CN114315504A - Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide - Google Patents
Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide Download PDFInfo
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Abstract
本发明涉及使用AxByOz型复合金属氧化物进行加氢脱氧反应,将2,5‑己二酮或3‑甲基‑2‑环戊烯‑1‑酮一步转化为甲基环戊二烯的方法。使用简单易操作的沉积沉淀法,水热法或者柠檬酸络合法可以合成多种AxByOz型复合金属氧化物,它们对于2,5‑己二酮以及3‑甲基‑2‑环戊烯‑1‑酮的加氢脱氧反应具有特殊的选择性,可以在固定床反应器中以较大的质量空速,通过羟醛缩合串联加氢脱氧反应或者直接的加氢脱氧反应,一步合成目标产物甲基环戊二烯。本发明工艺路线简单,对环境友好,催化剂制备简单,为甲基环戊二烯的合成提供了一种全新的催化方法。
The invention relates to a method for converting 2,5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into methylcyclopentadiene in one step by using AxByOz type composite metal oxide for hydrodeoxygenation reaction . A variety of AxByOz-type composite metal oxides can be synthesized using simple and easy-to-operate deposition precipitation methods, hydrothermal methods or citric acid complexation methods, which are suitable for 2,5-hexanedione and 3-methyl-2-cyclopentene- The hydrodeoxygenation reaction of 1-ketone has special selectivity, and the target product can be synthesized in one step through aldol condensation series hydrodeoxygenation reaction or direct hydrodeoxygenation reaction at a large mass space velocity in a fixed bed reactor. Methylcyclopentadiene. The invention has the advantages of simple process route, environmental friendliness and simple catalyst preparation, and provides a brand-new catalytic method for the synthesis of methylcyclopentadiene.
Description
技术领域technical field
本发明涉及2,5-己二酮和3-甲基-2-环戊烯-1-酮合成甲基环戊二烯的方法。The present invention relates to a method for synthesizing methylcyclopentadiene from 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one.
背景技术Background technique
甲基环戊二烯不仅可以合成高能火箭燃料,还是一种用途广泛的高端精细化工原料,可用于合成汽油抗爆剂甲基环戊二烯三羰基锰(MMT)、环氧树脂固化剂、染料添加剂、特种黏结剂、特殊香料等高附加值产品。目前工业上MCPD的生产主要有两种方法:一种是以石油高温裂解焦油为原料,首先蒸馏分离出其中的C6组分,然后经过多次聚合、减压蒸馏、解聚、精馏来制得MCPD;另外一种是将环戊二烯甲基化制备MCPD。然而,不论是通过分离还是甲基化合成的方法生产MCPD,产能都十分有限,远远不能满足各领域应用需求。因此,寻找使用大宗化学品作为原料生产甲基环戊二烯的绿色可再生合成工艺路线,具有重要的意义。Methylcyclopentadiene can not only synthesize high-energy rocket fuel, but also a high-end fine chemical raw material with a wide range of uses. It can be used to synthesize gasoline antiknock agent methylcyclopentadiene manganese tricarbonyl (MMT), epoxy resin curing agent, Dye additives, special binders, special spices and other high value-added products. At present, there are two main methods for the production of MCPD in industry: one is to use petroleum pyrolysis tar as raw material, first to separate the C 6 components by distillation, and then to obtain the Preparation of MCPD; another is the preparation of MCPD by methylation of cyclopentadiene. However, whether MCPD is produced by separation or methylation synthesis, the production capacity is very limited, which is far from meeting the application needs of various fields. Therefore, it is of great significance to find a green and renewable synthetic process route for the production of methylcyclopentadiene using bulk chemicals as raw materials.
近年来,随着人们对环境和能源问题的日益关注,以二氧化碳中性、可再生的生物质资源为原料合成高附加值化学品已得到世界各国的广泛关注。例如,将纤维素经过催化氢解反应可得到2,5-己二酮(Appl.Catal.A,2015,504,664-671)。使用2,5-己二酮作为原料,在碱性催化剂Mg-Al-O的作用下,使用水-甲苯混合溶剂,进行羟醛缩合反应可以得到3-甲基-2-环戊烯-1-酮(MCP),MCP在催化剂Pt/NbOPO4的作用下,可以进行加氢脱氧,得到产物为甲基环戊烷,碳数较低,失去了进一步聚合的能力(Green Chem.,2015,17,2393-2397)。使用MCP作为原料,可以一步加氢脱氧得到甲基环戊二烯,甲基环戊二烯选择性最高仅达到80%,目标产物收率较低,且存在仅能使用单一物质,即价格相对较高的MCP作为原料的问题。In recent years, with people's increasing attention to environmental and energy issues, the synthesis of high value-added chemicals from carbon dioxide-neutral and renewable biomass resources has received extensive attention from countries around the world. For example, 2,5-hexanedione can be obtained by subjecting cellulose to catalytic hydrogenolysis (Appl. Catal. A, 2015, 504, 664-671). Using 2,5-hexanedione as raw material, under the action of basic catalyst Mg-Al-O, and using water-toluene mixed solvent, aldol condensation reaction can be carried out to obtain 3-methyl-2-cyclopentene-1 - Ketone (MCP), MCP can undergo hydrodeoxygenation under the action of catalyst Pt/NbOPO 4 to obtain methylcyclopentane, which has a lower carbon number and loses the ability to further polymerize (Green Chem., 2015, 17, 2393-2397). Using MCP as a raw material, methylcyclopentadiene can be obtained by one-step hydrodeoxygenation. The highest selectivity of methylcyclopentadiene is only 80%, the yield of the target product is low, and only a single substance can be used, that is, the price is relatively high. Higher MCP as a raw material problem.
发明内容SUMMARY OF THE INVENTION
针对上述技术问题,本发明采用多种合成方法,提供新型的AxByOz型复合金属氧化物催化剂,高效地将2,5-己二酮或者3-甲基-2-环戊烯-1-酮一步转化为目标产物甲基环戊二烯,为高附加值甲基环戊二烯的合成提供一种新型、简易、高效的合成方法。In view of the above technical problems, the present invention adopts a variety of synthesis methods to provide a novel AxByOz type composite metal oxide catalyst, which can efficiently convert 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one in one step It is converted into the target product methylcyclopentadiene, and provides a novel, simple and efficient synthesis method for the synthesis of high value-added methylcyclopentadiene.
本发明是通过以下技术方案实现的:The present invention is achieved through the following technical solutions:
本发明的技术方案包括方法1或方法2,所述方法1、方法2路径如下:The technical solution of the present invention includes method 1 or method 2, and the paths of the method 1 and method 2 are as follows:
方法1 method 1
方法2 Method 2
所述AxByOz型复合金属氧化物催化剂中包括:CuMoO4、Cu3Mo2O9、ZnMoO4、Zn3Mo2O9、NiMoO4、CoMoO4、MnMoO4、FeMoO4、Fe2(MoO4)3、Cr2(MoO4)3、CuWO4、NiWO4、CoWO4、FeWO4、ZnWO4、Zn3(VO4)2中的一种或多种。The AxByOz type composite metal oxide catalyst includes: CuMoO 4 , Cu 3 Mo 2 O 9 , ZnMoO 4 , Zn 3 Mo 2 O 9 , NiMoO 4 , CoMoO 4 , MnMoO 4 , FeMoO 4 , Fe 2 (MoO 4 ) 3. One or more of Cr 2 (MoO 4 ) 3 , CuWO 4 , NiWO 4 , CoWO 4 , FeWO 4 , ZnWO 4 , and Zn 3 (VO 4 ) 2 .
上述的原料2,5-己二酮、3-甲基-2-环戊烯-1-酮及目标产物甲基环戊二烯的化学结构式见表1。The chemical structural formulas of above-mentioned raw material 2,5-hexanedione, 3-methyl-2-cyclopenten-1-one and target product methylcyclopentadiene are shown in Table 1.
基于上述方案,优选地,以2,5-己二酮或3-甲基-2-环戊烯-1-酮为原料,于固定床连续式反应器中,在沉积沉淀法,水热法或者柠檬酸络合法合成的AxByOz型复合金属氧化物催化剂的作用下,通过羟醛缩合串联加氢脱氧反应或直接的加氢脱氧反应,在反应温度300-600℃,氢气压力0.0001-1MPa(优选0.0001-0.9MPa,更优选0.0001-0.8MPa),氢气与底物的摩尔比为20-300∶1,底物的质量空速为0.01-10h-1(优选0.05-9h-1,更优选0.1-8h-1)下,一步获得甲基环戊二烯目标产物。Based on the above scheme, preferably, using 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one as a raw material, in a fixed-bed continuous reactor, in a sedimentation precipitation method, a hydrothermal method Or under the action of AxByOz type composite metal oxide catalyst synthesized by citric acid complex method, through aldol condensation series hydrodeoxygenation reaction or direct hydrodeoxygenation reaction, at reaction temperature 300-600 ℃, hydrogen pressure 0.0001-1MPa ( Preferably 0.0001-0.9MPa, more preferably 0.0001-0.8MPa), the molar ratio of hydrogen to the substrate is 20-300:1, the mass space velocity of the substrate is 0.01-10h -1 (preferably 0.05-9h -1 , more preferably 0.1-8h -1 ), the target product of methylcyclopentadiene is obtained in one step.
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂采用水热法、沉积沉淀法或柠檬酸络合法制备,且使用前在氢气中进行还原处理,其中,还原条件为氢气压力0.001-2.0MPa(优选0.005-1.5MPa,更优选0.01-1MPa)、氢气流速2-300mL/min(优选5-250mL/min,更优选10-200mL/min)、还原温度200-600℃(优选250-550℃,更优选300-500℃)、还原时间0.5-12h(优选0.7-10h,更优选1-8h)。Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst is prepared by a hydrothermal method, a deposition precipitation method or a citric acid complex method, and is subjected to reduction treatment in hydrogen before use, wherein the reduction condition is a hydrogen pressure of 0.001 -2.0MPa (preferably 0.005-1.5MPa, more preferably 0.01-1MPa), hydrogen flow rate 2-300mL/min (preferably 5-250mL/min, more preferably 10-200mL/min), reduction temperature 200-600°C (preferably 250 -550°C, more preferably 300-500°C), reduction time 0.5-12h (preferably 0.7-10h, more preferably 1-8h).
基于上述方案,优选地,所述水热法具体制备过程为:将一定量A的金属盐与B的金属盐混合溶解在去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的不锈钢反应釜中,在80-220℃下反应5-48h后过滤洗涤,得到的粉末于80℃烘干3h后于300-800℃下焙烧1-6h,即可得到AxByOz型复合金属氧化物催化剂。Based on the above scheme, preferably, the specific preparation process of the hydrothermal method is as follows: a certain amount of the metal salt of A and the metal salt of B are mixed and dissolved in deionized water, and the suspension is obtained by ultrasound at room temperature; In a stainless steel reaction kettle lined with tetrafluoroethylene, react at 80-220 °C for 5-48 hours, filter and wash the obtained powder, dry at 80 °C for 3 hours and then roast at 300-800 °C for 1-6 hours to obtain AxByOz type composite metal oxide catalyst.
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂也可以使用沉积沉淀法进行合成,具体过程为:将一定量的B的金属盐溶于去离子水中,使用浓度为0.5mol/L-14mol/L(优选1mol/L-8mol/L,更优选1.5mol/L-6mol/L)氨水溶液作为沉淀剂调节该溶液的PH值调节为8-12后,滴加A的金属酸盐水溶液,搅拌0.5-4h(优选1-3h)后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在100-200℃烘箱内烘干4-48h,再在300-800℃(优选350-750℃,更优选400-700℃)焙烧0.5-10h(优选1-8h,更优选1-6h)即得AxByOz型复合金属氧化物催化剂。Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst can also be synthesized by the deposition precipitation method, and the specific process is as follows: a certain amount of B metal salt is dissolved in deionized water, and the concentration is 0.5mol/L -14mol/L (preferably 1mol/L-8mol/L, more preferably 1.5mol/L-6mol/L) ammonia solution as a precipitant to adjust the pH value of the solution to be adjusted to 8-12, dropwise add the metal salt of A Aqueous solution, after stirring for 0.5-4h (preferably 1-3h), the obtained precipitate was filtered out, washed with deionized water and ethanol, dried in an oven at 100-200°C for 4-48h, and then dried at 300-800°C (preferably 350-750°C, more preferably 400-700°C) calcination for 0.5-10h (preferably 1-8h, more preferably 1-6h) to obtain AxByOz type composite metal oxide catalyst.
基于上述方案,优选地,所述AxByOz型复合金属氧化物催化剂还可以使用柠檬酸络合法制备,具体过程为:按摩尔比M∶柠檬酸=1∶1-1∶3(优选1∶1.05-1∶2,更优选1∶1.1-1∶1.5)称取B的金属酸盐、A的金属酸盐、柠檬酸,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在300-800℃(优选350-750℃,更优选400-700℃)焙烧0.5-10h(优选1-8h,更优选1-6h)后,即得AxByOz型复合金属氧化物催化剂。Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst can also be prepared by a citric acid complex method, and the specific process is: molar ratio M:citric acid=1:1-1:3 (preferably 1:1.05 -1:2, more preferably 1:1.1-1:1.5) Weigh the metal salt of B, the metal salt of A, citric acid, M is the molar sum of the metal B in the anion and the cationic metal A; After the ionized water is dissolved separately, the three solutions are mixed evenly, heated in an evaporating dish until only solids are formed; after drying at 120°C for 12 hours, the temperature is 300-800°C (preferably 350-750°C, more preferably 400-700°C) After calcination for 0.5-10h (preferably 1-8h, more preferably 1-6h), the AxByOz type composite metal oxide catalyst is obtained.
本发明所述的方法,可以大量合成AxByOz型复合金属氧化物催化剂,制备方法简单、反应条件温和。同时该类催化剂经过还原能够在无溶剂条件下,于固定床反应器上将2,5-己二酮或3-甲基-2-环戊烯-1-酮经过羟醛缩合串联加氢脱氧反应或者直接加氢脱氧反应,一步转化为甲基环戊二烯,操作步骤少,底物的质量空速大,转化效率高,是一条绿色简易的新合成路线,可用于实际的工业化生产,催化性能良好。The method of the invention can synthesize the AxByOz type composite metal oxide catalyst in large quantities, and the preparation method is simple and the reaction conditions are mild. At the same time, after reduction of this type of catalyst, 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one can be hydrodeoxygenated in series through aldol condensation in a fixed bed reactor without solvent. Reaction or direct hydrodeoxygenation reaction, one-step conversion to methylcyclopentadiene, few operation steps, high mass space velocity of substrate, high conversion efficiency, is a green and simple new synthetic route, which can be used for actual industrial production, Good catalytic performance.
本发明的有益效果是:The beneficial effects of the present invention are:
本发明不仅可以使用MCP作为底物,还可以使用合成MCP的源头原料2,5-己二酮为底物,一步制取甲基环戊二烯,且得到的目标产物选择性更高。The present invention can not only use MCP as a substrate, but also can use 2,5-hexanedione, the source material for synthesizing MCP, as a substrate to prepare methylcyclopentadiene in one step, and the obtained target product has higher selectivity.
本发明使用简单易操作的沉积沉淀法,水热法或者柠檬酸络合法可以合成多种AxByOz型复合金属氧化物,首次将其应用加氢脱氧反应,可以于无溶剂条件下,在固定床反应器中以较大的质量空速,通过羟醛缩合串联加氢脱氧反应或者直接的加氢脱氧反应将2,5-己二酮或3-甲基-2-环戊烯-1-酮一步转化为目标产物甲基环戊二烯。The present invention can synthesize a variety of AxByOz type composite metal oxides by using simple and easy-to-operate deposition precipitation method, hydrothermal method or citric acid complex method. In the reactor, 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one is converted to 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one through aldol condensation series hydrodeoxygenation reaction or direct hydrodeoxygenation reaction at a large mass space velocity in the reactor. One-step conversion into the target product methylcyclopentadiene.
本发明工艺路线简单,对环境友好,催化剂制备简单,为甲基环戊二烯的合成提供了一种全新的催化方法。The invention has the advantages of simple process route, environmental friendliness and simple catalyst preparation, and provides a brand-new catalytic method for the synthesis of methylcyclopentadiene.
本发明采用固定床连续流动反应器,在多种AxByOz型复合金属氧化物催化剂的作用下,能够将2,5-己二酮或3-甲基-2-环戊烯-1-酮一步转化为甲基环戊二烯,具有工艺路线简单、转化效率高、可操作性大、能耗低、催化剂制备简单、环境污染小的优势。The invention adopts a fixed-bed continuous flow reactor, and under the action of various AxByOz type composite metal oxide catalysts, 2,5-hexanedione or 3-methyl-2-cyclopenten-1-one can be converted in one step It is methylcyclopentadiene and has the advantages of simple process route, high conversion efficiency, large operability, low energy consumption, simple catalyst preparation and low environmental pollution.
附图说明Description of drawings
图1为实施例6中2,5-己二酮合成甲基环戊二烯的产物的气相色谱图。FIG. 1 is a gas chromatogram of the product of synthesizing methylcyclopentadiene from 2,5-hexanedione in Example 6. FIG.
图2为实施例41中3-甲基-2-环戊烯-1-酮合成甲基环戊二烯的产物的气相色谱图。FIG. 2 is a gas chromatogram of the product of synthesizing methylcyclopentadiene from 3-methyl-2-cyclopenten-1-one in Example 41. FIG.
图3为目标产物甲基环戊二烯的质谱对照图。Fig. 3 is the mass spectrometry comparison chart of the target product methylcyclopentadiene.
图4-6为部分合成催化剂的XRD图谱。Figures 4-6 are XRD patterns of partially synthesized catalysts.
图7为本发明提供的反应路径。Figure 7 is the reaction pathway provided by the present invention.
具体实施方式Detailed ways
以下结合具体实施例进一步详细描述本发明的技术方案,但本发明的保护范围不局限于这些实施例。The technical solutions of the present invention are further described in detail below with reference to specific embodiments, but the protection scope of the present invention is not limited to these embodiments.
实施例1Example 1
(1)AxByOz型复合金属氧化物催化剂CoMoO4的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为2mol/L的氨水溶液作为沉淀剂将该溶液的PH值调节为9.5,滴加硝酸钴(4.07g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在100℃烘箱内烘干5h,再在400℃下焙烧2h,即得CoMoO4复合金属氧化物催化剂。(1) Preparation of AxByOz type composite metal oxide catalyst CoMoO 4 : Weigh 2.47 g of ammonium molybdate and dissolve it in 200 mL of deionized water. The pH value of the solution was adjusted to 9.5 by using an aqueous ammonia solution with a concentration of 2 mol/L as a precipitant, and an aqueous solution of cobalt nitrate (4.07 g dissolved in 100 mL of deionized water) was added dropwise. After stirring for 2 h, the obtained precipitate was filtered out. After washing with deionized water and ethanol, drying in an oven at 100 °C for 5 hours, and then calcining at 400 °C for 2 hours, the CoMoO 4 composite metal oxide catalyst was obtained.
(2)将上述CoMoO4催化剂0.3g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.2MPa、氢气流量90mL/min、还原温度400℃下还原2h,然后控制反应温度420℃,反应压力0.05MPa,2,5-己二酮的时空速为2h-1,氢气与2,5-己二酮的摩尔比为70∶1,其2,5-己二酮的转化率为90%,甲基环戊二烯的选择性为80%。(2) 0.3 g of the above-mentioned CoMoO catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.2 MPa, a hydrogen flow of 90 mL/min, and a reduction temperature of 400 ° C. Reduction for 2h, then control the reaction temperature to 420°C, the reaction pressure to 0.05MPa, the hourly space velocity of 2,5-hexanedione to be 2h -1 , and the molar ratio of hydrogen to 2,5-hexanedione to be 70:1. The conversion of 5-hexanedione was 90% and the selectivity to methylcyclopentadiene was 80%.
实施例2Example 2
(1)AxByOz型复合金属氧化物催化剂NiMoO4可使用柠檬酸络合法制备,具体过程为:按摩尔比n(M)/n(柠檬酸)=1/1.2称取钼酸铵1.24g、硝酸镍2.04g、柠檬酸3.53g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得NiMoO4催化剂。(1) AxByOz type composite metal oxide catalyst NiMoO 4 can be prepared by citric acid complex method, and the specific process is as follows: Weigh 1.24 g of ammonium molybdate, 1.24 g of ammonium molybdate, Nickel nitrate 2.04g, citric acid 3.53g, M is the molar sum of metal B and cationic metal A in the anion; after dissolving with deionized water respectively, the three solutions are evenly mixed, and heated in an evaporating dish until only A solid is formed; after drying at 120°C for 12h and then calcining at 600°C for 5h, NiMoO 4 catalyst is obtained.
(2)将上述NiMoO4催化剂0.3g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.08MPa、氢气流量90mL/min、还原温度400℃下还原2h,然后控制反应温度380℃,反应压力0.05MPa,2,5-己二酮的时空速为2.3h-1,氢气与2,5-己二酮的摩尔比为70∶1,其2,5-己二酮的转化率为90%,甲基环戊二烯的选择性为84%。(2) 0.3 g of the above-mentioned NiMoO catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.08 MPa, a hydrogen flow of 90 mL/min, and a reduction temperature of 400° C. Reduction was carried out for 2h, then the reaction temperature was controlled at 380°C, the reaction pressure was 0.05MPa, the hourly space velocity of 2,5-hexanedione was 2.3h -1 , the molar ratio of hydrogen to 2,5-hexanedione was 70:1, and the 2,5-hexanedione molar ratio was 70:1. , the conversion of 5-hexanedione was 90%, and the selectivity of methylcyclopentadiene was 84%.
实施例3Example 3
(1)AxByOz型复合金属氧化物催化剂ZnMoO4的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为2mol/L的氨水溶液作为沉淀剂调节该溶液的PH值调节为8.9后,滴加硝酸锌(4.16g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在100℃烘箱内烘干5h,再在400℃下焙烧2h,即得ZnMoO4复合金属氧化物催化剂。(1) Preparation of AxByOz-type composite metal oxide catalyst ZnMoO 4 : Weigh 2.47 g of ammonium molybdate and dissolve it in 200 mL of deionized water. The pH value of the solution was adjusted to 8.9 by using an ammonia solution with a concentration of 2 mol/L as a precipitant, and then an aqueous solution of zinc nitrate (4.16 g dissolved in 100 mL of deionized water) was added dropwise, and after stirring for 2 h, the obtained precipitate was filtered out. After being washed with deionized water and ethanol, dried in an oven at 100 °C for 5 h, and then calcined at 400 °C for 2 h, the ZnMoO 4 composite metal oxide catalyst was obtained.
(2)将上述ZnMoO4催化剂0.2g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.05MPa、氢气流量150mL/min、还原温度400℃下还原1h,然后控制反应温度400℃,反应压力0.05MPa,2,5-己二酮的时空速为3h-1,氢气与2,5-己二酮的摩尔比为70∶1,其2,5-己二酮的转化率为100%,甲基环戊二烯的选择性为89%。(2) 0.2 g of the above-mentioned ZnMoO catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.05 MPa, a hydrogen flow of 150 mL/min, and a reduction temperature of 400 ° C. Reduction was carried out for 1 h, and then the reaction temperature was controlled at 400 °C, the reaction pressure was 0.05 MPa, the hourly space velocity of 2,5-hexanedione was 3 h -1 , and the molar ratio of hydrogen to 2,5-hexanedione was 70:1. The conversion of 5-hexanedione was 100% and the selectivity to methylcyclopentadiene was 89%.
实施例4Example 4
(1)AxByOz型复合金属氧化物催化剂Cu3Mo2O9可使用水热法制备,具体过程为:将0.50g醋酸酮与0.44g四水合钼酸铵溶解在40mL去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的不锈钢反应釜中,在120℃下反应12h后过滤洗涤,得到的粉末于80℃烘干3h后于600℃下焙烧3h,即可得到Cu3Mo2O9催化剂。(1) AxByOz type composite metal oxide catalyst Cu 3 Mo 2 O 9 can be prepared by hydrothermal method. The specific process is as follows: 0.50g of acetone acetate and 0.44g of ammonium molybdate tetrahydrate are dissolved in 40mL of deionized water, and ultrasonicated at room temperature. A suspension was obtained; the mixed solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted at 120 °C for 12 hours, filtered and washed, and the obtained powder was dried at 80 °C for 3 hours and then calcined at 600 °C for 3 hours, namely A Cu 3 Mo 2 O 9 catalyst can be obtained.
(2)将上述Cu3Mo2O9催化剂0.2g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.05MPa、氢气流量150mL/min、还原温度400℃下还原1h,然后控制反应温度400℃,反应压力0.05MPa,2,5-己二酮的时空速为2.3h-1,氢气与2,5-己二酮的摩尔比为67∶1,其2,5-己二酮的转化率为100%,甲基环戊二烯的选择性为90%。(2) 0.2 g of the above-mentioned Cu 3 Mo 2 O 9 catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then reduced at a hydrogen pressure of 0.05 MPa, a hydrogen flow of 150 mL/min, and reduced The reduction was carried out at a temperature of 400°C for 1 h, and then the reaction temperature was controlled to 400°C, the reaction pressure was 0.05MPa, the hourly space velocity of 2,5-hexanedione was 2.3h -1 , and the molar ratio of hydrogen to 2,5-hexanedione was 67: 1. The conversion of 2,5-hexanedione is 100%, and the selectivity of methylcyclopentadiene is 90%.
实施例5Example 5
(1)AxByOz型复合金属氧化物催化剂Fe2(MoO4)3可使用柠檬酸络合法制备,具体过程为:按摩尔比n(M)/n(柠檬酸)=1/1.2称取钼酸铵1.24g、九水合硝酸铁1.89g、柠檬酸2.94g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得Fe2(MoO4)3催化剂。(1) AxByOz type composite metal oxide catalyst Fe 2 (MoO 4 ) 3 can be prepared by citric acid complexing method, and the specific process is as follows: molar ratio n(M)/n(citric acid)=1/1.2 to weigh molybdenum Ammonium acid 1.24g, ferric nitrate nonahydrate 1.89g, citric acid 2.94g, M is the molar sum of metal B and cationic metal A in the anion; after dissolving them in deionized water, the three solutions are evenly mixed, Heat in an evaporating dish until only solids are formed; after drying at 120°C for 12h, and calcining at 600°C for 5h, Fe 2 (MoO 4 ) 3 catalyst is obtained.
(2)将上述Fe2(MoO4)3催化剂0.3g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.08MPa、氢气流量120mL/min、还原温度400℃下还原2h,然后控制反应温度420℃,反应压力0.05MPa,2,5-己二酮的时空速为2h-1,氢气与2,5-己二酮的摩尔比为90∶1,其2,5-己二酮的转化率为93%,甲基环戊二烯的选择性为86%。(2) 0.3 g of the above-mentioned Fe 2 (MoO 4 ) 3 catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.08 MPa, a hydrogen flow of 120 mL/min, The reduction temperature was 400°C for 2h, and then the reaction temperature was controlled to 420°C, the reaction pressure was 0.05MPa, the hourly space velocity of 2,5-hexanedione was 2h -1 , and the molar ratio of hydrogen to 2,5-hexanedione was 90: 1, the conversion of 2,5-hexanedione is 93%, and the selectivity of methylcyclopentadiene is 86%.
实施例6Example 6
(1)AxByOz型复合金属氧化物催化剂NiWO4可使用水热法制备,具体过程为:将0.71g醋酸镍与1.32g二水合钨酸钠溶解在80mL去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的不锈钢反应釜中,在120℃下反应12h后过滤洗涤,得到的粉末于80℃烘干3h后于600℃下焙烧3h,即可得到NiWO4催化剂。(1) The AxByOz type composite metal oxide catalyst NiWO 4 can be prepared by a hydrothermal method. The specific process is as follows: 0.71 g of nickel acetate and 1.32 g of sodium tungstate dihydrate are dissolved in 80 mL of deionized water, and the suspension is obtained by ultrasound at room temperature; The mixed solution was transferred to a stainless steel reaction kettle with a Teflon lining, reacted at 120 °C for 12 h, filtered and washed, and the obtained powder was dried at 80 °C for 3 h and then calcined at 600 °C for 3 h to obtain NiWO 4 catalyst.
(2)将上述NiWO4催化剂0.25g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.50MPa、氢气流量160mL/min、还原温度450℃下还原2.5h,然后控制反应温度400℃,反应压力0.05MPa,2,5-己二酮的时空速为1.8h-1,氢气与2,5-己二酮的摩尔比为80∶1,其2,5-己二酮的转化率为96%,甲基环戊二烯的选择性为88%。(2) 0.25g of the above-mentioned NiWO 4 catalyst was uniformly mixed with 4mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.50MPa, a hydrogen flow rate of 160mL/min, and a reduction temperature of 450°C Reduction was carried out for 2.5h, then the reaction temperature was controlled at 400°C, the reaction pressure was 0.05MPa, the hourly space velocity of 2,5-hexanedione was 1.8h -1 , and the molar ratio of hydrogen to 2,5-hexanedione was 80:1. The conversion of 2,5-hexanedione was 96% and the selectivity to methylcyclopentadiene was 88%.
实施例7Example 7
(1)AxByOz型复合金属氧化物催化剂Cr2(MoO4)3可使用柠檬酸络合法制备,具体过程为:按摩尔比n(M)/n(柠檬酸)=1/1.2称取钼酸铵1.24g、九水合硝酸铬1.87g、柠檬酸2.94g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得Cr2(MoO4)3催化剂。(1) AxByOz type composite metal oxide catalyst Cr 2 (MoO 4 ) 3 can be prepared by citric acid complexing method. The specific process is: molar ratio n(M)/n(citric acid)=1/1.2 to weigh molybdenum Ammonium acid 1.24g, chromium nitrate nonahydrate 1.87g, citric acid 2.94g, M is the molar sum of metal B and cationic metal A in the anion; after dissolving them in deionized water, the three solutions are evenly mixed, Heating in an evaporating dish until only solids are formed; after drying at 120°C for 12h and then calcining at 600°C for 5h, Cr 2 (MoO 4 ) 3 catalyst is obtained.
(2)将上述Cr2(MoO4)3催化剂0.1g与实施例3中合成的ZnMoO4催化剂0.2g机械混合后,与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.03MPa、氢气流量150mL/min、还原温度400℃下还原2h,然后控制反应温度400℃,反应压力0.03MPa,2,5-己二酮的时空速为2.5h-1,氢气与2,5-己二酮的摩尔比为70∶1,其2,5-己二酮的转化率为100%,甲基环戊二烯的选择性为92%。(2) After mechanically mixing 0.1 g of the above-mentioned Cr 2 (MoO 4 ) 3 catalyst and 0.2 g of the ZnMoO 4 catalyst synthesized in Example 3, uniformly mixed with 4 mL of 40-70 mesh quartz sand, and filled in a fixed bed for continuous reaction In the reactor, the hydrogen pressure was 0.03MPa, the hydrogen flow rate was 150mL/min, and the reduction temperature was 400℃ for 2h, and then the reaction temperature was controlled to 400℃, the reaction pressure was 0.03MPa, and the hourly space velocity of 2,5-hexanedione was 2.5h - 1. The molar ratio of hydrogen to 2,5-hexanedione is 70:1, the conversion rate of 2,5-hexanedione is 100%, and the selectivity of methylcyclopentadiene is 92%.
上述的实施例1-7的实验结果见表2。The experimental results of the above-mentioned embodiments 1-7 are shown in Table 2.
表2由2,5-己二酮加氢脱氧合成甲基环戊二烯Table 2 Synthesis of methylcyclopentadiene by hydrodeoxygenation of 2,5-hexanedione
以实施例7中的Cr2(MoO4)3+ZnMoO4作为催化剂,0.2g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,以2,5-己二酮为底物,然后在氢气压力0.05MPa,还原温度400℃下还原1h,在一定的氢气与2,5-己二酮的摩尔比、反应温度、反应压力、时空速为下进行反应。Using Cr 2 (MoO 4 ) 3 +ZnMoO 4 in Example 7 as a catalyst, 0.2 g was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and 2,5-hexanedi Ketone was used as the substrate, and then reduced at a hydrogen pressure of 0.05 MPa and a reduction temperature of 400 °C for 1 h. The reaction was carried out under a certain molar ratio of hydrogen to 2,5-hexanedione, reaction temperature, reaction pressure and hourly space velocity.
表3 Cr2(MoO4)3+ZnMoO4催化由2,5-己二酮加氢脱氧合成甲基环戊二烯Table 3 Cr 2 (MoO 4 ) 3 +ZnMoO 4 catalyzed the synthesis of methylcyclopentadiene by hydrodeoxygenation of 2,5-hexanedione
实施例24Example 24
(1)AxByOz型复合金属氧化物催化剂Zn3Mo2O9的制备:称取2.47g钼酸铵,溶于200mL去离子水中。使用浓度为4mol/L的氨水溶液作为沉淀剂调节该溶液的PH值调节为9.2后,滴加硝酸锌(4.16g溶于100mL去离子水中)水溶液,搅拌2h后,将得到的沉淀过滤出来,经去离子水和乙醇洗涤后,于在100℃烘箱内烘干5h,再在400℃下焙烧2h,即得Zn3Mo2O9复合金属氧化物催化剂。(1) Preparation of AxByOz type composite metal oxide catalyst Zn 3 Mo 2 O 9 : Weigh 2.47 g of ammonium molybdate and dissolve it in 200 mL of deionized water. The pH value of the solution was adjusted to 9.2 by using an ammonia solution with a concentration of 4 mol/L as a precipitant, and an aqueous solution of zinc nitrate (4.16 g dissolved in 100 mL of deionized water) was added dropwise. After stirring for 2 h, the obtained precipitate was filtered out. After washing with deionized water and ethanol, drying in an oven at 100°C for 5h, and then calcining at 400°C for 2h, the Zn 3 Mo 2 O 9 composite metal oxide catalyst was obtained.
(2)将上述Zn3Mo2O9催化剂0.2g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.05MPa、氢气流量150mL/min、还原温度400℃下还原1小时,然后控制反应温度400℃,反应压力0.05MPa,3-甲基-2-环戊烯-1-酮的时空速为3h-1,氢气与3-甲基-2-环戊烯-1-酮的摩尔比为70∶1,其3-甲基-2-环戊烯-1-酮的转化率为100%,甲基环戊二烯的选择性为91%。(2) 0.2 g of the above-mentioned Zn 3 Mo 2 O 9 catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then reduced under a hydrogen pressure of 0.05 MPa, a hydrogen flow of 150 mL/min, and a The reduction was performed at a temperature of 400°C for 1 hour, and then the reaction temperature was controlled to 400°C, the reaction pressure was 0.05MPa, the hourly space velocity of 3-methyl-2-cyclopenten-1-one was 3h -1 , and the hydrogen and 3-methyl-2 -The molar ratio of cyclopenten-1-one is 70:1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 91% .
实施例25Example 25
(1)AxByOz型复合金属氧化物催化剂CuMoO4可使用柠檬酸络合法制备,具体过程为:按摩尔比n(M)/n(柠檬酸)=1/1.2称取钼酸铵1.24g、硝酸铜1.69g、柠檬酸3.53g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得CuMoO4催化剂。(1) AxByOz type composite metal oxide catalyst CuMoO 4 can be prepared by citric acid complexing method. The specific process is as follows: Weigh 1.24 g of ammonium molybdate, 1.24 g of ammonium molybdate, Copper nitrate 1.69g, citric acid 3.53g, M is the molar sum of metal B and cationic metal A in the anion; after dissolving them in deionized water, mix the solutions of the three evenly, and heat them in an evaporating dish until only A solid is formed; after drying at 120°C for 12h and then calcining at 600°C for 5h, the CuMoO 4 catalyst is obtained.
(2)将上述CuMoO4催化剂0.15g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.5MPa、氢气流量150mL/min、还原温度400℃下还原2h,然后控制反应温度400℃,反应压力0.05MPa,3-甲基-2-环戊烯-1-酮的时空速为2.5h-1,氢气与3-甲基-2-环戊烯-1-酮的摩尔比为70∶1,其3-甲基-2-环戊烯-1-酮的转化率为100%,甲基环戊二烯的选择性为82%。(2) 0.15 g of the above-mentioned CuMoO catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.5 MPa, a hydrogen flow of 150 mL/min, and a reduction temperature of 400° C. Reduction for 2h, then control the reaction temperature to 400°C, the reaction pressure to 0.05MPa, the hourly space velocity of 3-methyl-2-cyclopenten-1-one to be 2.5h -1 , the hydrogen and 3-methyl-2-cyclopentene The molar ratio of -1-one was 70:1, the conversion of 3-methyl-2-cyclopenten-1-one was 100%, and the selectivity of methylcyclopentadiene was 82%.
实施例26Example 26
(1)AxByOz型复合金属氧化物催化剂Zn3(VO4)2可使用水热法制备,具体过程为:将1.10g醋酸锌与0.47g偏钒酸铵溶解在60mL去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的不锈钢反应釜中,在120℃下反应12h后过滤洗涤,得到的粉末于80℃烘干3h后于600℃下焙烧3h,即可得到Zn3(VO4)2催化剂。(1) AxByOz type composite metal oxide catalyst Zn 3 (VO 4 ) 2 can be prepared by hydrothermal method. The specific process is as follows: dissolve 1.10g of zinc acetate and 0.47g of ammonium metavanadate in 60mL of deionized water, and sonicate at room temperature A suspension was obtained; the mixed solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted at 120 °C for 12 hours, filtered and washed, and the obtained powder was dried at 80 °C for 3 hours and then calcined at 600 °C for 3 hours, namely Zn 3 (VO 4 ) 2 catalyst can be obtained.
(2)将上述Zn3(VO4)2催化剂0.25g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.50MPa、氢气流量160mL/min、还原温度450℃下还原2.5h,然后控制反应温度400℃,反应压力0.05MPa,3-甲基-2-环戊烯-1-酮的时空速为2.5h-1,氢气与3-甲基-2-环戊烯-1-酮的摩尔比为70∶1,其3-甲基-2-环戊烯-1-酮的转化率为100%,甲基环戊二烯的选择性为86%。(2) 0.25 g of the above-mentioned Zn 3 (VO 4 ) 2 catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.50 MPa, a hydrogen flow of 160 mL/min, The reduction temperature was 450°C for 2.5h, and then the reaction temperature was controlled to 400°C, the reaction pressure was 0.05MPa, the hourly space velocity of 3-methyl-2-cyclopenten-1-one was 2.5h -1 , and the hydrogen and 3-methyl The molar ratio of -2-cyclopenten-1-one is 70:1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 86%.
实施例27Example 27
(1)AxByOz型复合金属氧化物催化剂MnMoO4可使用柠檬酸络合法制备,具体过程为:按摩尔比n(M)/n(柠檬酸)=1/1.2称取钼酸铵1.24g、50wt%的硝酸锰水溶液2.51g、柠檬酸3.53g,M为处于阴离子中的金属B和阳离子金属A的摩尔总和;用去离子水分别溶解后,将三者的溶液均匀混合,在蒸发皿中加热至仅有固体生成;经120℃干燥12h后在600℃下焙烧5h后,即得MnMoO4催化剂。(1) AxByOz type composite metal oxide catalyst MnMoO 4 can be prepared by citric acid complex method. The specific process is as follows: Weigh 1.24 g of ammonium molybdate, 1.24 g of ammonium molybdate, 2.51 g of 50 wt% manganese nitrate aqueous solution, 3.53 g of citric acid, M is the molar sum of metal B and cationic metal A in the anion; after dissolving them in deionized water, the three solutions are evenly mixed, and placed in an evaporating dish. Heating until only solid is formed; after drying at 120°C for 12h, and calcining at 600°C for 5h, MnMoO 4 catalyst is obtained.
(2)将上述MnMoO4催化剂0.5g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.5MPa、氢气流量150mL/min、还原温度400℃下还原2h,然后控制反应温度400℃,反应压力0.05MPa,3-甲基-2-环戊烯-1-酮的时空速为1.1h-1,氢气与3-甲基-2-环戊烯-1-酮的摩尔比为70∶1,其3-甲基-2-环戊烯-1-酮的转化率为100%,甲基环戊二烯的选择性为89%。(2) 0.5 g of the above-mentioned MnMoO catalyst was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and then at a hydrogen pressure of 0.5 MPa, a hydrogen flow of 150 mL/min, and a reduction temperature of 400° C. Reduction for 2h, then control the reaction temperature to 400℃, the reaction pressure to 0.05MPa, the hourly space velocity of 3-methyl-2-cyclopenten-1-one to be 1.1h -1 , the hydrogen and 3-methyl-2-cyclopentene The molar ratio of -1-one was 70:1, the conversion of 3-methyl-2-cyclopenten-1-one was 100%, and the selectivity of methylcyclopentadiene was 89%.
实施例28Example 28
(1)AxByOz型复合金属氧化物催化剂ZnWO4可使用水热法制备,具体过程为:将0.55g醋酸锌与0.99g二水合钨酸钠溶解在60mL去离子水中,室温下超声得到悬浮液;将混合溶液转移至带聚四氟乙烯内衬的不锈钢反应釜中,在120℃下反应12h后过滤洗涤,得到的粉末于80℃烘干3h后于600℃下焙烧3h,即可得到ZnWO4催化剂。(1) AxByOz type composite metal oxide catalyst ZnWO 4 can be prepared by hydrothermal method. The specific process is as follows: dissolve 0.55g zinc acetate and 0.99g sodium tungstate dihydrate in 60mL deionized water, and ultrasonically obtain a suspension at room temperature; The mixed solution was transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted at 120 °C for 12 hours, filtered and washed, and the obtained powder was dried at 80 °C for 3 hours and then calcined at 600 °C for 3 hours to obtain ZnWO 4 catalyst.
(2)将上述ZnWO4催化剂0.1g与实施例8中合成的Zn3Mo2O9催化剂0.1g机械混合后,与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,然后在氢气压力0.01MPa、氢气流量200mL/min、还原温度450℃下还原1h,然后控制反应温度400℃,反应压力0.01MPa,3-甲基-2-环戊烯-1-酮的时空速为3.5h-1,氢气与3-甲基-2-环戊烯-1-酮的摩尔比为100∶1,其3-甲基-2-环戊烯-1-酮的转化率为100%,甲基环戊二烯的选择性为95%。(2) After mechanically mixing 0.1 g of the above-mentioned ZnWO 4 catalyst with 0.1 g of the Zn 3 Mo 2 O 9 catalyst synthesized in Example 8, uniformly mixed with 4 mL of 40-70 mesh quartz sand, and filled in a fixed-bed continuous reactor , and then reduced at a hydrogen pressure of 0.01 MPa, a hydrogen flow of 200 mL/min, and a reduction temperature of 450 °C for 1 h, and then controlled the reaction temperature to 400 °C and the reaction pressure of 0.01 MPa. The hourly space velocity is 3.5h -1 , the molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 100:1, and the conversion rate of 3-methyl-2-cyclopenten-1-one is is 100% and the selectivity to methylcyclopentadiene is 95%.
上述的实施例24-28的实验结果见表4。The experimental results of the above-mentioned Examples 24-28 are shown in Table 4.
表4由3-甲基-2-环戊烯-1-酮加氢脱氧合成甲基环戊二烯Table 4 Synthesis of methylcyclopentadiene by hydrodeoxygenation of 3-methyl-2-cyclopenten-1-one
以实施例28中的ZnWO4+Zn3Mo2O9作为催化剂,0.2g与4mL 40-70目石英砂均匀混合,填装于固定床连续式反应器中,以2,5-己二酮为底物,然后在氢气压力0.05MPa,还原温度400℃下还原1h,在一定的氢气与2,5-己二酮的摩尔比、反应温度、反应压力、时空速为下进行反应。Using the ZnWO 4 +Zn 3 Mo 2 O 9 in Example 28 as the catalyst, 0.2 g was uniformly mixed with 4 mL of 40-70 mesh quartz sand, filled in a fixed-bed continuous reactor, and 2,5-hexanedione was used as the catalyst. As the substrate, and then reduced at a hydrogen pressure of 0.05 MPa and a reduction temperature of 400 ° C for 1 h, the reaction was carried out under a certain molar ratio of hydrogen to 2,5-hexanedione, reaction temperature, reaction pressure and hourly space velocity.
表5 ZnWO4+Zn3Mo2O9催化由3-甲基-2-环戊烯-1-酮加氢脱氧合成甲基环戊二烯Table 5 Hydrodeoxygenation of methylcyclopentadiene from 3-methyl-2-cyclopenten-1-one catalyzed by ZnWO 4 +Zn 3 Mo 2 O 9
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