CN106883087A - 一种气相光催化氧化乙醇制乙烯、乙醛和丙酮的Cu/TiO2催化剂及反应工艺 - Google Patents
一种气相光催化氧化乙醇制乙烯、乙醛和丙酮的Cu/TiO2催化剂及反应工艺 Download PDFInfo
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- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 4
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 3
- 229960004643 cupric oxide Drugs 0.000 abstract description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 3
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
本发明提供了一种二氧化钛负载的铜基复合型光催化剂的制备方法及其在气相条件下光催化部分氧化乙醇制备乙烯、乙醛和丙酮等产物的工艺。以锐钛矿型或锐钛矿与少量金红石的混相二氧化钛为载体，可溶性铜盐为铜物种（金属铜、氧化铜、氧化亚铜）的前驱体，硼氢化钠为还原剂，制备二氧化钛负载的纳米铜复合型催化剂，该催化剂在紫外光照射下，可以在含氧气氛中将乙醇气体部分氧化脱氢制备乙烯、乙醛和丙酮等产物。所制备的催化剂具有稳定性好，转化率高，主产物选择性高的特点。
Description
技术领域
本发明涉及一种光催化剂的制备及其应用，属能源化工和精细化工领域，主要适用于低温下气相光催化部分氧化乙醇制乙烯、乙醛和丙酮的反应，提供催化剂的制备方法和催化反应条件。
背景技术
乙烯是世界上产量最大的化学产品之一，乙烯工业是石油化工产业的核心，乙烯产品占石化产品的75%以上，在国民经济中占有重要的地位。世界上已将乙烯产量作为衡量一个国家石油化工发展水平的重要标志之一。[Minhua Zhang. Ind. Eng. Chem. Res.2013, 52, 9505−9514]
传统的乙烯生产方法主要有石油制乙烯、煤制乙烯、甲醇制乙烯、甲烷制乙烯和甜高粱制乙烯。其中石油制乙烯比例较大。煤制乙烯路线流程短、副产物较少、烯烃收率高，但是缺点是比石油基路线水耗高、CO2排放多。热催化法乙醇转乙烯催化剂有HZSM-5 zeolite[Bi, J. D.; Guo, X. W.; Liu, M.; Wang, X. S. Catal. Today 2010,149, 143−147]和H-ZSM-5 [Varisli, D.; Dogu, T.; Dogu, G. Chem. Eng. Sci. 2007, 62, 5349−5352.]等。
乙醛用于制造醋酸、醋酐和合成树脂。主要合成方法有乙烯直接氧化法、乙醇氧化法、乙炔直接水合法、乙醇脱氧法等。其中乙烯直接氧化法生产乙醛和工业化，使其成为主要方法。原因是乙烯来源丰富且廉价，具有反应条件温和、选择性好、收率高、工艺流程简单及三废处理容易等特点。
丙酮在工业上主要作为溶剂用于炸药、塑料、橡胶、纤维、制革、油脂、喷漆等行业中，也可作为合成烯酮、醋酐、碘仿、聚异戊二烯橡胶、甲基丙烯酸甲酯、氯仿、环氧树脂等物质的重要原料。丙酮的工业生产以异丙苯法为主。以乙醇为原料生产丙酮，一般需要铬酸锌作催化剂，反应高温比较高，通常超过400℃以上。
乙酸乙酯是应用广泛的酯类化合物，具有优异的溶解性、快干性，可用作有机溶剂。乙酸乙酯还被广泛用于合成橡胶工业、乙烯树脂纤维素、乙酸酯纤维素、乙酸丁酯、乙基纤维、硝酸纤维等产品的生产。[刘冲等编.石油化工手册(三).北京:化学工业出版社,1987: P259.]。[程能林,胡声闻.溶剂手册(下册)[M].北京:化学工业出版社,1987:14-15]。乙酸乙酯合成方法通常有直接酯化法，乙醛缩合法，乙醇催化脱氢法，乙酸乙烯酯化法等。其中直接酯化法存在以下缺点：反应温度高、乙酸利用率低、易发生副反应，同时生产过程中由于催化剂浓硫酸的强腐蚀性，导致设备腐蚀严重，废液污染环境，副产物处理困难，导致生产成本高。乙醛缩合法受原料乙醛的限制，催化剂难制备、易水解、反应过程需冷却。乙醇催化脱氢法不仅生产流程简单、条件温和、产品浓度高、生产成本低，而且对设备材质要求低、无含酸废水及环境污染，是一种高产率、无腐蚀、低原料成本的合成路线。
发明内容
本发明的目的主要是提供一种反应温度在10-50℃，在气相和光照条件下能够将乙醇部分氧化脱氢制乙烯、乙醛和丙酮等化合物的高效二氧化钛负载的纳米金Cu-TiO2光催化剂制备方法及生产工艺。
本发明首次将Cu-TiO2光催化剂（其中铜物种为金属铜、氧化铜、氧化亚铜）用于乙醇气相光催化部分氧化乙醇制乙烯、乙醛和丙酮等化合物反应。实验结果表明，催化剂具有较高的乙醇转化率和目标产物的选择性。在实验温度范围内和光照条件下，转化率达到60-80%，乙烯、乙醛和丙酮产物总选择性达到75-95%。
本发明的催化剂Cu/TiO2由2-10% 的铜物种（金属铜、氧化铜、氧化亚铜）和90-98%的二氧化钛构成，二氧化钛晶型为锐钛矿型或锐钛矿与少量（低于25%）金红石混相构成。
本发明催化剂的制备方法是采用化学还原法制备。
制备方法如下。
（1）取一定量的铜盐与蒸馏水以1:10 的比例配置成含有铜离子的水溶液，搅拌；
（2）称取一定量的二氧化钛超声分散于蒸馏水中，并加入步骤（1）配制的含铜离子的溶液中，搅拌15 min；
（3）以Cu:NaBH4=1:2（摩尔比）称取适量硼氢化钠，溶于蒸馏水中，在快速搅拌下将其迅速加入上述混合液中，搅拌24 h；
(4)离心分离，洗涤，50℃下干燥，得到催化剂。
本发明制备的催化剂比表面积与二氧化钛前体的比表面积接近，一般在50-300m2/g；
如上所述的二氧化钛可以是商用混相二氧化钛P25、商用锐钛矿型二氧化钛ST-01、自制锐钛矿型或锐钛矿与金红石的混相二氧化钛。
如上所述的铜盐可以是硝酸铜、氯化铜、醋酸铜、硫酸铜的一种或几种。
本发明的催化剂应用于气相光催化乙醇部分氧化制乙烯、乙醛和丙酮等反应工艺如下：
催化剂粉末喷涂在固体表面上，该固体可以是玻璃、不锈钢、塑料、陶瓷, 光源为紫外光或太阳光，反应温度为10-50℃ ,甲醇/ 氧气摩尔比例为1-6, 乙醇体积百分含量1-3%，氮气为平衡气，反应空速为100-400 L.g-1.h-1。
本发明与已有技术相比具有以下创新与特点：
首次将Cu-TiO2催化剂用于气相光催化乙醇部分氧化脱氢制乙烯、乙醛和丙酮等化合物。
催化反应温度为10-50℃,是目前乙醇部分氧化脱氢制乙烯、乙醛和丙酮等反应温度最低操作条件。
附图说明
图1 为制备的CuO 液体紫外可见光谱（UV-Vis）图；
图2 为制备的Cu/TiO2复合光催化剂的X 射线衍射（XRD）图谱；
图3 为制备的Cu/TiO2复合光催化剂的透射电镜（TEM）图；
图4 为制备的Cu/TiO2复合光催化剂的高分辨透射电镜（TEM）图。
具体实施方式
下面结合实施例对本发明作进一步的说明，本发明包括但不限于下面的实施例。
量取10 mL 0.01mol/L Cu(NO3)2水溶液于500 ml 圆底烧瓶中；称取0.4 g P25 二氧化钛粉末超声分散于5 ml 蒸馏水中，再加入到上述溶液中，搅拌；称取0.0038 g NaBH4，将其溶于5 ml 蒸馏水中并迅速加入到上述二氧化钛与硝酸铜的悬浮液中；继续搅拌24 h，离心分离，洗涤，50℃下真空干燥6 h，即得2%Cu/TiO2复合光催化剂。以类似的方法，改变加入P25 的量，制备不同摩尔比（4%、6%、8%、10%）的Cu/TiO2复合催化剂。
将上述方法制备的2%Cu/TiO2复合催化剂喷涂在玻璃基底上，并将涂有催化剂的玻璃基底安放在光催化反应器中，通入反应原料气并打开紫外灯开始反应，利用气相色谱检测反应尾气的成份。催化剂用量0.02g，反应温度10-50℃，原料气组成1% 乙醇，2%氧气，97% 氮气，原料气流量55 ml/min, 空速150 L.g-1.h-1。
以上催化剂进行光催化性能评价结果显示，该催化剂的乙醇转化率为60%，乙醛择性达55%，乙烯选择性达33%，丙酮选择性达10%，乙酸乙酯选择性达1.5%，催化剂对乙醇转化率和乙烯、乙醛和丙酮总选择性高，反应稳定性好，是优良的光催化氧化乙醇制乙烯、乙醛和丙酮的催化剂。
Claims (1)
1.一种气相光催化部分氧化乙醇制备乙烯、乙醛和丙酮等产物的工艺和催化剂制备方法，其特征在于催化剂为二氧化钛负载的铜催化剂，其活性组分为二氧化钛和不同种类的铜物种；二氧化钛为锐钛矿或锐钛矿含量低于25%金红石的混相结构；铜物种的摩尔分数为2-10%；催化剂的制备方法为：在一定量的可溶性铜盐水溶液中加入已经超声好的二氧化钛水溶液并搅拌，将适量的硼氢化钠溶解在少量蒸馏水中快速加入到上述溶液中并继续搅拌24h；离心分离并用蒸馏水、乙醇洗涤；50℃下干燥后得到Cu/TiO2复合光催化剂；反应条件也是该发明的重要特征之一：紫外光或者太阳光照射，反应温度为10-50℃，原料气中乙醇体积含量为1%-3%左右，乙醇/氧气比为CH3OH: O2=1:1-6:1，平衡气为氮气，空速100-400L.g-1.h-1。
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| CN113105300A (zh) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | 一种均相光催化乙醇产乙烯的方法 |
| WO2023232998A1 (fr) * | 2022-06-03 | 2023-12-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Utilisation de particules de dioxyde de titane portant un metal ou un oxyde de metal pour l'obtention d'alcenes par photocatalyse |
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| CN106955705A (zh) * | 2017-03-30 | 2017-07-18 | 内蒙古大学 | 一种气相光催化甲醇和乙醇一次性合成多种酯类化合物的铜催化剂的制备及应用 |
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| CN110721685A (zh) * | 2019-11-14 | 2020-01-24 | 山东师范大学 | 一种复合光催化材料及其制备方法和应用 |
| CN110721685B (zh) * | 2019-11-14 | 2022-09-27 | 山东师范大学 | 一种复合光催化材料及其制备方法和应用 |
| CN113105300A (zh) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | 一种均相光催化乙醇产乙烯的方法 |
| CN113105300B (zh) * | 2021-03-26 | 2022-05-24 | 华南理工大学 | 一种均相光催化乙醇产乙烯的方法 |
| WO2023232998A1 (fr) * | 2022-06-03 | 2023-12-07 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Utilisation de particules de dioxyde de titane portant un metal ou un oxyde de metal pour l'obtention d'alcenes par photocatalyse |
| FR3136177A1 (fr) * | 2022-06-03 | 2023-12-08 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Utilisation de particules de dioxyde de titane portant un metal ou un oxyde de metal pour l’obtention d’alcenes par photocatalyse |
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