技术领域Technical field
本发明属于生物质转化技术领域，尤其涉及一种NiCoAl/C催化剂及其在糠醛转化中的应用。The invention belongs to the technical field of biomass conversion, and in particular relates to a NiCoAl/C catalyst and its application in furfural conversion.
背景技术Background technique
化石燃料和石油化学品的枯竭给人类带来了能源危机和环境污染的挑战。由于这些原因，生物质及其衍生物在可再生生物燃料和增值化合物的生产中越来越受到关注，尤其是面向第二代生物燃料和平台分子的转化。糠醛通常是通过木糖脱水获得的，木糖是一种半纤维素衍生的戊糖，存在于农业废物中，如玉米秸秆、玉米芯和花生壳。糠醛作为原料可以通过催化转化为一系列高附加值的化学品，如糠醇(FOL)、四氢糠醇(THFOL)、戊二醇(PeD)、2-甲基呋喃(MeF)、2-甲基四氢呋喃(MTHF)、环戊酮(CPO)等。加氢产物高度依赖于催化剂和反应条件。The depletion of fossil fuels and petrochemicals has brought the challenges of energy crisis and environmental pollution to mankind. For these reasons, biomass and its derivatives are receiving increasing attention in the production of renewable biofuels and value-added compounds, especially for the conversion of second-generation biofuels and platform molecules. Furfural is typically obtained by dehydration of xylose, a hemicellulose-derived pentose sugar found in agricultural wastes such as corn stover, corn cobs, and peanut shells. Furfural as a raw material can be converted into a series of high value-added chemicals through catalysis, such as furfuryl alcohol (FOL), tetrahydrofurfuryl alcohol (THFOL), pentanediol (PeD), 2-methylfuran (MeF), 2-methyl Tetrahydrofuran (MTHF), cyclopentanone (CPO), etc. Hydrogenation products are highly dependent on the catalyst and reaction conditions.
环戊酮是制药、杀虫剂和橡胶化学品生产中的一种重要化学中间体。目前的工业实践中，环戊酮是通过己二酸及其衍生物的热解或环戊烯的氧化产生的，这些工艺以化石产品为原料，能耗高，对环境有害，成本效益低。Cyclopentanone is an important chemical intermediate in the production of pharmaceuticals, pesticides and rubber chemicals. In current industrial practice, cyclopentanone is produced through the pyrolysis of adipic acid and its derivatives or the oxidation of cyclopentene. These processes use fossil products as raw materials, are high in energy consumption, harmful to the environment, and have low cost-effectiveness.
四氢糠醇是全氢化产物，作为绿色溶剂广泛应用于医药、工农业等领域。在工业上，从糠醛生产四氢糠醇包括两个连续的步骤：一是将糠醛加氢生产糠醇，二是将糠醇进一步加氢生产四氢糠醇。从糠醛一步合成四氢糠醇是非常理想的。Tetrahydrofurfuryl alcohol is a fully hydrogenated product and is widely used in medicine, industry and agriculture as a green solvent. Industrially, the production of tetrahydrofurfuryl alcohol from furfural involves two consecutive steps: one is to hydrogenate furfural to produce furfuryl alcohol, and the other is to further hydrogenate furfuryl alcohol to produce tetrahydrofurfuryl alcohol. The one-step synthesis of tetrahydrofurfuryl alcohol from furfural is highly desirable.
相比之下，从糠醛生产环戊酮和四氢糠醇是一种可行与可持续的方法。若能将生物质资源转化为环戊酮与四氢糠醇等高价值化学品，一方面可以实现生物质资源的高值化利用，另一方面还能缓解能源日益紧缺的局面，同时还可以降低碳排放量，本发明提供一种高效NiCoAl/C催化剂，通过对催化剂的简单调控，可以得到高产率的环戊酮或四氢糠醇，符合当前可持续发展理念。In contrast, the production of cyclopentanone and tetrahydrofurfuryl alcohol from furfural is a feasible and sustainable method. If biomass resources can be converted into high-value chemicals such as cyclopentanone and tetrahydrofurfuryl alcohol, on the one hand, it can achieve high-value utilization of biomass resources, on the other hand, it can also alleviate the increasing shortage of energy, and at the same time, it can also reduce In terms of carbon emissions, the present invention provides a high-efficiency NiCoAl/C catalyst. Through simple control of the catalyst, high yields of cyclopentanone or tetrahydrofurfuryl alcohol can be obtained, which is in line with the current concept of sustainable development.
发明内容Contents of the invention
为解决上述技术问题，本发明提出了一种NiCoAl/C催化剂及其在糠醛转化中的应用，本发明以糠醛为原料，以NiCoAl/C为催化剂，通过对催化剂的简单调控，高选择性催化糠醛制备环戊酮或四氢糠醇。In order to solve the above technical problems, the present invention proposes a NiCoAl/C catalyst and its application in the conversion of furfural. The present invention uses furfural as the raw material and NiCoAl/C as the catalyst. Through simple control of the catalyst, it can catalyze with high selectivity Furfural is used to prepare cyclopentanone or tetrahydrofurfuryl alcohol.
为实现上述目的，本发明提供了以下技术方案：In order to achieve the above objects, the present invention provides the following technical solutions:
本发明的技术方案之一：One of the technical solutions of the present invention:
本发明提供了一种NiCoAl/C催化剂，所述NiCoAl/C催化剂中Ni、Co和Al的摩尔比为(0-1)∶(0-1)∶(0-4)；所述NiCoAl/C催化剂中Ni、Co和Al不同时为0。The invention provides a NiCoAl/C catalyst. The molar ratio of Ni, Co and Al in the NiCoAl/C catalyst is (0-1):(0-1):(0-4); the NiCoAl/C Ni, Co and Al in the catalyst are not 0 at the same time.
进一步地，所述NiCoAl/C催化剂中Ni、Co和Al的摩尔比为(0.5-1)∶(0.5-1)∶(0.5-2)。Further, the molar ratio of Ni, Co and Al in the NiCoAl/C catalyst is (0.5-1): (0.5-1): (0.5-2).
进一步地，所述NiCoAl/C催化剂中Ni、Co和Al的摩尔比为1∶1∶1。Further, the molar ratio of Ni, Co and Al in the NiCoAl/C catalyst is 1:1:1.
本发明的技术方案之二：The second technical solution of the present invention:
本发明提供一种所述的NiCoAl/C催化剂的制备方法，包括以下步骤：The invention provides a preparation method of the NiCoAl/C catalyst, which includes the following steps:
将氢氧化钠(NaOH)溶于水中，加入愈创木酚，搅拌均匀，得到混合溶液；Dissolve sodium hydroxide (NaOH) in water, add guaiacol, stir evenly to obtain a mixed solution;
将镍盐、钴盐和铝盐加入所述混合溶液中，搅拌均匀，将沉淀物过滤，洗涤或者不洗涤，干燥，焙烧，氢气气氛下还原，得到NiCoAl/C催化剂。Add nickel salt, cobalt salt and aluminum salt to the mixed solution, stir evenly, filter the precipitate, wash or not wash, dry, roast, and reduce under hydrogen atmosphere to obtain NiCoAl/C catalyst.
进一步地，所述镍盐、钴盐和铝盐分别为Ni(NO3)2、Co(NO3)2和Al(CH3COO)3。Further, the nickel salt, cobalt salt and aluminum salt are Ni(NO3 )2 , Co(NO3 )2 and Al(CH3 COO)3 respectively.
进一步地，氢氧化钠和愈创木酚的摩尔比为1∶1。Further, the molar ratio of sodium hydroxide and guaiacol is 1:1.
进一步地，氢氧化钠和镍盐的摩尔比为(1.5-2.5)∶1，优选为2∶1。Further, the molar ratio of sodium hydroxide and nickel salt is (1.5-2.5):1, preferably 2:1.
进一步地，所述焙烧的温度为500-700℃；Further, the roasting temperature is 500-700°C;
所述还原的温度为400-500℃。The temperature of the reduction is 400-500°C.
更进一步地，所述NiCoAl/C催化剂的制备方法，包括以下步骤：Furthermore, the preparation method of the NiCoAl/C catalyst includes the following steps:
步骤一、将NaOH溶解到超纯水中，向其中加入愈创木酚，将混合物搅拌均匀，最后变为深棕色的混合溶液；Step 1: Dissolve NaOH into ultrapure water, add guaiacol to it, stir the mixture evenly, and finally turn into a dark brown mixed solution;
步骤二、分别将Ni(NO3)2、Co(NO3)2和Al(CH3COO)3加入到上述混合溶液中，然后进行搅拌；Step 2: Add Ni(NO3 )2 , Co(NO3 )2 and Al(CH3 COO)3 to the above mixed solution respectively, and then stir;
步骤三、将上述溶液中的沉淀物过滤，多次用超纯水洗涤，然后在烘箱中干燥以彻底去除水分；Step 3: Filter the precipitate in the above solution, wash it with ultrapure water several times, and then dry it in an oven to completely remove the water;
步骤四、将干燥后的沉淀物固体用研钵磨碎后过筛后在管式炉中N2气氛下500℃-700℃焙烧，而后在H2气氛下400℃-500℃还原，最后得到的催化剂记为NiCoAl/C(W)催化剂；Step 4: Grind the dried precipitate solid with a mortar and sieve, roast it in a tube furnace at 500°C-700°C under N2 atmosphere, and then reduce it under H2 atmosphere at 400°C-500°C to finally obtain The catalyst is recorded as NiCoAl/C(W) catalyst;
或者在步骤三中，沉淀物过滤后未经洗涤，而其它步骤相同，则最后得到的催化剂记为NiCoAl/C(UW)催化剂。Or in step three, if the precipitate is filtered without washing and other steps are the same, then the final catalyst obtained is recorded as NiCoAl/C (UW) catalyst.
进一步地，步骤一中，NaOH与愈创木酚的摩尔比为1∶1，搅拌时间为30min，搅拌速度为600r/min；步骤二中，NaOH与Ni(NO3)2的摩尔比为2∶1；步骤三中，烘箱中的干燥时间为24h，干燥温度为80℃；步骤四中的筛子目数为80-100目；管式炉升温速率为10℃/min，N2焙烧温度优选为600℃，焙烧时间为1h，氢气还原温度优选为450℃，还原时间为4h。Further, in step one, the molar ratio of NaOH to guaiacol is 1:1, the stirring time is 30min, and the stirring speed is 600r/min; in step two, the molar ratio of NaOH to Ni(NO3 )2 is 2 ∶1; In step three, the drying time in the oven is 24h, and the drying temperature is 80°C; the sieve mesh size in step four is 80-100 mesh; the tube furnace heating rate is 10°C/min, and the N2 roasting temperature is preferred. The temperature is 600°C, the roasting time is 1 hour, the hydrogen reduction temperature is preferably 450°C, and the reduction time is 4 hours.
本发明通过调节催化剂制备过程中的pH(即通过洗涤至中性或者不洗涤的方式)，对催化剂进行了简单改性，改变了催化剂的相组成。NiCoAl/C(UW)催化剂中存在铝酸钴，而NiCoAl/C(W)催化剂中未检测出该物质。NiCoAl/C(UW)催化剂含有大量还原态金属，有利于生成四氢糠醇，而NiCoAl/C(W)催化剂含有丰富的酸性位点，有利于转化为环戊酮。糠醛在两种催化剂上的吸附构型也不同，糠醛在NiCoAl/C(UW)催化剂上为平行吸附构型，有利于双键进行加氢作用；而糠醛在NiCoAl/C(W)催化剂上为垂直吸附构型，从而有利于开环作用。The present invention simply modifies the catalyst and changes the phase composition of the catalyst by adjusting the pH during the preparation process of the catalyst (that is, by washing to neutral or without washing). Cobalt aluminate exists in the NiCoAl/C(UW) catalyst, but this substance is not detected in the NiCoAl/C(W) catalyst. The NiCoAl/C(UW) catalyst contains a large amount of reduced metals, which is beneficial to the production of tetrahydrofurfuryl alcohol, while the NiCoAl/C(W) catalyst contains abundant acidic sites, which is beneficial to the conversion into cyclopentanone. The adsorption configurations of furfural on the two catalysts are also different. Furfural has a parallel adsorption configuration on the NiCoAl/C(UW) catalyst, which is conducive to hydrogenation of double bonds; while furfural on the NiCoAl/C(W) catalyst has a parallel adsorption configuration. Vertical adsorption configuration, thus facilitating ring opening.
本发明的技术方案之三：The third technical solution of the present invention:
本发明提供所述NiCoAl/C催化剂在糠醛转化中的应用。The present invention provides the application of the NiCoAl/C catalyst in furfural conversion.
进一步地，所述NiCoAl/C催化剂用于催化糠醛制备环戊酮或四氢糠醇。Further, the NiCoAl/C catalyst is used to catalyze the preparation of cyclopentanone or tetrahydrofurfuryl alcohol from furfural.
进一步地，本发明以糠醛为原料，以水为溶剂，在NiCoAl/C催化剂的作用下催化转化高选择性制备环戊酮或四氢糠醇，反应温度为120-180℃，优选为150-170℃，反应时间为2-16h，优选为4-12h，反应体系中的氢气压力为1-6MPa，优选为2-5MPa。Further, the present invention uses furfural as raw material, water as solvent, and catalytically converts cyclopentanone or tetrahydrofurfuryl alcohol with high selectivity under the action of NiCoAl/C catalyst. The reaction temperature is 120-180°C, preferably 150-170°C. ℃, the reaction time is 2-16h, preferably 4-12h, and the hydrogen pressure in the reaction system is 1-6MPa, preferably 2-5MPa.
糠醛的质量是水的0.1-2wt％，优选0.64wt％，NiCoAl/C催化剂的质量是糠醛的10-50wt％，优选30-35wt％，最优选为31.2wt％。The mass of furfural is 0.1-2wt% of water, preferably 0.64wt%, and the mass of NiCoAl/C catalyst is 10-50wt% of furfural, preferably 30-35wt%, and most preferably 31.2wt%.
与现有技术相比，本发明具有如下优点和技术效果：Compared with the existing technology, the present invention has the following advantages and technical effects:
1、本发明提供了一种NiCoAl/C催化剂及其在糠醛转化中的应用，本发明NiCoAl/C催化剂中通过三种金属的协同作用，实现了糠醛高转化率、高选择性地催化转化生成环戊酮或四氢糠醇的目的。1. The present invention provides a NiCoAl/C catalyst and its application in the conversion of furfural. Through the synergistic effect of three metals, the NiCoAl/C catalyst of the present invention achieves high conversion rate and highly selective catalytic conversion of furfural to generate furfural. Purpose of cyclopentanone or tetrahydrofurfuryl alcohol.
2、本发明通过对催化剂的简单调控，通过催化剂的是否洗涤，从而调节pH，以改变催化剂的性质，来调节环戊酮或四氢糠醇两种产物的产率。2. The present invention adjusts the productivity of the two products of cyclopentanone or tetrahydrofurfuryl alcohol by simply controlling the catalyst and adjusting the pH by whether the catalyst is washed or not, so as to change the properties of the catalyst.
3、本发明的催化剂采用非贵金属原材料，原材料获取简单低廉，工艺简单，具有良好的应用前景。3. The catalyst of the present invention uses non-noble metal raw materials. The raw materials are simple and low-cost to obtain, the process is simple, and it has good application prospects.
附图说明Description of the drawings
构成本申请的一部分的附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings that form a part of this application are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an improper limitation of this application. In the attached picture:
图1是实施例6中由糠醛催化转化为环戊酮和四氢糠醇的GC-MS谱图；Figure 1 is a GC-MS spectrum of catalytic conversion of furfural into cyclopentanone and tetrahydrofurfuryl alcohol in Example 6;
图2是实施例1-17催化剂的XRD图；Figure 2 is the XRD pattern of the catalyst of Example 1-17;
图3是实施例1、4、5、8-17催化剂的NH3-TPD图；Figure 3 is the NH3 -TPD diagram of the catalysts of Examples 1, 4, 5, and 8-17;
图4是实施例4催化剂的吡啶红外图；Figure 4 is the pyridine infrared pattern of the catalyst in Example 4;
图5是实施例8-17催化剂的吡啶红外图。Figure 5 is the pyridine infrared pattern of the catalyst of Example 8-17.
具体实施方式Detailed ways
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the invention will now be described in detail. This detailed description should not be construed as limitations of the invention, but rather as a more detailed description of certain aspects, features and embodiments of the invention.
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terms used in the present invention are only used to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges in the present invention, it should be understood that every intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or value intermediate within a stated range and any other stated value or value intermediate within a stated range is also included within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded from the range.
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials in connection with which the documents relate. In the event of conflict with any incorporated document, the contents of this specification shall prevail.
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to the skilled person from the description of the invention. The specification and examples of the present invention are exemplary only.
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。The words "includes", "includes", "has", "contains", etc. used in this article are all open terms, which mean including but not limited to.
本发明实施例所用各原料均为通过市售购买得到。All raw materials used in the examples of the present invention were purchased from the market.
以下通过实施例对本发明的技术方案做进一步说明。The technical solutions of the present invention will be further described below through examples.
实施例1Example 1
催化剂制备：Catalyst preparation:
(1)将0.02mol NaOH溶解到50mL超纯水中，向其中加入0.02mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.02 mol NaOH into 50 mL ultrapure water, and add 0.02 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 and Co(NO3 )2 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution and then dry it in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCo/C(UW)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained is designated as NiCo/C(UW) catalyst.
反应评价：将上述方法制备的NiCo/C(UW)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入2MPa的氢气，在160℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，四氢糠醇产率为58.58％。反应评价条件及结果见表1。Reaction evaluation: Add the NiCo/C (UW) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; among them, the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 2MPa hydrogen, react at 160°C for 8 hours, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the tetrahydrofurfuryl alcohol yield was 58.58%. The reaction evaluation conditions and results are shown in Table 1.
实施例2Example 2
催化剂制备：Catalyst preparation:
(1)将0.025mol NaOH溶解到50mL超纯水中，向其中加入0.025mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.025 mol NaOH into 50 mL ultrapure water, and add 0.025 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 and Al(CH3 COO)3 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution and then dry it in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiAl/C(UW)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained was designated as NiAl/C(UW) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表1。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 1.
实施例3Example 3
催化剂制备：Catalyst preparation:
(1)将0.025mol NaOH溶解到50mL超纯水中，向其中加入0.025mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.025 mol NaOH into 50 mL ultrapure water, and add 0.025 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Co(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Co(NO3 )2 and Al(CH3 COO)3 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution and then dry it in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为CoAl/C(UW)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained was designated as CoAl/C(UW) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表1。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 1.
实施例4Example 4
催化剂制备：Catalyst preparation:
(1)将0.035mol NaOH溶解到50mL超纯水中，向其中加入0.035mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.035 mol NaOH into 50 mL ultrapure water, and add 0.035 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 , Co(NO3 )2 , and Al(CH3 COO)3 (all 0.005 mol, 10 mL aqueous solution) into the above dark brown mixed solution, and then stir at 400 r/min 30 minutes.
(3)将上述溶液中的沉淀物过滤，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution and then dry it in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCoAl/C(UW)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained is designated as NiCoAl/C(UW) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表1。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 1.
实施例5Example 5
催化剂制备：Catalyst preparation:
(1)将0.02mol NaOH溶解到50mL超纯水中，向其中加入0.02mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.02 mol NaOH into 50 mL ultrapure water, and add 0.02 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 and Co(NO3 )2 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCo/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained is designated as NiCo/C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
实施例6Example 6
催化剂制备：Catalyst preparation:
(1)将0.025mol NaOH溶解到50mL超纯水中，向其中加入0.025mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.025 mol NaOH into 50 mL ultrapure water, and add 0.025 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 and Al(CH3 COO)3 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiAl/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour under an N2 atmosphere, and then reduce it at 450°C for 4 hours under anH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. The finally obtained catalyst is designated as NiAl/C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
实施例7Example 7
催化剂制备：Catalyst preparation:
(1)将0.025mol NaOH溶解到50mL超纯水中，向其中加入0.025mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.025 mol NaOH into 50 mL ultrapure water, and add 0.025 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Co(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Co(NO3 )2 and Al(CH3 COO)3 (both 0.005 mol, 10 mL aqueous solution) to the above dark brown mixed solution, and then stir at 400 r/min for 30 min.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为CoAl/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained was designated as CoAl/C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
实施例8Example 8
催化剂制备：Catalyst preparation:
(1)将0.035mol NaOH溶解到50mL超纯水中，向其中加入0.035mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.035 mol NaOH into 50 mL ultrapure water, and add 0.035 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2、Al(CH3COO)3(均为0.005mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 , Co(NO3 )2 , and Al(CH3 COO)3 (all 0.005 mol, 10 mL aqueous solution) into the above dark brown mixed solution, and then stir at 400 r/min 30 minutes.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCoAl/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The final catalyst obtained is designated as NiCoAl/C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
实施例9Example 9
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入2MPa的氢气，在160℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为95.45％，环戊酮产率为87.48％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 2MPa hydrogen, react at 160°C for 8 hours, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components, and the furfural conversion rate was 95.45%, and the cyclopentanone yield was 87.48%. The reaction evaluation conditions and results are shown in Table 2.
实施例10Example 10
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入4MPa的氢气，在160℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，环戊酮产率为95.37％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 4MPa hydrogen, react at 160°C for 8h, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the cyclopentanone yield was 95.37%. The reaction evaluation conditions and results are shown in Table 2.
实施例11Example 11
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入5MPa的氢气，在160℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，环戊酮产率为92.21％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 5MPa hydrogen, react at 160°C for 8 hours, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the cyclopentanone yield was 92.21%. The reaction evaluation conditions and results are shown in Table 2.
实施例12Example 12
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在150℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为93.87％，环戊酮产率为88.87％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 150°C for 8 hours, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 93.87%, and the cyclopentanone yield was 88.87%. The reaction evaluation conditions and results are shown in Table 2.
实施例13Example 13
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在170℃下反应8h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，环戊酮产率为89.36％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 170°C for 8 hours, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the cyclopentanone yield was 89.36%. The reaction evaluation conditions and results are shown in Table 2.
实施例14Example 14
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在160℃下反应4h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为92.76％，环戊酮产率为84.10％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 160°C for 4h, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components, and the furfural conversion rate was 92.76%, and the cyclopentanone yield was 84.10%. The reaction evaluation conditions and results are shown in Table 2.
实施例15Example 15
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在160℃下反应6h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为98.33％，环戊酮产率为90.34％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 160°C for 6h, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components, and the furfural conversion rate was 98.33%, and the cyclopentanone yield was 90.34%. The reaction evaluation conditions and results are shown in Table 2.
实施例16Example 16
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在160℃下反应10h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，环戊酮产率为96.08％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 160°C for 10h, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the cyclopentanone yield was 96.08%. The reaction evaluation conditions and results are shown in Table 2.
实施例17Example 17
催化剂制备：与实施例8相同。Catalyst preparation: same as Example 8.
反应评价：将上述方法制备的NiCoAl/C(W)催化剂加入高压反应釜中，加入糠醛和水，混合均匀，密封反应釜；其中，糠醛的质量为水质量的0.64wt％；催化剂质量为糠醛质量的31.2wt％；然后用氢气置换高压釜内的空气5次，之后充入3MPa的氢气，在160℃下反应12h，升温速率为5℃/min，反应完冷却至室温，用气相色谱和GC-MS分析液相组分和气相组分，糠醛转化率为100％，环戊酮产率为91.77％。反应评价条件及结果见表2。Reaction evaluation: Add the NiCoAl/C(W) catalyst prepared by the above method into a high-pressure reactor, add furfural and water, mix evenly, and seal the reactor; where the mass of furfural is 0.64wt% of the mass of water; the mass of the catalyst is furfural. 31.2wt% of the mass; then replace the air in the autoclave with hydrogen 5 times, then fill it with 3MPa hydrogen, react at 160°C for 12h, with a heating rate of 5°C/min, cool to room temperature after the reaction, and use gas chromatography and GC-MS analyzed the liquid phase components and gas phase components. The furfural conversion rate was 100% and the cyclopentanone yield was 91.77%. The reaction evaluation conditions and results are shown in Table 2.
实施例18Example 18
催化剂制备：Catalyst preparation:
(1)将0.05mol NaOH溶解到50mL超纯水中，向其中加入0.05mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.05 mol NaOH into 50 mL ultrapure water, and add 0.05 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2(均为0.005mol，10mL水溶液)、Al(CH3COO)3(0.01mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 , Co(NO3 )2 (both 0.005 mol, 10 mL aqueous solution), and Al(CH3 COO)3 (0.01 mol, 10 mL aqueous solution) into the above dark brown mixed solution. , then stir at 400r/min for 30min.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCoAl2/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The finally obtained catalyst is designated as NiCoAl2 /C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
实施例19Example 19
催化剂制备：Catalyst preparation:
(1)将0.08mol NaOH溶解到50mL超纯水中，向其中加入0.08mol的愈创木酚。将混合物以400r/min搅拌30min，最后变为深棕色混合溶液。(1) Dissolve 0.08 mol NaOH into 50 mL ultrapure water, and add 0.08 mol guaiacol to it. The mixture was stirred at 400 r/min for 30 min, and finally turned into a dark brown mixed solution.
(2)分别将Ni(NO3)2、Co(NO3)2(均为0.005mol，10mL水溶液)、Al(CH3COO)3(0.02mol，10mL水溶液)加入到上述深棕色混合溶液中，然后以400r/min搅拌30min。(2) Add Ni(NO3 )2 , Co(NO3 )2 (both 0.005 mol, 10 mL aqueous solution), and Al(CH3 COO)3 (0.02 mol, 10 mL aqueous solution) into the above dark brown mixed solution. , then stir at 400r/min for 30min.
(3)将上述溶液中的沉淀物过滤，用水洗涤直至pH为7左右，然后在80℃烘箱中干燥24h以彻底去除水分。(3) Filter the precipitate in the above solution, wash with water until the pH is about 7, and then dry in an oven at 80°C for 24 hours to completely remove moisture.
(4)将干燥后的固体用研钵磨碎后在管式炉中N2气氛下600℃焙烧1h，而后在H2气氛下450℃还原4h，管式炉的升温速率为10℃/min。最后得到的催化剂记为NiCoAl4/C(W)催化剂。(4) Grind the dried solid with a mortar and roast it in a tube furnace at 600°C for 1 hour underN2 atmosphere, and then reduce it at 450°C for 4 hours underH2 atmosphere. The temperature rise rate of the tube furnace is 10°C/min. . The finally obtained catalyst is designated as NiCoAl4 /C(W) catalyst.
反应评价：反应评价的操作程序与实施例1一致，但其反应条件及结果见表2。Reaction evaluation: The operating procedures for reaction evaluation are consistent with Example 1, but the reaction conditions and results are shown in Table 2.
表1Table 1
表2Table 2
实施例6中由糠醛催化转化为环戊酮和四氢糠醇的GC-MS谱图见图1；The GC-MS spectrum of the catalytic conversion of furfural into cyclopentanone and tetrahydrofurfuryl alcohol in Example 6 is shown in Figure 1;
实施例1-17催化剂的XRD图见图2；The XRD pattern of the catalyst of Examples 1-17 is shown in Figure 2;
实施例1、4、5、8-17催化剂的NH3-TPD图见图3；The NH3 -TPD diagrams of the catalysts of Examples 1, 4, 5, and 8-17 are shown in Figure 3;
实施例4催化剂的吡啶红外图见图4；The pyridine infrared pattern of the catalyst of Example 4 is shown in Figure 4;
实施例8-17催化剂的吡啶红外图见图5。The pyridine infrared pattern of the catalyst of Examples 8-17 is shown in Figure 5.
实施例4与实施例8对比可知，NiCoAl/C催化剂洗涤处理前后分别高转化率高选择性地催化糠醛生成四氢糠醇和环戊酮，具体而言NiCoAl/C催化剂洗涤处理前后，改变了催化剂的相组成，从而改变糠醛在催化剂上的吸附构型，使糠醛分别高转化率、高选择性地转化为四氢糠醇和环戊酮。Comparing Example 4 with Example 8, it can be seen that the NiCoAl/C catalyst can catalyze furfural to produce tetrahydrofurfuryl alcohol and cyclopentanone with high conversion rates and high selectivity before and after the NiCoAl/C catalyst washing treatment. Specifically, the catalyst has changed before and after the NiCoAl/C catalyst washing treatment. The phase composition of the catalyst changes the adsorption configuration of furfural on the catalyst, allowing furfural to be converted into tetrahydrofurfuryl alcohol and cyclopentanone with high conversion rate and high selectivity respectively.
实施例4与实施例8对比可知，NiCoAl/C催化剂通过制备过程中调节pH，从而简易调控催化剂的性质，从而改变主要产物的产率。Comparing Example 4 with Example 8, it can be seen that the NiCoAl/C catalyst can easily control the properties of the catalyst by adjusting the pH during the preparation process, thereby changing the yield of the main product.
实施例1、2、3、4对比可知，Ni、Co、Al协同作用促进糠醛高选择性转化成环戊酮。Comparing Examples 1, 2, 3, and 4, it can be seen that Ni, Co, and Al synergistically promote the highly selective conversion of furfural into cyclopentanone.
实施例5、6、7、8对比可知，Co与Al协同作用，而Ni起辅助加氢作用促进糠醛高选择性转化成环戊酮。Comparison of Examples 5, 6, 7 and 8 shows that Co and Al act synergistically, while Ni acts as an auxiliary hydrogenation to promote the highly selective conversion of furfural into cyclopentanone.
实施例8与实施例18、19对比可知，增加催化剂中Al的占比，催化剂加氢作用降低，底物更多转化为中间产物糠醇，从而使环戊酮产率降低，证明实施例8中催化剂摩尔比为最优选。Comparing Example 8 with Examples 18 and 19, it can be seen that when the proportion of Al in the catalyst is increased, the hydrogenation effect of the catalyst is reduced, and more of the substrate is converted into the intermediate product furfuryl alcohol, thereby reducing the cyclopentanone yield, proving that in Example 8 Catalyst molar ratio is most preferred.
以上，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应该以权利要求的保护范围为准。The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any person familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application. All are covered by the protection scope of this application. Therefore, the protection scope of this application should be subject to the protection scope of the claims.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311528048.5ACN117563600B (en) | 2023-11-16 | 2023-11-16 | NiCoAl/C catalyst and application thereof in furfural conversion |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311528048.5ACN117563600B (en) | 2023-11-16 | 2023-11-16 | NiCoAl/C catalyst and application thereof in furfural conversion |
| Publication Number | Publication Date |
|---|---|
| CN117563600Atrue CN117563600A (en) | 2024-02-20 |
| CN117563600B CN117563600B (en) | 2025-01-17 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311528048.5AActiveCN117563600B (en) | 2023-11-16 | 2023-11-16 | NiCoAl/C catalyst and application thereof in furfural conversion |
| Country | Link |
|---|---|
| CN (1) | CN117563600B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073109A (en)* | 2001-06-20 | 2003-03-12 | Osaka Gas Co Ltd | Carbonous complex material involving cobalt compound and its producing method |
| CN104888863A (en)* | 2015-04-22 | 2015-09-09 | 华东理工大学 | Preparation method of alkaline carbonaceous carrier for preparing furan dicarboxylic acid |
| CN106268823A (en)* | 2015-06-11 | 2017-01-04 | 佛山市德品高新材料有限公司 | A kind of catalyst containing Cu (I) and the method with its catalysis furfural hydrogenation |
| CN107999081A (en)* | 2017-12-13 | 2018-05-08 | 太原理工大学 | A kind of carbon coating structure nano iron-base fischer-tropsch synthesis catalyst and its preparation method and application |
| US20200306733A1 (en)* | 2019-03-29 | 2020-10-01 | Research & Business Foundation Sungkyunkwan University | Heterogeneous catalyst, method of producing the heterogeneous catalyst, and method of producing lignin-derived high-substituted aromatic monomer from woody biomass material |
| CN113786837A (en)* | 2021-09-16 | 2021-12-14 | 厦门大学 | A kind of method for preparing cyclopentanone and cyclopentanol by hydrogenation rearrangement of furfural |
| CN115920897A (en)* | 2022-12-27 | 2023-04-07 | 安徽师范大学 | Metal catalyst and its preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073109A (en)* | 2001-06-20 | 2003-03-12 | Osaka Gas Co Ltd | Carbonous complex material involving cobalt compound and its producing method |
| CN104888863A (en)* | 2015-04-22 | 2015-09-09 | 华东理工大学 | Preparation method of alkaline carbonaceous carrier for preparing furan dicarboxylic acid |
| CN106268823A (en)* | 2015-06-11 | 2017-01-04 | 佛山市德品高新材料有限公司 | A kind of catalyst containing Cu (I) and the method with its catalysis furfural hydrogenation |
| CN107999081A (en)* | 2017-12-13 | 2018-05-08 | 太原理工大学 | A kind of carbon coating structure nano iron-base fischer-tropsch synthesis catalyst and its preparation method and application |
| US20200306733A1 (en)* | 2019-03-29 | 2020-10-01 | Research & Business Foundation Sungkyunkwan University | Heterogeneous catalyst, method of producing the heterogeneous catalyst, and method of producing lignin-derived high-substituted aromatic monomer from woody biomass material |
| CN113786837A (en)* | 2021-09-16 | 2021-12-14 | 厦门大学 | A kind of method for preparing cyclopentanone and cyclopentanol by hydrogenation rearrangement of furfural |
| CN115920897A (en)* | 2022-12-27 | 2023-04-07 | 安徽师范大学 | Metal catalyst and its preparation method and application |
| Title |
|---|
| QI GUO，ET AL.: "Efficient conversion of furfural to cyclopentanol over lignin activated carbon supported Ni–Co catalyst", RSC ADVANCES, vol. 12, 19 April 2022 (2022-04-19), pages 11843 - 11852* |
| ZHEN LI，ET AL.: "High-sensitive sensor for the simultaneous determination of phenolics based on multi-walled carbon nanotube/NiCoAl hydrotalcite electrode material", MICROCHIMICA ACTA, vol. 188, 27 August 2021 (2021-08-27), XP037564320, DOI: 10.1007/s00604-021-04948-1* |
| Publication number | Publication date |
|---|---|
| CN117563600B (en) | 2025-01-17 |
| Publication | Publication Date | Title |
|---|---|---|
| CN107365286B (en) | Method for synthesizing 2, 5-furandicarboxylic acid | |
| CN110041168B (en) | A kind of method for preparing cyclopentanone and cyclopentanol by hydrogenation of furfural | |
| CN111233626B (en) | A kind of method that benzophenone hydrogenation prepares diphenylmethanol | |
| CN104998659B (en) | It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method | |
| CN104557801B (en) | Method for preparing γ-valerolactone from furfural on a metal/solid acid catalyst | |
| CN110508287A (en) | Ni-Cu/Al2O3 bimetallic catalyst, its preparation method and its application in the preparation of tert-butylaminoethoxyethanol | |
| CN101444740A (en) | Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof | |
| CN108558608A (en) | A kind of method of the nickel-base material Catalytic lignin selectivity hydrogenolysis of basic zirconium phosphate load | |
| CN108325548B (en) | Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof | |
| CN113061122B (en) | Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran | |
| CN114602554A (en) | CoMn-MOF supported catalyst and preparation method thereof | |
| CN101632932A (en) | Dimethyl carbonate supported catalyst directly synthesized by methanol and carbon dioxide | |
| CN114870837B (en) | Alkali metal modified supported metal catalyst and preparation method and application thereof | |
| CN110694656A (en) | Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion | |
| CN106238051A (en) | Catalyst for ethyl acetate preparation of ethanol by hydrogenating and its preparation method and application | |
| CN117019147A (en) | Synthesis method of high-dispersity supported catalyst and method for preparing furfuryl alcohol by catalyzing furfural by using high-dispersity supported catalyst | |
| CN106582666B (en) | Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran | |
| CN104174397B (en) | A kind of catalyst for acetic acid gas phase catalysis assimilation acetone and method for making and application | |
| CN112403472B (en) | Method for preparing carbon-based transition metal hydrogenation catalyst based on pyrolysis bio-oil | |
| CN102166519B (en) | Method for preparing loaded amorphous nickel-based catalyst | |
| CN106540743A (en) | A kind of catalyst that biological Aviation Fuel is prepared for jatropha oil and preparation method thereof | |
| CN112295571B (en) | PtNi cage catalyst and application thereof in furfuryl alcohol preparation by catalyzing selective hydrogenation of furfural | |
| CN119972089A (en) | A ternary metal oxide catalyst for synthesizing 2,5-furandicarboxylic acid and a preparation method thereof | |
| CN117563600A (en) | A NiCoAl/C catalyst and its application in furfural conversion | |
| CN106905109A (en) | A kind of method that catalytic hydrogenolysis cellulose produces propane diols |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |