CN104693002A - Method for preparing benzaldehyde by oxidizing toluene - Google Patents
Method for preparing benzaldehyde by oxidizing toluene Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种制备苯甲醛的方法，特别是涉及一种甲苯氧化制备苯甲醛的方法。The invention relates to a method for preparing benzaldehyde, in particular to a method for preparing benzaldehyde by oxidation of toluene.
背景技术Background technique
苯甲醛广泛存在于植物界，特别是在蔷薇科植物中，主要以苷的形式存在于植物的茎皮、叶或种子中，例如苦杏仁中的苦杏仁苷。苯甲醛天然存在于苦杏仁油、藿香油、风信子油、依兰依兰油等精油中。有时也称苦杏仁油。苯甲醛作为重要的化工原料，用于制月桂醛、月桂酸、苯乙醛和苯甲酸苄酯等，也可用作测定臭氧、酚、生物碱和位于羧基旁的亚甲基试剂，还可作为特殊的头香香料，微量用于花香配方。Benzaldehyde exists widely in the plant kingdom, especially in Rosaceae plants, mainly in the form of glycosides in the bark, leaves or seeds of plants, such as amygdalin in bitter almonds. Benzaldehyde occurs naturally in essential oils such as bitter almond oil, ageratum oil, hyacinth oil, and ylang ylang oil. It is also sometimes called bitter almond oil. As an important chemical raw material, benzaldehyde is used to produce lauric aldehyde, lauric acid, phenylacetaldehyde and benzyl benzoate, etc. It can also be used to determine ozone, phenol, alkaloids and methylene reagents next to carboxyl groups. As a special top-note fragrance, it is used in trace amounts in floral fragrance formulations.
传统的苯甲醛的工业生产方法主要有三大类：分别以甲苯、苯甲醇和苯为原料。甲苯氯化再水解法、苯甲醇氧化法、苯的加压取代法There are three main types of traditional industrial production methods of benzaldehyde: using toluene, benzyl alcohol and benzene as raw materials respectively. Chlorination and rehydrolysis of toluene, oxidation of benzyl alcohol, pressurized substitution of benzene
传统的苯甲醛的工业生产方法都存在污染严重、毒性大、成本高等缺点，因此，能够针对现有工艺的不足，研究出一种对环境友好而又工艺简单的同时制备苯甲醛的新工艺具有十分重要的现实意义。The traditional industrial production methods of benzaldehyde all have shortcomings such as serious pollution, high toxicity, and high cost. Therefore, a new process for preparing benzaldehyde that is environmentally friendly and simple in process can be developed for the deficiencies of existing processes. very important practical significance.
目前，甲苯在气相或者液相条件下直接氧化生成苯甲醛是较为经济和环保的方法，在近些年绿色氧化甲苯成为大家关注的热点，早在2004年专利号为CN1528726的中国专利中，公开了一种在酸性或中性离子液体以及醋酸混合溶剂中，通过液相氧化甲苯来制备苯甲醛的方法，在115-120℃条件下氧化甲苯，当甲苯转化率为42％时，苯甲醛的选择性仅为48％，该法大量使用了昂贵的离子液体和醋酸溶剂，大大提高了生产成本，且产品分离较为困难，工业生产不经济。大连化物所在专利CN02143361.5公开了一种用于甲苯氧化制备苯甲醛的催化剂的制备方法。该催化剂的活性组分为锆及其他过渡金属、碱金属或碱土金属、第IIIA、IVA、VA等主族金属等。使用该催化剂，在温度180-195℃，通入氧气，在压力0.8-1.2MPa条件下反应，甲苯转化率13.0％时，苯甲醛的选择性为86.6％。该方法催化剂制备工艺比较复杂，而且氧化不易控制在醛的阶段，更易生成苯甲酸。CN200410065322.0公开了一种高选择性甲苯气相氧化法制备苯甲醛的催化剂，其苯甲醛的选择性最高可达94.4％。但该方法反应温度高(320-420℃)，工艺较液相氧化法难于控制，工业化前景并不乐观。CN200510020671.5使用非贵金属钒和钼负载在三氧化二铝上做催化剂，用过氧化氢做氧化剂，以冰乙酸做溶剂，在比较温和的条件下(常压、50-90℃)反应，苯甲醛选择性达到77％，收率13％。该方法需要乙酸做溶剂，且需消耗大量的过氧化氢，废水量大，工艺复杂。因此，虽然此法反应条件温和，但很难实现工业化生产。2014年，Wei Deng等人采用金属卟啉配合物催化氧化甲苯，在100℃条件下反应，甲苯转化率达到41％时候，苯甲醛的选择性仅仅为28.61％，该法使用了昂贵的金属配合物催化剂，副产物较多，提高了生产成本，且造成较大污染。综上所述，现有的技术存在工艺复杂、污染严重、高成本、高能耗、苯甲醛选择性低等诸多缺点。At present, the direct oxidation of toluene to generate benzaldehyde under gas phase or liquid phase conditions is a relatively economical and environmentally friendly method. In recent years, green oxidation of toluene has become a hot spot for everyone. As early as in 2004, the Chinese patent No. CN1528726 disclosed that A method for preparing benzaldehyde by liquid-phase oxidation of toluene in an acidic or neutral ionic liquid and acetic acid mixed solvent, oxidizing toluene at 115-120°C, when the conversion rate of toluene is 42%, the benzaldehyde The selectivity is only 48%. This method uses a large amount of expensive ionic liquid and acetic acid solvent, which greatly increases the production cost, and the separation of products is relatively difficult, so the industrial production is uneconomical. The patent CN02143361.5 of Dalian Institute of Chemical Technology discloses a method for preparing a catalyst for the oxidation of toluene to prepare benzaldehyde. The active components of the catalyst are zirconium and other transition metals, alkali metals or alkaline earth metals, main group metals such as IIIA, IVA, VA and the like. The catalyst is used at a temperature of 180-195 DEG C, fed with oxygen, and reacted under the condition of a pressure of 0.8-1.2 MPa. When the conversion rate of toluene is 13.0%, the selectivity of benzaldehyde is 86.6%. The catalyst preparation process of this method is relatively complicated, and the oxidation is not easy to be controlled at the aldehyde stage, and benzoic acid is more likely to be generated. CN200410065322.0 discloses a catalyst for preparing benzaldehyde by gas-phase oxidation of toluene with high selectivity, and the selectivity of benzaldehyde can reach up to 94.4%. However, the reaction temperature of this method is high (320-420°C), and the process is more difficult to control than the liquid phase oxidation method, and the industrialization prospect is not optimistic. CN200510020671.5 uses non-precious metals vanadium and molybdenum supported on aluminum oxide as a catalyst, uses hydrogen peroxide as an oxidant, and uses glacial acetic acid as a solvent to react under relatively mild conditions (atmospheric pressure, 50-90°C), and benzene The formaldehyde selectivity reaches 77%, and the yield is 13%. This method requires acetic acid as a solvent, and consumes a large amount of hydrogen peroxide, resulting in a large amount of waste water and complicated processes. Therefore, although the reaction conditions of this method are mild, it is difficult to realize industrial production. In 2014, Wei Deng et al. used metal porphyrin complexes to catalyze the oxidation of toluene. When the conversion rate of toluene reached 41% at 100°C, the selectivity of benzaldehyde was only 28.61%. This method used expensive metal complexes. Material catalyst, more by-products, increased production costs, and caused greater pollution. To sum up, the existing technology has many shortcomings such as complex process, serious pollution, high cost, high energy consumption, and low selectivity of benzaldehyde.
因此本发明是在前人的基础上，将催化剂换成绿色环保、经济廉价、可重复使用的负载在载体上的金属及其金属氧化物，在50-100℃条件下反应，转化率达到10％-50％，选择性达到60％-98％。Therefore, on the basis of the predecessors, the present invention replaces the catalyst with a metal and its metal oxide loaded on a carrier that is environmentally friendly, economical, and reusable, and reacts at a temperature of 50-100 ° C, and the conversion rate reaches 10. %-50%, the selectivity reaches 60%-98%.
发明内容Contents of the invention
本发明针对现有技术存在的缺陷，提供一种制备苯甲醛的方法，能有效提升苯甲醛的收率，降低副产物的生成率，降低生产成本，减少污染。Aiming at the defects in the prior art, the present invention provides a method for preparing benzaldehyde, which can effectively increase the yield of benzaldehyde, reduce the formation rate of by-products, reduce production costs, and reduce pollution.
本发明的内容是包括如下步骤：Content of the present invention comprises the following steps:
将1-10mol/L浓度的甲苯，负载在载体上的金属及其金属氧化物作为主催化剂0.05-1mol/L，助催化剂1-5mol/L依次加入反应釜中，通入氧气至压强为0.1-5MPa，升高温度至25-120℃，条件进行反应1-80h通过HPLC监测并得到产率。Add 1-10mol/L concentration of toluene, metals and their metal oxides loaded on the carrier as the main catalyst 0.05-1mol/L, and the co-catalyst 1-5mol/L into the reactor in sequence, and feed oxygen until the pressure is 0.1 -5MPa, raise the temperature to 25-120°C, and carry out the reaction under the conditions of 1-80h and monitor the yield by HPLC.
所述的反应温度为50-120℃；The reaction temperature is 50-120°C;
所述的反应压力为0.2-6MPa；The reaction pressure is 0.2-6MPa;
所述的反应时间为1-80h；The reaction time is 1-80h;
所述的催化氧化甲苯制备苯甲醛的方法，其特征在于，所述的助催化剂为：过氧化氢、过氧化环己酮、叔丁基过氧化氢的一种或二种以上；The method for preparing benzaldehyde by catalytic oxidation of toluene is characterized in that the cocatalyst is: one or more of hydrogen peroxide, cyclohexanone peroxide, and tert-butyl hydroperoxide;
所述载体为石墨烯、分子筛、硅胶、海泡石、壳聚糖、硅藻土、中空纤维、环糊精、生物膜中的一种或二种以上；The carrier is one or more of graphene, molecular sieve, silica gel, sepiolite, chitosan, diatomaceous earth, hollow fiber, cyclodextrin, and biofilm;
具体实施方式Detailed ways
实施例1Example 1
本发明的内容是包括如下步骤：Content of the present invention comprises the following steps:
将甲苯12g，甲醇溶剂150mL，催化剂石墨烯负载金属铜纳米粒子0.05g，助催化剂过氧化氢70mg依次加入充满氧气的反应釜中，在温度为70℃，压强为2.0MPa条件进行反应10h，甲苯转化率6％，苯甲醛选择性85％，苯甲醇选择性13％及苯甲酸选择性2％。Add 12g of toluene, 150mL of methanol solvent, 0.05g of catalyst graphene-supported metal copper nanoparticles, and 70mg of cocatalyst hydrogen peroxide into a reaction kettle filled with oxygen in sequence, and react at a temperature of 70°C and a pressure of 2.0MPa for 10h, and toluene The conversion rate is 6%, the selectivity of benzaldehyde is 85%, the selectivity of benzyl alcohol is 13% and the selectivity of benzoic acid is 2%.
实施例2Example 2
按照实施例1的反应条件，不同的是将金属铜纳米粒子替换成金属锰纳米醇选择性14％及苯甲酸选择性5％。According to the reaction conditions of Example 1, the difference is that the metallic copper nanoparticles are replaced with metallic manganese nanoalcohol selectivity of 14% and benzoic acid selectivity of 5%.
实施例3Example 3
按照实施例1的反应条件，不同的是将金属铜纳米粒子替换成金属钴纳米粒子，通过HPLC监测，得到产率，甲苯转化率11％，苯甲醛选择性79％，苯甲醇选择性16％及苯甲酸选择性5％。According to the reaction conditions of Example 1, the difference is that the metal copper nanoparticles are replaced by metal cobalt nanoparticles, and the yield is obtained by monitoring by HPLC. The conversion rate of toluene is 11%, the selectivity of benzaldehyde is 79%, and the selectivity of benzyl alcohol is 16%. And benzoic acid selectivity 5%.
实施例4Example 4
按照实施例1的反应条件，不同的是将反应温度替换成100℃，通过HPLC监测，得到产率，甲苯转化率13％，苯甲醛选择性70％，苯甲醇选择性23％及苯甲酸选择性7％。According to the reaction conditions of Example 1, the difference is that the reaction temperature is replaced by 100°C, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 13%, the selectivity of benzaldehyde is 70%, the selectivity of benzyl alcohol is 23% and the selectivity of benzoic acid Sex 7%.
实施例5Example 5
按照实施例1的反应条件，不同的是将反应温度替换成120℃，通过HPLC监测，得到产率，甲苯转化率15％，苯甲醛选择性68％，苯甲醇选择性24％及苯甲酸选择性8％。According to the reaction conditions of Example 1, the difference is that the reaction temperature is replaced by 120°C, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 15%, the selectivity of benzaldehyde is 68%, the selectivity of benzyl alcohol is 24% and the selectivity of benzoic acid sex 8%.
实施例6Example 6
按照实施例1的反应条件，不同的是将反应压力替换成4.0MPa，通过HPLC监测，得到产率，甲苯转化率19％，苯甲醛选择性71％，苯甲醇选择性19％及苯甲酸选择性10％。According to the reaction conditions of Example 1, the difference is that the reaction pressure is replaced by 4.0MPa, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 19%, the selectivity of benzaldehyde is 71%, the selectivity of benzyl alcohol is 19% and the selectivity of benzoic acid Sex 10%.
实施例7Example 7
按照实施例1的反应条件，不同的是将反应压力替换成6.0MPa，通过HPLC监测，得到产率，甲苯转化率22％，苯甲醛选择性73％，苯甲醇选择性16％及苯甲酸选择性11％。According to the reaction conditions of Example 1, the difference is that the reaction pressure is replaced by 6.0MPa, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 22%, the selectivity of benzaldehyde is 73%, the selectivity of benzyl alcohol is 16% and the selectivity of benzoic acid sex 11%.
实施例8Example 8
按照实施例1的反应条件，不同的是将助催化剂过氧化氢替换成过氧化环己酮，通过HPLC监测，得到产率，甲苯转化率25％，苯甲醛选择性81％，苯甲醇选择性10％及苯甲酸选择性9％。According to the reaction conditions of Example 1, the difference is that the cocatalyst hydrogen peroxide is replaced by cyclohexanone peroxide, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 25%, the selectivity of benzaldehyde is 81%, and the selectivity of benzyl alcohol 10% and benzoic acid selectivity 9%.
实施例9Example 9
按照实施例1的反应条件，不同的是将助催化剂过氧化氢替换成叔丁基过氧化氢，通过HPLC监测，得到产率，甲苯转化率28％，苯甲醛选择性90％，苯甲醇选择性3％及苯甲酸选择性7％。According to the reaction conditions of Example 1, the difference is that the cocatalyst hydrogen peroxide is replaced by tert-butyl hydroperoxide, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 28%, the selectivity of benzaldehyde is 90%, and the selectivity of benzyl alcohol is 90%. 3% and benzoic acid selectivity 7%.
实施例10Example 10
按照实施例1的反应条件，不同的将负载金属载体石墨烯替换成壳聚糖，通过HPLC监测，得到产率，甲苯转化率30％，苯甲醛选择性92％，苯甲醇选择性2％及苯甲酸选择性6％。According to the reaction conditions of Example 1, the different loaded metal carrier graphene is replaced by chitosan, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 30%, the selectivity of benzaldehyde is 92%, the selectivity of benzyl alcohol is 2% and Benzoic acid selectivity 6%.
实施例12Example 12
按照实施例1的反应条件，不同的将负载金属载体石墨烯氢替换成中空纤维，通过HPLC监测，得到产率，甲苯转化率33％，苯甲醛选择性94％，苯甲醇选择性1％及苯甲酸选择性5％。According to the reaction conditions of Example 1, different metal carrier graphene hydrogen is replaced by a hollow fiber, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 33%, the selectivity of benzaldehyde is 94%, the selectivity of benzyl alcohol is 1% and Benzoic acid selectivity 5%.
实施例13Example 13
按照实施例1的反应条件，不同的将催化剂的质量0.05g替换成0.4g，通过HPLC监测，得到产率，甲苯转化率38％，苯甲醛选择性89％，苯甲醇选择性6％及苯甲酸选择性5％。According to the reaction conditions of Example 1, different quality 0.05g of the catalyst was replaced by 0.4g, and monitored by HPLC, the yield was obtained, the conversion rate of toluene was 38%, the selectivity of benzaldehyde was 89%, the selectivity of benzyl alcohol was 6% and benzene Formic acid selectivity 5%.
实施例14Example 14
按照实施例1的反应条件，不同的将催化剂的质量0.05g替换成0.6g，通过HPLC监测，得到产率，甲苯转化率41％，苯甲醛选择性95％，苯甲醇选择性2％及苯甲酸选择性3％。According to the reaction conditions of Example 1, different quality 0.05g of the catalyst was replaced by 0.6g, and monitored by HPLC, the yield was obtained, the conversion rate of toluene was 41%, the selectivity of benzaldehyde was 95%, the selectivity of benzyl alcohol was 2% and benzene Formic acid selectivity 3%.
实施例15Example 15
按照实施例1的反应条件，不同的将反应时间10h替换成40h，通过HPLC监测，得到产率，甲苯转化率45％，苯甲醛选择性88％，苯甲醇选择性1％及苯甲酸选择性11％。According to the reaction conditions of Example 1, the different reaction time 10h was replaced by 40h, and the yield was obtained by monitoring by HPLC, the conversion rate of toluene was 45%, the selectivity of benzaldehyde was 88%, the selectivity of benzyl alcohol was 1% and the selectivity of benzoic acid 11%.
实施例16Example 16
按照实施例1的反应条件，不同的将反应时间10h替换成80h，通过HPLC监测，得到产率，甲苯转化率51％，苯甲醛选择性85％，苯甲醇选择性2％及苯甲酸选择性13％。According to the reaction conditions of Example 1, the different reaction time 10h was replaced by 80h, and the yield was obtained by monitoring by HPLC, the conversion rate of toluene was 51%, the selectivity of benzaldehyde was 85%, the selectivity of benzyl alcohol was 2% and the selectivity of benzoic acid 13%.
实施例17Example 17
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化铜纳米粒子，通过HPLC监测，得到产率，甲苯转化率47％，苯甲醛选择性88％，苯甲醇选择性4％及苯甲酸选择性8％。According to the reaction conditions of Example 1, different metal copper nanoparticles were replaced by copper oxide nanoparticles, and the yield was obtained by monitoring by HPLC, the conversion rate of toluene was 47%, the selectivity of benzaldehyde was 88%, the selectivity of benzyl alcohol was 4% and Benzoic acid selectivity 8%.
实施例18Example 18
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化铁纳米粒子，通过HPLC监测，得到产率，甲苯转化率46％，苯甲醛选择性91％，苯甲醇选择性7％及苯甲酸选择性2％。According to the reaction conditions of Example 1, different metal copper nanoparticles were replaced by iron oxide nanoparticles, and the yield was obtained by monitoring by HPLC, the conversion rate of toluene was 46%, the selectivity of benzaldehyde was 91%, the selectivity of benzyl alcohol was 7% and Benzoic acid selectivity 2%.
实施例19Example 19
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化锰纳米粒子，通过HPLC监测，得到产率，甲苯转化率43％，苯甲醛选择性82％，苯甲醇选择性9％及苯甲酸选择性9％。According to the reaction conditions of Example 1, different metal copper nanoparticles are replaced by manganese oxide nanoparticles, and the yield is obtained by monitoring by HPLC, the conversion rate of toluene is 43%, the selectivity of benzaldehyde is 82%, the selectivity of benzyl alcohol is 9% and Benzoic acid selectivity 9%.
实施例20Example 20
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化锰和金属锰复合纳米粒子，通过HPLC监测，得到产率，甲苯转化率46％，苯甲醛选择性83％，苯甲醇选择性11％及苯甲酸选择性6％。According to the reaction conditions of Example 1, different metal copper nanoparticles are replaced by manganese oxide and metal manganese composite nanoparticles, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 46%, the selectivity of benzaldehyde is 83%, and the selectivity of benzyl alcohol 11% and benzoic acid selectivity 6%.
实施例21Example 21
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化铜和金属铜复合纳米粒子，通过HPLC监测，得到产率，甲苯转化率51％，苯甲醛选择性80％，苯甲醇选择性13％及苯甲酸选择性7％。According to the reaction conditions of Example 1, different metal copper nanoparticles are replaced with copper oxide and metal copper composite nanoparticles, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 51%, the selectivity of benzaldehyde is 80%, and the selectivity of benzyl alcohol is 80%. The specificity is 13% and the selectivity of benzoic acid is 7%.
实施例22Example 22
按照实施例1的反应条件，不同的将金属铜纳米粒子替换成氧化钴和金属钴复合纳米粒子，通过HPLC监测，得到产率，甲苯转化率55％，苯甲醛选择性90％，苯甲醇选择性3％及苯甲酸选择性7％。According to the reaction conditions of Example 1, different metal copper nanoparticles are replaced by cobalt oxide and metal cobalt composite nanoparticles, and monitored by HPLC, the yield is obtained, the conversion rate of toluene is 55%, the selectivity of benzaldehyde is 90%, and the selectivity of benzyl alcohol is 90%. 3% and benzoic acid selectivity 7%.
以上所述仅为本发明的优选实施例而已，并不限制本发明，对于此领域的技术人员来说，本发明可以有各种变化，凡在本发明的技术领域之内所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, and does not limit the present invention. For those skilled in the art, the present invention can have various changes, and any modification done within the technical field of the present invention , equivalent replacements, improvements, etc., should all be included within the protection scope of the present invention.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126860A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Toluene direct oxidation catalyst and preparation method thereof |
| CN106478389A (en) * | 2016-08-26 | 2017-03-08 | 安徽金邦医药化工有限公司 | A kind of preparation method of 1-Phenylethanone. |
| CN106565394A (en) * | 2016-11-14 | 2017-04-19 | 山东金城石墨烯科技有限公司 | Method of using normal pressure oxygen to oxidize aromatic alcohols to prepare aldehyde in presence of graphene supported nano copper powder (catalyst) |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
| CN107056594A (en) * | 2017-03-29 | 2017-08-18 | 钦州学院 | Preparation method of benzaldehyde |
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| CN112973725A (en) * | 2021-03-08 | 2021-06-18 | 重庆化工职业学院 | Catalyst for synthesizing sclareolide by oxidizing sclareol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495726B1 (en) * | 1999-09-16 | 2002-12-17 | Council Of Scientific And Industrial Research | Process for the production of benzaldehyde by the catalytic liquid phase air oxidation of toluene |
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN102070382A (en) * | 2011-01-19 | 2011-05-25 | 山东瀛洋香精香料有限公司 | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene |
| CN104028269A (en) * | 2014-06-20 | 2014-09-10 | 南京工业大学 | Graphene-loaded metal nanocomposite, preparation method and application |
-
2015
- 2015-03-11 CN CN201510108688.XA patent/CN104693002A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495726B1 (en) * | 1999-09-16 | 2002-12-17 | Council Of Scientific And Industrial Research | Process for the production of benzaldehyde by the catalytic liquid phase air oxidation of toluene |
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN102070382A (en) * | 2011-01-19 | 2011-05-25 | 山东瀛洋香精香料有限公司 | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene |
| CN104028269A (en) * | 2014-06-20 | 2014-09-10 | 南京工业大学 | Graphene-loaded metal nanocomposite, preparation method and application |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126860A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Toluene direct oxidation catalyst and preparation method thereof |
| CN105126860B (en) * | 2015-07-31 | 2017-10-31 | 烟台智本知识产权运营管理有限公司 | A kind of toluene direct oxidation catalyst and preparation method thereof |
| CN106478389A (en) * | 2016-08-26 | 2017-03-08 | 安徽金邦医药化工有限公司 | A kind of preparation method of 1-Phenylethanone. |
| CN106565394B (en) * | 2016-11-14 | 2019-08-13 | 山东金城石墨烯科技有限公司 | A kind of graphene-supported Nanometer Copper powder catalysis atmospheric oxygen aoxidizes the fragrant and mellow method for preparing aldehyde |
| CN106565394A (en) * | 2016-11-14 | 2017-04-19 | 山东金城石墨烯科技有限公司 | Method of using normal pressure oxygen to oxidize aromatic alcohols to prepare aldehyde in presence of graphene supported nano copper powder (catalyst) |
| CN108503518A (en) * | 2017-02-28 | 2018-09-07 | 湖南师范大学 | A kind of preparation and its application of compound sepiolite base catalyst |
| CN107056594A (en) * | 2017-03-29 | 2017-08-18 | 钦州学院 | Preparation method of benzaldehyde |
| CN107056594B (en) * | 2017-03-29 | 2020-07-28 | 钦州学院 | Preparation method of benzaldehyde |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
| CN109482227A (en) * | 2018-08-30 | 2019-03-19 | 南京大学 | A kind of two-dimensional ultrathin Mo/CuO@SAPO-34 molecular sieve catalytic material and the preparation method and application thereof |
| CN109482227B (en) * | 2018-08-30 | 2021-09-28 | 南京大学 | Two-dimensional ultrathin Mo/CuO @ SAPO-34 molecular sieve catalytic material, and preparation method and application thereof |
| CN109482119A (en) * | 2018-12-12 | 2019-03-19 | 西南大学 | A kind of the nano molecular sieve microreactor and preparation method of efficient production benzaldehyde |
| CN109482119B (en) * | 2018-12-12 | 2021-05-07 | 西南大学 | A kind of nanometer molecular sieve microreactor for efficiently producing benzaldehyde and preparation method thereof |
| CN109999826A (en) * | 2019-04-08 | 2019-07-12 | 沈阳化工大学 | A kind of hollow micron tubulose manganese cobalt-base catalyst and preparation method thereof for toluene catalytically purification |
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