CN102728358B - Cobaltosic oxide/graphene catalyst for preparing benzamide by benzyl alcohol ammoxidation and preparation method thereof - Google Patents
Cobaltosic oxide/graphene catalyst for preparing benzamide by benzyl alcohol ammoxidation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 26
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 9
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- -1 aromatic alcohols Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 description 18
- 239000002994 raw material Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003800 Staudinger reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种苯甲醇与氨水和氧气直接氨氧化制备苯甲酰胺的石墨烯负载的四氧化三钴催化剂及其制备方法。在本发明中，首次使用石墨烯负载的四氧化三钴作为多相催化剂催化苯甲醇与氨水和氧气直接氨氧化反应。催化剂简单易得，并可以回收和重复使用，反应条件温和、且无废弃物生成，产物分离非常简单，具有很大的实际应用前景。上述催化剂在芳香醇的氨氧化反应中具有很好的活性。The invention relates to a graphene-loaded tricobalt tetroxide catalyst for preparing benzamide by direct ammoxidation of benzyl alcohol, ammonia water and oxygen and a preparation method thereof. In the present invention, for the first time, graphene-supported cobalt tetroxide is used as a heterogeneous catalyst to catalyze the direct ammoxidation reaction of benzyl alcohol with ammonia water and oxygen. The catalyst is simple and easy to obtain, and can be recycled and reused. The reaction conditions are mild, and no waste is generated. The product separation is very simple, and has great practical application prospects. The above catalysts have good activity in the ammoxidation of aromatic alcohols.
Description
Technical field
The present invention relates to the direct prepared by ammoxidation of a kind of phenmethylol and ammoniacal liquor and oxygen for the graphene-supported cobaltosic oxide Catalysts and its preparation method of benzamide.
Background technology
Acid amides is the important organic compound of a class, in biology, chemistry and polymer arts, has extremely important application.For example, acid amides can be used for producing the products such as medicine, fine chemicals, agrochemical formulations, polymer, dyestuff, pigment, emulsifying agent and plasticizer.But the formation of C-N key remains a great problem that people face.At present; the most general method of synthetic middle use of acid amides is the reaction that adopts active carboxylic acid derivative; for example acid, aldehyde, carboxylic acid halides, mixed acid anhydride and ester class and amine or acyl azide effect; or acid hydrazide compounds and the reducing agent (CN201010549817.6 that reacts; CN201010603154.1, CN94100107.5, CN00810821.8; CN01134270.6, CN03159472.7).Improved method has: under the effect of acid, alkali, homogeneous phase or heterogeneous transition-metal catalyst, catalysis itrile group derivative obtains corresponding acid amides (CN99810960.6, CN200710001709.3, CN200810060773.3, CN200810121730.1).In addition, Beckmann resets, Aube – Schmidt resets and Staudinger reaction is also to use commonplace method.Yet existing reaction has many shortcomings, such as: expensive raw material (acid, aldehyde, carboxylic acid halides, mixed acid anhydride etc.) in first method, used, in the second synthetic route, use poisonous inorganic cyanogen salt, produced a large amount of discarded inorganic salts, severe reaction conditions, reaction yield is low, and cost is high; Seriously hindered the production-scale expansion of acid amides.Therefore, developing low-cost, high yield, no waste, and also atom economy, eco-friendly acid amides synthetic catalyst are problem demanding prompt solutions more.
Current research shows, heterogeneous catalysis synthesizing amide has higher catalytic efficiency and is easy to the advantages such as recovery.For example, the people such as Milstein (Chem. Eur. J. 2011,17,11428 – 11431) have reported a kind of Ag/Al
2o
3the acid amides route of synthesis of the one-level of catalysis or secondary alcohol and secondary amine anaerobic dehydrogenation, this process need adds a large amount of alkali and adopts toluene to make solvent, and return time is grown (24 hours).The people such as Wang (Angew. Chem. Int. Ed. 2011,50,8917 – 8921) prepared a kind of water miscible DNA supported nanometer gold catalyst, under relatively gentle condition, catalytic alcohol is reacted synthesizing amide with amine effectively, but this process adopts one-level or secondary amine to be raw material, need to add highly basic (LiOH) and reaction time to grow (12 hours).In addition, ruthenium-based catalyst, because it has higher catalytic activity and selective, is also widely used in the synthetic reaction of acid amides, and raw material can adopt one-level nitrile (Angew. Chem. Int. Ed. 2004,43,1576 – 1580), (solvent is oxolane, sees Angew. Chem. Int. Ed. 2009,48 for primary alcohol or aldehyde, 6286 – 6288, Top Catal. 2010,53,479 – 486).Yet there are many drawbacks in these reactions, such as: use stability that one-level or secondary amine are nitrogenous source, highly basic, organic solvent, employing noble metal, catalyst too low etc.Therefore,, from environment and economic angle, use base metal to there is application prospect more widely as heterogeneous catalyst.
Adopt alcohol and ammoniacal liquor, oxygen directly reaction is prepared acid amides (as following reaction equation) to have raw material cheap and easy to get, Atom economy is high, the plurality of advantages such as waste discharge amount is low, the researcher of Tokyo Univ Japan once adopted hydroxide ruthenium (Top Catal (2010) 53:479 – 486) and porous oxidation manganese molecular sieve (the Angew. Chem. Int. Ed. 2011 of load, 50, 1 – 5) for catalyst carries out above-mentioned synthetic reaction, but above-mentioned catalyst only just has enough reactivities in expensive organic solvent (dioxane or oxolane), this has greatly limited it and has further applied.
Chinese patent application CN102295571A reported a kind of take methyl alcohol or formaldehyde as raw material, directly prepare the method for C2-C4 acid amides with ammonia and air multistep reaction, it is that raw material, multi-component Fe-Mo-Bi-P are catalyst that but reaction has adopted a plurality of reactor tandem process, gaseous ammonia, and reaction temperature higher (300-420 degree).
In the present patent application, we adopt a kind of simple two step method to prepare graphene-supported Co
3o
4nanoparticle catalyst, and this catalyst is directly reacted and prepares acid amides with ammoniacal liquor, oxygen for alcohol; This catalyst has very high catalytic activity and stability in the ammoxidation reaction of alcohol; What is more important, water is more conducive to this reaction as solvent to carry out.In whole reaction, without the generation of any discarded object, pollutant.
Summary of the invention
The object of this invention is to provide the direct prepared by ammoxidation of a kind of phenmethylol and ammoniacal liquor and oxygen for the graphene-supported cobaltosic oxide Catalysts and its preparation method of acyl benzene methanamine, concrete technical scheme is as follows:
One) the concrete preparation process of graphene-supported cobaltosic oxide catalyst is as follows:
1), Graphene is dispersed in absolute ethyl alcohol, ultrasonic 2 hours, obtain the suspension of homogeneous, control the mass ratio of ethanol and Graphene at 1500:1 ~ 3500:1;
2), in above-mentioned solution, add a certain amount of cobalt acetate aqueous solution (concentration is in 0.05 ~ 0.3 mol/L), add a certain amount of ammoniacal liquor (ammonia content is 28wt%) and a certain amount of water, control the volume ratio of cobalt acetate solution and ethanol at 1:30 ~ 1:10, control the volume ratio of ammoniacal liquor and ethanol at 0 ~ 1:50, control the water of interpolation and the volume ratio of ethanol at 1:34 ~ 1:20;
3), above-mentioned suspension is refluxed 10 hours under 60 ~ 80 degree;
4), proceed to 500 milliliters of reactors, 150 degree hydrothermal treatment consists 2 ~ 5 hours;
5), reacted suspension is cooled to room temperature, suction filtration, washing, then spend the night 50 ° of C vacuum drying.
Two) catalyst recited above directly reacts with ammoniacal liquor, oxygen the method for preparing benzamide for phenmethylol, and concrete preparation process is as follows:
1), get in the solvent that a certain amount of catalyst is dispersed in, add phenmethylol, ammoniacal liquor (ammonia content is 28 wt%), control the mass ratio of phenmethylol and catalyst at 1:5 ~ 1:1, the mass ratio of ammoniacal liquor and phenmethylol is at 0.5:1 ~ 5:1, and the mass ratio of solvent and phenmethylol is at 10:1 ~ 100:1;
2), be filled with oxygen to reactor pressure to 10 ~ 30 atmospheric pressure, be warming up to 120 ~ 150 degree, stir lower reaction 0.25 ~ 30 hour;
3), reactor is cooled to room temperature,, after centrifugation solid catalyst, by reactant liquor separated, can obtain purity is more than 99% benzamide.
Beneficial effect of the present invention is as follows: in the present invention, use first graphene-supported cobaltosic oxide as heterogeneous catalyst catalytic phenylmethanol and ammoniacal liquor and the direct ammoxidation reaction of oxygen.Catalyst is simply easy to get, and can reclaim and reuse, and reaction condition is gentle and without discarded object generation, product separation is very simple, has very large actual application prospect.Above-mentioned catalyst has good activity in the ammoxidation reaction of aromatic alcohol.
The specific embodiment
Below by specific embodiment, technical scheme of the present invention is described further, but the content of invention has more than the alcohols being confined in embodiment.
Embodiment 1
0.125 g Graphene is dispersed in 378 mL absolute ethyl alcohols to ultrasonic 2 h, the suspension of acquisition homogeneous.The cobalt acetate aqueous solution (concentration 0.2 mol/L) that adds 18.9 mL, adds the ammoniacal liquor (ammonia content is 28wt%) of 7.9 mL and the water of 11 mL.10 h reflux above-mentioned suspension under 80 ° of C.Proceed to 150 ° of C hydrothermal treatment consists 3h of 500 mL reactor.Reacted suspension is cooled to room temperature, suction filtration, washing, then 50 ° of C vacuum drying are spent the night.
Get the H that the above-mentioned catalyst of 0.073 g is dispersed in 4 mL
2in O, add 0.5 mmol phenmethylol, 100 μ L ammoniacal liquor (ammonia content is 28 wt%).Be filled with 3 Mpa O
2, be warming up to 150 ° of C, stir lower reaction 1h.Conversion ratio is 83.1%, and acid amides productive rate is 41.1%.
Embodiment 2
Adopt same catalyst preparation process Kaolinite Preparation of Catalyst in embodiment 1, then get the H that the above-mentioned catalyst of 0.073 g is dispersed in 4 mL
2in O, add 0.5 mmol phenmethylol, 100 μ L ammoniacal liquor (ammonia content is 28 wt%).Be filled with 3 Mpa O
2, be warming up to 150 ° of C, stir lower reaction 2h.Conversion ratio is 95.5%, and acid amides productive rate is 70.4%.
Embodiment 3
Adopt same catalyst preparation process Kaolinite Preparation of Catalyst in embodiment 1, then get the H that the above-mentioned catalyst of 0.073 g is dispersed in 4 mL
2in O, add 0.5 mmol phenmethylol, 100 μ L ammoniacal liquor (ammonia content is 28 wt%).Be filled with 3 Mpa O
2, be warming up to 150 ° of C, stir lower reaction 3 h.Conversion ratio is 98.6%, and acid amides productive rate is 84.9%.
Embodiment 4
Adopt same catalyst preparation process Kaolinite Preparation of Catalyst in embodiment 1, then get the H that the above-mentioned catalyst of 0.073 g is dispersed in 4 mL
2in O, add 0.5 mmol phenmethylol, 100 μ L ammoniacal liquor (ammonia content is 28 wt%).Be filled with 3 Mpa O
2, be warming up to 150 ° of C, stir lower reaction 4 h.Conversion ratio is 100%, and acid amides productive rate is 98.1%.
Embodiment 5
Adopt same catalyst preparation process Kaolinite Preparation of Catalyst in embodiment 1, different is that ammoniacal liquor is changed to isopyknic water.Then get the H that the above-mentioned catalyst of 0.073 g is dispersed in 4 mL
2in O, add 0.5 mmol phenmethylol, 100 μ L ammoniacal liquor (28 wt%).Be filled with 3 Mpa O
2, be warming up to 150 ° of C, stir lower reaction 4 h.Conversion ratio is 86.4%, and acid amides productive rate is 32.4%.
Claims (2)
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| CN119075985B (en) * | 2024-11-08 | 2025-02-21 | 电子科技大学长三角研究院(湖州) | Metal-oxygen vacancy dual-site synergistic catalyst, preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
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| Co3O4 nanocrystals on grapheme as a synergistic catalyst for oxygen reduction reaction;Yongye Liang;《Nature Materials》;20110807;第11卷;780-786 * |
| Yongye Liang.Co3O4 nanocrystals on grapheme as a synergistic catalyst for oxygen reduction reaction.《Nature Materials》.2011,第11卷780-786. |
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