化剂；和/或，Wherein, the metal catalyst is the metal catalyst described in
所述糠醛的质量浓度为0.01-0.05g/mL；和/或，The mass concentration of the furfural is 0.01-0.05g/mL; and/or,
所述氢气的压力为0.6-1MPa；和/或，The pressure of the hydrogen is 0.6-1MPa; and/or,
所述液相加氢反应包括：温度为180-260℃，时间为2-6h；优选为温度为220-240℃，时间为4h。The liquid-phase hydrogenation reaction includes: the temperature is 180-260°C, and the time is 2-6h; preferably, the temperature is 220-240°C, and the time is 4h.
在上述技术方案中，本发明通过利用有机酸处理改性Al2O3载体，有效改善了Al2O3载体的表面酸性基团特质，有利于促进Al2O3载体与Ni或Co的作用；另一方面，采用液相原位还原法制备催化剂，可以有效避免催化剂活性组分的热团聚和活性中心数量的降低，同时由于该法只需在低温下进行，可以缩短催化剂制备周期和有效降低能耗；并且所制备的催化剂展示出优异的糠醛液相加氢性能。In the above technical solution, the present invention effectively improves the surface acidic group characteristics of the Al2 O3 support by using an organic acid to modify the Al2 O3 support, which is beneficial to promote the interaction between the Al2 O3 support and Ni or Co ; On the other hand, the preparation of catalysts by liquid-phase in-situ reduction method can effectively avoid the thermal agglomeration of catalyst active components and the reduction of the number of active centers. Energy consumption is reduced; and the prepared catalyst exhibits excellent furfural liquid-phase hydrogenation performance.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the following detailed description.
附图说明Description of drawings
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:
图1为实施例1中制备的Co/Al2O3-N(1:15)催化剂进行糠醛液相加氢反应的产物气相色谱图；Fig. 1 is that Co/Al2O3- N (1:15) catalyst prepared in
图2为实施例1中制备的Co/Al2O3-N(1:15)催化剂的透射电子显微镜照片(TEM)；Fig. 2 is the transmission electron micrograph (TEM) of Co/Al2 O3 -N (1:15) catalyst prepared in
图3为实施例6中制备的Ni/Al2O3-A(1:15)催化剂的透射电子显微镜照片(TEM)。Fig. 3 is a transmission electron micrograph (TEM) of the Ni/Al2 O3 -A (1:15) catalyst prepared in Example 6.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, not to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明提供了一种金属催化剂，该金属催化剂的载体为Al2O3，活性组分为Co和/或Ni；The invention provides a metal catalyst, the carrier of the metal catalyst is Al2 O3 , and the active component is Co and/or Ni;
其中，所述Al2O3经过有机酸酸化处理进行改性。Wherein, the Al2 O3 is modified by an acidification treatment with an organic acid.
本发明的金属催化剂具有优异的糠醛液相加氢性能，糠醛可以实现完全转化。The metal catalyst of the invention has excellent furfural liquid-phase hydrogenation performance, and the furfural can be completely converted.
根据本发明一种优选的实施方式金属原子和Al原子的摩尔比可以在宽的范围内选择，但是为了使催化剂具有更好的催化性能，所述金属催化剂中金属原子与Al原子的摩尔比为1：5-40。According to a preferred embodiment of the present invention, the mol ratio of metal atoms and Al atoms can be selected in a wide range, but in order to make the catalyst have better catalytic performance, the mol ratio of metal atoms and Al atoms in the metal catalyst is: 1:5-40.
本发明还提供了一种所述金属催化剂的制备方法，该制备方法包括：The present invention also provides a kind of preparation method of described metal catalyst, and this preparation method comprises:
1)将Al2O3酸化处理，第一过滤，第一洗涤，第一干燥后得到载体Al2O3；1) acidifying Al2 O3 , first filtering, first washing, and first drying to obtain the carrier Al2 O3 ;
2)将金属盐溶解于溶剂中，加入载体Al2O3，再加入还原剂，得到混合溶液进行反应，第二过滤，第二洗涤，第二干燥，获得金属催化剂；2) dissolving the metal salt in a solvent, adding carrier Al2 O3 , and then adding a reducing agent to obtain a mixed solution for reaction, second filtering, second washing, and second drying to obtain a metal catalyst;
其中，所述金属盐为Co盐和/或Ni盐。Wherein, the metal salt is Co salt and/or Ni salt.
本发明所述的催化剂制备方法中，催化剂只需在氢化试剂下低温还原，制备工艺简单绿色环保。In the catalyst preparation method of the present invention, the catalyst only needs to be reduced under a hydrogenation reagent at low temperature, and the preparation process is simple and environmentally friendly.
根据本发明一种优选的实施方式，酸化处理的条件可以在宽的范围内选择，但是为了改善载体Al2O3表面酸性基团特质，促进载体与Ni或Co的作用，步骤1)中，所述酸化处理包括：在温度为80-150℃下于酸性试剂中处理1-3h。According to a preferred embodiment of the present invention, the conditions of the acidification treatment can be selected in a wide range, but in order to improve the characteristics of the acidic groups on the surface of the carrier Al2 O3 and promote the interaction between the carrier and Ni or Co, in step 1), The acidifying treatment includes: treating in an acidic reagent at a temperature of 80-150° C. for 1-3 hours.
根据本发明一种优选的实施方式，酸性试剂的种类可以在宽的范围内选择，但是为了使载体Al2O3表面酸性基团得到有效的改善，所述酸性试剂为柠檬酸、甲酸和醋酸中的至少一者。According to a preferred embodiment of the present invention, the type of acidic reagent can be selected in a wide range, but in order to make the carrierAl2O3 surface acidic groups are effectively improved, the acidic reagentis citric acid, formic acid and acetic acid at least one of the .
根据本发明一种优选的实施方式，酸性试剂的浓度可以在宽的范围内选择，但是为了使载体Al2O3改性完全，所述酸性试剂的质量分数为10％～30％。According to a preferred embodiment of the present invention, the concentration of the acidic reagent can be selected within a wide range, but in order to completely modify the carrier Al2 O3 , the mass fraction of the acidic reagent is 10%-30%.
根据本发明一种优选的实施方式，金属盐的种类可以在宽的范围内选择，但是为了使催化剂拥有更优异的催化加氢的性能，步骤2)中，所述金属盐为Co硝酸盐、Co卤化物、Co醋酸盐、Ni硝酸盐、Ni卤化物和Ni醋酸盐中的至少一者。According to a preferred embodiment of the present invention, the type of metal salt can be selected in a wide range, but in order to make the catalyst have better catalytic hydrogenation performance, in step 2), the metal salt is Co nitrate, At least one of Co halide, Co acetate, Ni nitrate, Ni halide, and Ni acetate.
根据本发明一种优选的实施方式，还原剂的种类可以在宽的范围内选择，但是为了使催化剂可以在低温下迅速被还原，步骤2)中，所述还原剂为硼氢化钠和/或硼氢化钾。According to a preferred embodiment of the present invention, the type of reducing agent can be selected in a wide range, but in order to make the catalyst can be reduced rapidly at low temperature, in step 2), the reducing agent is sodium borohydride and/or Potassium borohydride.
根据本发明一种优选的实施方式，步骤2)中，溶剂的种类可以在宽的范围内选择，但是为了使得还原反应迅速完全的进行，步骤2)中，所述溶剂为去离子水。According to a preferred embodiment of the present invention, in step 2), the type of solvent can be selected in a wide range, but in order to make the reduction reaction proceed quickly and completely, in step 2), the solvent is deionized water.
根据本发明一种优选的实施方式，步骤2)中的反应条件可以在宽的范围内选择，但是为了使得载体和金属原子可以更好的反应结合，步骤2)中，所述反应条件包括：将混合溶液加盖密封，于40-80℃的温度下搅拌3-24h。According to a preferred embodiment of the present invention, the reaction conditions in step 2) can be selected in a wide range, but in order to make the carrier and the metal atom can react better, in step 2), the reaction conditions include: The mixed solution was covered and sealed, and stirred at a temperature of 40-80°C for 3-24h.
根据本发明一种优选的实施方式，步骤2)中，第二洗涤的条件包括可以在宽的范围内选择，但是为了使得催化剂拥有更好的催化加氢的性能，步骤2)中，所述第二洗涤的条件包括：用去离子水将过滤产物洗至中性。According to a preferred embodiment of the present invention, in step 2), the conditions of the second washing can be selected in a wide range, but in order to make the catalyst have better catalytic hydrogenation performance, in step 2), the The conditions for the second washing include: washing the filtered product with deionized water to neutrality.
本发明进一步提供了一种所述的金属催化剂在糠醛液相加氢制取2-甲基呋喃反应中的应用。The present invention further provides an application of the metal catalyst in the reaction of furfural liquid-phase hydrogenation to prepare 2-methylfuran.
本发明进一步提供了一种糠醛加氢制取2-甲基呋喃的方法，该方法包括：在氢气环境中，金属催化剂催化糠醛在微型浆态床反应装置上进行液相加氢反应，使其转化为2-甲基呋喃；The present invention further provides a method for preparing 2-methylfuran by hydrogenating furfural, the method comprising: in a hydrogen environment, a metal catalyst catalyzes furfural in a micro-slurry bed reaction device to carry out a liquid-phase hydrogenation reaction to make it Converted to 2-methylfuran;
其中，所述金属催化剂为上述制备方法所述的金属催化剂；Wherein, the metal catalyst is the metal catalyst described in the above preparation method;
根据本发明一种优选的实施方式，糠醛的质量浓度可以在宽的范围内选择，但是为了使反应的转化效率更高，所述糠醛的质量浓度为0.01-0.05g/mL。According to a preferred embodiment of the present invention, the mass concentration of furfural can be selected within a wide range, but in order to make the conversion efficiency of the reaction higher, the mass concentration of furfural is 0.01-0.05g/mL.
根据本发明一种优选的实施方式，氢气的压力可以在宽的范围内选择，但是为了使得糠醛能完全转化为2-甲基呋喃，所述氢气的压力为0.6-1MPa。According to a preferred embodiment of the present invention, the pressure of hydrogen can be selected within a wide range, but in order to completely convert furfural into 2-methylfuran, the pressure of hydrogen is 0.6-1 MPa.
根据本发明一种优选的实施方式，液相加氢反应的条件可以在宽的范围内选择，但是为了使得糠醛能完全转化为2-甲基呋喃，所述液相加氢反应的条件包括：温度为180-260℃，时间为2-6h。According to a preferred embodiment of the present invention, the conditions of the liquid-phase hydrogenation reaction can be selected in a wide range, but in order to make furfural fully convert into 2-methylfuran, the conditions of the liquid-phase hydrogenation reaction include: The temperature is 180-260°C, and the time is 2-6h.
根据本发明一种优选的实施方式，液相加氢反应的条件可以在宽的范围内选择，但是为了使得糠醛能完全转化为2-甲基呋喃，所述液相加氢反应的条件包括：温度为220-240℃，时间为4h。According to a preferred embodiment of the present invention, the conditions of the liquid-phase hydrogenation reaction can be selected in a wide range, but in order to make furfural fully convert into 2-methylfuran, the conditions of the liquid-phase hydrogenation reaction include: The temperature is 220-240°C, and the time is 4h.
本发明的金属催化剂在糠醛液相加氢制取2-甲基呋喃反应中的应用，糠醛转化率高达100％，2-甲基呋喃收率高达99％。The application of the metal catalyst of the invention in the reaction of furfural liquid-phase hydrogenation to prepare 2-methylfuran has the furfural conversion rate as high as 100 percent and the 2-methylfuran yield as high as 99 percent.
以下将通过实例对本发明进行详细描述。以下实例中，药品和药剂均为常规市售品。The present invention will be described in detail below by way of examples. In the following examples, the medicines and medicaments are all conventional commercial products.
实施例1Example 1
(1)称取10g Al2O3粉状小颗粒，置于10％柠檬酸溶液，在100℃下进行酸化处理3h，之后用去离子水清洗，110℃干燥后备用。(1) Weigh 10g of Al2 O3 powdery particles, place them in 10% citric acid solution, carry out acidification treatment at 100°C for 3 hours, then wash with deionized water, dry at 110°C and set aside.
(2)称取2.31g六水合硝酸钴，充分溶解于15mL去离子水中，并与步骤(1)中处理后的Al2O3载体充分搅拌、混合0.5h，添加硼氢化钠，加盖密封，40℃下搅拌12h，用去离子水清洗至中性，放置真空干燥器内于40℃干燥10h，得到Co/Al2O3-N(1:15)催化剂，记为Cat 1。(2) Weigh 2.31g of cobalt nitrate hexahydrate, fully dissolve in 15mL of deionized water, and fully stir and mix with theAl2O3 carrier treated in step (1) for 0.5h, add sodium borohydride, cover andseal , stirred at 40°C for 12h, washed with deionized water until neutral, and dried in a vacuum dryer at 40°C for 10h to obtain a Co/Al2 O3 -N (1:15) catalyst, which was designated as
其TEM图如图2所示，可以看出，粒径分布最多在3.5-4.0nm，平均粒径为3.98nm。Its TEM image is shown in Figure 2. It can be seen that the particle size distribution is at most 3.5-4.0 nm, and the average particle size is 3.98 nm.
实施例2Example 2
实施步骤和条件同实施例1，只是将10％柠檬酸溶液换成10％乙酸溶液，获得Co/Al2O3-A(1:15)催化剂，记为Cat 2。The implementation steps and conditions are the same as in Example 1, except that the 10% citric acid solution is replaced by 10% acetic acid solution to obtain a Co/Al2 O3 -A (1:15) catalyst, which is designated as
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
实施例3Example 3
实施步骤和条件同实施例1，只是将六水合硝酸钴质量由2.31g，调换为3.46g，获得Co/Al2O3-A(1:10)催化剂，记为Cat 3。The implementation steps and conditions are the same as in Example 1, except that the mass of cobalt nitrate hexahydrate is changed from 2.31 g to 3.46 g to obtain a Co/Al2 O3 -A (1:10) catalyst, which is designated as
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
实施例4Example 4
实施步骤和条件同实施例1，只是将六水合硝酸钴质量由2.31g，调换为6.92g，获得Co/Al2O3-A(1:5)催化剂，记为Cat 4。The implementation steps and conditions are the same as in Example 1, except that the mass of cobalt nitrate hexahydrate is changed from 2.31 g to 6.92 g to obtain a Co/Al2 O3 -A (1:5) catalyst, which is designated as
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
实施例5Example 5
实施步骤和条件同实施例1，只是将六水合硝酸钴质量由2.31g，调换为0.87g，获得Co/Al2O3-A(1:40)催化剂，记为Cat 5。The implementation steps and conditions are the same as in Example 1, except that the mass of cobalt nitrate hexahydrate is changed from 2.31 g to 0.87 g to obtain a Co/Al2 O3 -A (1:40) catalyst, which is designated as
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
实施例6Example 6
实施步骤和条件同实施例1，只是将六水合硝酸钴改为硝酸镍，质量为1.91g，获得Ni/Al2O3-A(1:15)催化剂，记为Cat 6。The implementation steps and conditions are the same as in Example 1, except that cobalt nitrate hexahydrate is replaced by nickel nitrate, the mass is 1.91g, and the Ni/Al2 O3 -A (1:15) catalyst is obtained, which is recorded as
其TEM图如图3所示，可知，其粒径分布主要在2.0-3.5nm，平均粒径为2.97nm。Its TEM image is shown in Figure 3. It can be seen that the particle size distribution is mainly in the range of 2.0-3.5nm, and the average particle size is 2.97nm.
实施例7Example 7
实施步骤和条件同实施例6，只是将硝酸镍质量由1.91g，调换为2.85g，获得Ni/Al2O3-A(1:10)催化剂，记为Cat 7。The implementation steps and conditions are the same as in Example 6, except that the mass of nickel nitrate is changed from 1.91 g to 2.85 g to obtain a Ni/Al2 O3 -A (1:10) catalyst, which is designated as
其TEM图与实施例6基本一致。Its TEM picture is basically consistent with
实施例8Example 8
实施步骤和条件同实施例6，只是将硝酸镍改为氯化镍，质量为1.56g，获得Ni/Al2O3-A(1:15)催化剂，记为Cat 8。The implementation steps and conditions are the same as in Example 6, except that the nickel nitrate is changed to nickel chloride, and the mass is 1.56g to obtain a Ni/Al2 O3 -A (1:15) catalyst, which is designated as
其TEM图与实施例6基本一致。Its TEM picture is basically consistent with
实施例9Example 9
实施步骤和条件同实施例7，只是将糠醛质量由0.5g，调换为0.25g，获得Ni/Al2O3-A(1:15)催化剂，记为Cat 9。The implementation steps and conditions are the same as in Example 7, except that the mass of furfural is changed from 0.5 g to 0.25 g to obtain a Ni/Al2 O3 -A (1:15) catalyst, which is designated as
其TEM图与实施例6基本一致。Its TEM picture is basically consistent with
实施例10Example 10
实施步骤和条件同实施例1，只是将糠醛质量由0.5g，调换为0.1g，获得Ni/Al2O3-N(1:15)催化剂，记为Cat 10。The implementation steps and conditions are the same as in Example 1, except that the mass of furfural is changed from 0.5 g to 0.1 g to obtain a Ni/Al2 O3 -N (1:15) catalyst, which is designated as
其TEM图与实施例6基本一致。Its TEM picture is basically consistent with
实施例11Example 11
(1)称取10g Al2O3粉状小颗粒，置于30％柠檬酸溶液，在80℃下进行酸化处理1h，之后用去离子水清洗，100℃干燥后备用。(1) Weigh 10g of Al2 O3 powdery particles, place them in 30% citric acid solution, carry out acidification treatment at 80°C for 1 hour, then wash them with deionized water, dry them at 100°C and set aside.
(2)称取2.31g六水合硝酸钴，充分溶解于15mL去离子水中，并与步骤(1)中处理后的Al2O3载体充分搅拌、混合0.5h，添加硼氢化钾，加盖密封，80℃下搅拌3h，用去离子水清洗至中性，放置真空干燥器内于40℃干燥10h，得到Co/Al2O3-N(1:15)催化剂，记为Cat 11。(2) Weigh 2.31g of cobalt nitrate hexahydrate, fully dissolve in 15mL of deionized water, and fully stir and mix with theAl2O3 carrier treated in step (1) for 0.5h, add potassium borohydride, cover andseal , stirred at 80°C for 3h, washed with deionized water until neutral, and dried in a vacuum dryer at 40°C for 10h to obtain a Co/Al2 O3 -N (1:15) catalyst, which was designated as
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
实施例12Example 12
(1)称取10g Al2O3粉状小颗粒，置于10％柠檬酸溶液，在150℃下进行酸化处理3h，之后用去离子水清洗，120℃干燥后备用。(1) Weigh 10g of Al2 O3 powdery particles, put them in 10% citric acid solution, carry out acidification treatment at 150°C for 3 hours, then wash them with deionized water, dry them at 120°C for later use.
(2)称取2.31g六水合硝酸钴，充分溶解于15mL去离子水中，并与步骤(1)中处理后的Al2O3载体充分搅拌、混合0.5h，添加硼氢化钠，加盖密封，40℃下搅拌24h，用去离子水清洗至中性，放置真空干燥器内于40℃干燥10h，得到Co/Al2O3-N(1:15)催化剂，记为Cat 12。(2) Weigh 2.31g of cobalt nitrate hexahydrate, fully dissolve in 15mL of deionized water, and fully stir and mix with theAl2O3 carrier treated in step (1) for 0.5h, add sodium borohydride, cover andseal , stirred at 40°C for 24h, washed with deionized water until neutral, and dried in a vacuum dryer at 40°C for 10h to obtain a Co/Al2 O3 -N (1:15) catalyst, which was designated as Cat 12.
其TEM图与实施例1基本一致。Its TEM figure is basically consistent with Example 1.
对比例1Comparative example 1
实施步骤和条件同实施例1，只是将10％柠檬酸溶液换成10％氢氧化钠溶液，获得Co/Al2O3-S(1:15)催化剂，记为Cat A。The implementation steps and conditions are the same as in Example 1, except that the 10% citric acid solution is replaced by 10% sodium hydroxide solution to obtain a Co/Al2 O3 -S (1:15) catalyst, which is designated as Cat A.
对比例2Comparative example 2
实施步骤和条件同实施例1，Al2O3不用进行10％柠檬酸溶液预先处理，获得Co/Al2O3-NE(1:15)催化剂，记为Cat B。The implementation steps and conditions are the same as in Example 1, except that Al2 O3 is not pre-treated with 10% citric acid solution to obtain a Co/Al2 O3 -NE (1:15) catalyst, which is designated as Cat B.
应用例1Application example 1
分别称取0.2g催化剂Cat1-Cat5、Cat 10-12、Cat A和Cat B，0.5g糠醛、10mL的异丙醇放入浆态床反应器中，利用氢气将反应器中空气置换，并维持在1.0MPa压力，反应温度控制为220℃，加热搅拌4h反应，冷却至室温收集滤液，利用气相色谱进行产物分析，糠醛液相加氢反应性能如表1所示。Weigh 0.2g of catalysts Cat1-Cat5, Cat 10-12, Cat A and Cat B, 0.5g of furfural, and 10mL of isopropanol into a slurry bed reactor, replace the air in the reactor with hydrogen, and maintain Under the pressure of 1.0MPa, the reaction temperature was controlled at 220°C, the reaction was heated and stirred for 4 hours, the filtrate was collected after cooling to room temperature, and the product was analyzed by gas chromatography. The performance of furfural liquid phase hydrogenation reaction is shown in Table 1.
实施例1制备的催化剂Cat1进行糠醛反应的产物气相色谱图如图1所示。Catalyst Cat1 prepared in
应用例2Application example 2
分别称取0.2g催化剂Cat 6-9，0.5g糠醛、10ml异丙醇放入浆态床反应器中，利用氢气将反应器中空气置换，并维持在0.6MPa压力，反应温度控制为240℃，加热搅拌4h反应，冷却至室温收集滤液，利用气相色谱进行产物分析，糠醛液相加氢反应性能如表1所示。Weigh 0.2g of catalyst Cat 6-9, 0.5g of furfural, and 10ml of isopropanol into a slurry bed reactor, replace the air in the reactor with hydrogen, and maintain the pressure at 0.6MPa, and control the reaction temperature at 240°C , heated and stirred for 4h to react, cooled to room temperature to collect the filtrate, and analyzed the product by gas chromatography. The performance of the furfural liquid phase hydrogenation reaction is shown in Table 1.
表1不同催化剂上的糠醛液相加氢性能Table 1 The performance of furfural liquid phase hydrogenation on different catalysts
通过上述表1可知，催化剂中Co原子或Ni原子与Al原子的比例在1:5-40之间时，糠醛的转化率均高达100％，且Co原子或Ni原子与Al原子在摩尔比为1:15-40之间，不仅糠醛的转化率均高达100％，而且2-甲基呋喃收率也均在80％以上。As can be seen from the above table 1, when the ratio of Co atoms or Ni atoms to Al atoms in the catalyst is between 1:5-40, the conversion rate of furfural is as high as 100%, and the molar ratio of Co atoms or Ni atoms to Al atoms is Between 1:15-40, not only the conversion rate of furfural is as high as 100%, but also the yield of 2-methylfuran is above 80%.
进一步，通过图1的实施例1制备的催化剂Cat1进行糠醛液相加氢反应的产物气相色谱图所示，没有糠醛峰，说明糠醛被全部转化，催化剂Cat1-Cat12进行糠醛液相加氢反应的产物气相色谱图基本一致，在此不进行赘述。Further, as shown in the product gas chromatogram of the furfural liquid-phase hydrogenation reaction carried out by the catalyst Cat1 prepared by the
同时，对比例1中载体Al2O3进行碱性处理得到的催化剂Cat A和对比例2中载体Al2O3未进行处理得到的催化剂Cat B在糠醛液相加氢反应中，糠醛的转化率分别为97％和88％，2-甲基呋喃收率分别为53％和27％，均小于本发明中对载体Al2O3进行酸性处理制得的催化剂的糠醛的转化率和2-甲基呋喃收率，可见，本发明中对载体Al2O3进行酸性处理，有效改善了Al2O3载体的表面酸性基团特质，有利于促进载体与Ni或Co的作用，使得制备的催化剂展示出优异的糠醛液相加氢性能。Simultaneously, in the furfural liquid-phase hydrogenation reaction of the catalyst Cat A obtained by the carrierAl2O3 in the comparative example 1 and the catalyst CatB obtained by the carrierAl2O3 without the treatment in thecomparative example 2, the conversion of furfural Yield is respectively 97% and 88%, and 2-methyl furanyield is respectively 53% and 27%, is all less than carrier Al in the present invention2 O Carry out the conversion ratio of the furfural of the catalyzer that acid treatment makes and 2- Methylfuranyield , it can be seen that inthe present invention, the carrierAl2O3 is acid-treated, which effectively improves the surface acidic group characteristics of theAl2O3 carrier, which is conducive to promoting the effect of the carrier and Ni or Co, making the prepared The catalyst exhibited excellent performance in the liquid phase hydrogenation of furfural.
不仅如此，由图2-3的Co催化剂和Ni催化剂的TEM图可知，本发明制备的催化剂的粒径小，Co催化剂的平均粒径为3.98nm，Ni催化剂的平均粒径为2.97nm，说明本发明的催化剂分散性好。Not only that, as can be seen from the TEM images of the Co catalyst and Ni catalyst of Fig. 2-3, the particle diameter of the catalyst prepared by the present invention is little, and the average particle diameter of Co catalyst is 3.98nm, and the average particle diameter of Ni catalyst is 2.97nm, illustrates The catalyst of the invention has good dispersibility.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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