CN113731441B - Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof - Google Patents
Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113731441B CN113731441B CN202111143175.4A CN202111143175A CN113731441B CN 113731441 B CN113731441 B CN 113731441B CN 202111143175 A CN202111143175 A CN 202111143175A CN 113731441 B CN113731441 B CN 113731441B
- Authority
- CN
- China
- Prior art keywords
- rgo
- reaction
- catalyst
- cobalt
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 23
- 230000002829 reductive effect Effects 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 14
- 239000010941 cobalt Substances 0.000 title claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229960001867 guaiacol Drugs 0.000 claims abstract description 39
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940094933 n-dodecane Drugs 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000010453 quartz Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IOZFUGDROBQPNP-UHFFFAOYSA-N 1-methylcyclohexane-1,2-diol Chemical compound CC1(O)CCCCC1O IOZFUGDROBQPNP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101100379079 Emericella variicolor andA gene Proteins 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
Abstract
The invention relates to a cobalt-reduced graphene oxide Co/rGO catalyst, a preparation method and application thereof. The catalyst reacts for 2 hours in n-dodecane solution under the conditions of 1MPa hydrogen pressure and 200 ℃, and can completely convert guaiacol, and the yield of cyclohexanol is 95%. The Co/rGO catalyst without reduction pretreatment has higher catalytic activity and selectivity than Ni/rGO and Fe/rGO catalysts and Co/Al 2O3, co/HY and Co/AC catalysts, is cheaper than noble metal catalysts such as Pt, pd and the like, and has industrial application value.
Description
Technical Field
The invention belongs to the field of cyclohexanol preparation, and particularly relates to a cobalt-reduced graphene oxide Co/rGO catalyst, and a preparation method and application thereof.
Background
With the continuous development of society, great consumption of energy brings great pressure to natural environment, and it is urgent to find new energy which can replace fossil fuel and reduce environmental pollution. Biomass energy is a novel renewable clean energy source, and is mainly composed of C, H, O and other elements because of the similar composition with fossil fuel, so that biomass energy is expected to become a traditional fossil fuel substitute, and is widely paid attention to students in all countries of the world. Wherein lignin accounts for 30-40% of the mass of biomass, is a sufficient renewable raw material, and lignin biomass chemical conversion reaction is widely paid attention to domestic and foreign students in recent years.
Guaiacol (Guaiacol, GUA for short) is one of the simplest model compounds of lignin, on the one hand, its chemical structure contains hydroxyl and methoxy groups, which are widely present in lignin polymers. Therefore, a large number of researchers generally select the lignin as a lignin model compound to conduct hydrodeoxygenation reaction research. Under the action of a catalyst, the guaiacol can be subjected to Hydrodeoxygenation (HDO) reaction to obtain cyclohexanol (Cyclohexanol). Cyclohexanol is colorless viscous liquid at normal temperature and pressure, can be used as industrial raw material with wide application, can be used as synthetic raw material for producing adipic acid and caprolactam, and can obtain important chemical intermediate (nylon-66) in industrial production, so that the cyclohexanol has wide application. Currently, catalysts used in this field mainly include noble metal catalysts (Ru/C, pd/C, pt/C) and non-noble metal catalysts, such as cobalt-based catalysts (Co/rGO, niCo/gamma-Al 2O3), nickel-based catalysts (Ni/Al 2O3, ni/C), molybdenum-based catalysts (Mo 2C/CNT、MoS2/C), and the like. Although some precious metal catalysts have been able to achieve better catalytic results, their use on a large scale has been limited due to their high cost. Some researchers focused on non-noble metal catalysts .R.Olcese,M.M.Bettahar,B.Malaman,J.Ghanbaja,L.Tibavizco,D.Petitjean andA.Dufour,Appl.Catal.B,2013,129,528-538. on iron-based catalysts supported on SiO 2 and Activated Carbon (AC) for HDO reactions of guaiacol model compounds. At 400℃and 1bar, the conversion of guaiacol reached 74% with Fe/SiO 2 as catalyst and the yields of aromatics and other aromatic oxygenates (i.e. phenol, anisole and cresol) were 38%, and the products were almost free of cyclohexanol .I.T.Ghampson,C.Sepúlveda,R.Garcia,B.G.Frederick,M.C.Wheeler,N.Escalona and W.J.DeSisto,Appl.Catal.A,2012,413-414,78-84, and Mo 2 N and CoMoNx catalysts were studied in the HDO reaction of guaiacol. These nitrides can cleave the benzene ring-OCH 3 bond directly in guaiacol to form phenol, but then in the HDO process, at 300 ℃ and 50bar H 2 pressure, the cleavage of the benzene ring-OH bond occurs to form cyclohexene and cyclohexane. In addition, non-noble metal catalysts reported in the literature generally require a reductive pretreatment prior to being put into the reaction system. The catalyst needs pre-reduction treatment, which not only complicates the catalyst preparation and maintenance process and increases energy consumption, but also some reduced catalyst may lose activity due to oxidation.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a cobalt-reduced graphene oxide Co/rGO catalyst, and a preparation method and application thereof.
The invention aims at realizing the following technical scheme:
The preparation method of the cobalt-reduced graphene oxide Co/rGO catalyst comprises the following specific steps:
(1) Preparation of a graphene carrier: taking 230mL of concentrated sulfuric acid and 5.0gNaNO 3, stirring, adding 10g of natural crystalline flake graphite powder, stirring for 2.5 hours, adding 30g of KMnO 4, transferring to 35 ℃ constant-temperature water bath for reaction for 2 hours, adding 460mL of deionized water, stirring for 15 minutes in 98 ℃ oil bath, finally adding 1.4L of deionized water for terminating reaction, simultaneously adding 25mL of 30% H 2O2, cooling to room temperature, centrifugally washing deionized water, washing to neutrality, taking the prepared GO paste with the dry content of 1g, dispersing in 1000mL of deionized water, performing ultrasonic treatment for 30 minutes, standing and ageing, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing for 3 hours in 95 ℃ oil bath, adding 4mL of 80% hydrazine hydrate for reaction for 30 minutes, adding 4% hydrochloric acid solution, filtering while hot, and freeze-drying to obtain a rGO carrier for standby;
(2) Preparation of salt solution: putting Co (NO 3)2·6H2 O into a beaker, dissolving with deionized water to prepare a salt solution, adding absolute ethyl alcohol, and shaking uniformly for later use;
(3) Dipping: weighing the rGO carrier prepared in the step (1), adding the rGO carrier into the beaker in the step (2), continuously stirring the rGO carrier with a glass rod, and standing the sample at room temperature;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12 hours, and grinding the sample into powder by an agate mortar;
(5) Roasting: placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by a program of 10 ℃/min under nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 1-4h, cooling the quartz tube to room temperature, taking out the quartz tube, and sealing and storing the quartz tube.
Further, the sample in the step (3) is placed at room temperature for standing for 2-5h.
Further, the sample in the step (4) is formed into 80-100 mesh powder.
Furthermore, the ratio of Co (NO 3)2·6H2 O to the carrier rGO) in the step (2) and the step (3) is 0.5-3.0 mmol/g, the volume ratio of water to ethanol is 10:1-5:5, and the salt solution prepared in the step (2) can be just absorbed by the rGO weighed in the step (3).
The application of the cobalt-reduced graphene oxide Co/rGO catalyst is used for preparing cyclohexanol by catalytic hydrogenation of guaiacol, and specifically comprises the following steps: n-dodecane is used as a solvent, and guaiacol reacts with H 2 under the action of a Co/rGO catalyst to obtain cyclohexanol.
Further, the reaction temperature for preparing cyclohexanol by catalytic hydrogenation of guaiacol is 180-220 ℃, the hydrogen pressure is 1-4 MPa, and the reaction time is 0.25-3h.
Compared with the prior art, the invention has the following advantages and effects:
(1) Co is non-noble metal, the cost is low, and in addition, the Co/rGO catalyst does not need to be subjected to high-temperature pre-reduction treatment and cannot be deactivated due to oxidation. Furthermore, the Co/rGO catalyst does not precipitate active metal components in the reaction.
(2) The Co/rGO catalyst is prepared by adopting an impregnation-roasting method, and the preparation method is simple and is suitable for large-scale industrial preparation. The Co/rGO catalyst can not cause the decomposition of cyclohexanol, and the yield of cyclohexanol can reach 95% under the conditions of 200 ℃ and 1MPa H 2 and 2 hours, thus showing high selectivity to cyclohexanol.
In conclusion, the Co/rGO catalyst has the characteristics of high reaction activity, high selectivity and the like when catalyzing the hydrogenation reaction of the guaiacol, the conversion rate of the hydrogenation reaction of the guaiacol catalyzed by the Co/rGO catalyst can reach 100%, the cyclohexanol selectivity can reach 95%, and metal components are not separated out.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and all experimental equipment, materials, reagents and the like used can be purchased from chemical companies.
Graphene (Graphene) is a planar film with hexagonal lattice of honeycomb lattice composed of carbon atoms in sp2 hybridized orbitals, and is a two-dimensional material with a thickness of only one carbon atom. Graphene has a plurality of unique physicochemical properties, such as high specific surface area, high conductivity, high mechanical strength, easy modification, large-scale production of graphite, and the like, and has high application value in the field of catalysis. The graphene serving as a carrier not only can provide a large specific surface area, but also can form a strong electronic synergistic effect with active components such as supported metal, metal oxide and the like, and the electronic characteristics of the metal active components are modulated so as to generate excellent catalytic performance.
The invention is characterized in that: the catalyst takes cheap transition metal Co as a hydrogenation active component and reduced graphene oxide rGO as a carrier, and the prepared catalyst does not need high-temperature pre-reduction treatment and can be used for catalyzing the reaction of preparing cyclohexanol by hydrogenating guaiacol. The catalyst reacts for 2 hours in n-dodecane solution under the conditions of 1MPa hydrogen pressure and 200 ℃, and can completely convert guaiacol, and the yield of cyclohexanol is 95%. The graphene with the two-dimensional plane structure not only plays a role in dispersing and carrying Co active components, but also further enhances the catalytic function due to the electronic synergistic effect of Co and graphene. The synthesized catalyst does not need reduction pretreatment, generates higher catalytic activity and product selectivity under mild conditions, and provides a novel high-efficiency catalyst for preparing cyclohexanol by selective hydrogenation of guaiacol.
Examples 1-3 batch reactions at different reaction temperatures
1. And (3) preparing a catalyst: the method for preparing the Co/rGO catalyst by adopting the dipping-roasting method comprises the following specific steps:
(1) Preparation of a graphene carrier: taking 230mL of concentrated sulfuric acid and 5.0gNaNO 3, stirring, adding 10g of natural crystalline flake graphite powder, stirring for 2.5h, adding KMnO 4, transferring to a constant-temperature water bath at 35 ℃ for reaction for 2h, adding 460mL of deionized water, stirring for 15min at 98 ℃ in an oil bath, finally adding 1.4L of deionized water for terminating reaction, simultaneously adding 25mL of 30% H 2O2, cooling to room temperature, centrifugally washing with deionized water, washing to neutrality, taking 1g of the prepared GO paste with a dry basis, dispersing in 1000mL of deionized water, carrying out ultrasonic treatment for 30min, standing and aging, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing for 3h in an oil bath at 95 ℃, adding 4mL of 80% hydrazine hydrate for reaction for 30min, adding 4% hydrochloric acid solution, carrying out suction filtration while hot, and freeze-drying to obtain the rGO carrier for standby.
(2) Preparation of salt solution: 72.8mg of Co (NO 3)2·6H2 O was dissolved in 0.82mL of deionized water to form a salt solution;
(3) Dipping: adding 0.2mL of absolute ethyl alcohol into the prepared salt solution, and shaking uniformly for later use. 100mg rGO was weighed into a beaker and stirred continuously with a glass rod. Standing the sample at room temperature for 3 hours;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12 hours, and grinding the sample into powder by an agate mortar;
(5) Roasting: placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by a program of 10 ℃/min under nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, cooling the quartz tube to room temperature, taking out the quartz tube, and sealing and storing the quartz tube;
2. reaction test: the performance of the Co/rGO catalyst for catalyzing the guaiacol hydrogenation reaction is tested by adopting intermittent reaction, and the specific steps are as follows:
(1) Taking a mechanically-stirring high-pressure reaction kettle, adding 300.0mg of guaiacol, 10ml of n-decane, 120mg of internal standard substance tetradecane and 30mg of Co/rGO catalyst into the high-pressure reaction kettle, screwing the reaction kettle, checking the air tightness of the device, ensuring that the device is airtight, introducing 1MPa H 2, stirring at 700rpm, setting a designated temperature, and reacting for 2 hours.
(2) After the reaction, the liquid phase product was collected and analyzed by gas chromatography. The catalyst was recovered by centrifugation.
Wherein: conversion of guaiacol= (amount of guaiacol substance at the beginning of reaction-amount of guaiacol substance at the end of reaction)/amount of guaiacol substance at the beginning of reaction x 100%
Yield of cyclohexanol = amount of cyclohexanol material at end of reaction/amount of guaiacol material at start of reaction x 100%
Selectivity of cyclohexanol = yield of cyclohexanol/conversion of guaiacol x 100%
The chromatographic conditions were: the hydrogen flame detector FID is adopted, hydrogen is used as carrier gas, an internal standard method is adopted, and tetradecane is used as an internal standard.
3. The reaction results are shown in Table 1
TABLE 1 results for different reaction temperatures
Examples 1-3 show that guaiacol can also be converted at 180℃with a lower reaction rate, and that 100% conversion and 95% cyclohexanol yield can be achieved with guaiacol at 200 ℃. When the temperature is higher than 220 ℃, the cyclohexanol selectivity is slightly reduced, indicating that the catalyst will continue to decompose at high temperatures.
Examples 2 and 4 to 6 batch reactions at different reaction pressures
1. And (3) preparing a catalyst: the procedure was as for the preparation of the catalysts in examples 1-3.
2. Reaction test: the procedure is as in examples 1-3, with specific reaction conditions set: after the device is airtight, different specified pressures H 2 and stirring rates of 700rpm are introduced, and the temperature is set to be 200 ℃ for reaction for 2 hours.
3. The reaction results are shown in Table 2.
TABLE 2 results for different reaction pressures
Examples 2 and 4-6 show that the guaiacol conversion rate can reach 100% when the reaction is carried out for 2 hours under the conditions of 1MPa-4 MPa and 200 ℃. When the H 2 pressure is 1.0MPa, the catalyst has better catalytic activity, and the cyclohexanol yield can reach 95%; when the pressure is increased to 2.0MPa, the yield of cyclohexanol slightly decreases. Increasing the pressure of H 2 continuously reduces the yield of cyclohexanol, which shows that H 2 of 1.0MPa in the reaction system can promote the reaction of guaiacol to generate cyclohexanol in a directional manner through a Co/rGO catalyst. Too high a pressure will cause a rapid conversion of guaiacol to 1-methyl-1, 2-cyclohexanediol.
Examples 2 and 7 to 11 batch reactions at different reaction times
1. And (3) preparing a catalyst: the procedure was as for the preparation of the catalysts in examples 1-3.
2. Reaction test: the procedure is the same as in examples 1-3 for the reaction test procedure, the specific reaction conditions: after ensuring that the apparatus was air-tight, stirring rates of 1MPaH 2, 700rpm were set at 200℃and the reaction was run for various times.
3. The reaction results are shown in Table 3.
TABLE 3 results for different reaction times
Examples 2 and 7-11 show that, when the reaction time is 1H, the guaiacol is converted to 95% and the yield of cyclohexanol is 81% under the conditions of 200 ℃ and 1MPa H 2, and after the reaction time reaches 2H, the yield of cyclohexanol reaches 95%, and the yield of cyclohexanol is not reduced by continuing to prolong the reaction time, which shows that the catalyst is catalytically inert to cyclohexanol at 200 ℃ and does not generate excessive hydrogenation products and ring-opening products which break benzene rings.
Comparative example 1 Ni/rGO batch reaction
1. And (3) preparing a catalyst: preparing a Ni/rGO catalyst by adopting an impregnation-roasting method, wherein the specific steps are as follows except for the preparation of a salt solution in the step (2): 72.8mg of Ni (NO 3)2·6H2 O, dissolved in deionized water to form a salt solution;
the remaining preparation steps were the same as in examples 1-3.
2. Reaction test: the performance of the Ni/rGO catalyst for catalyzing the hydrogenation reaction of guaiacol was tested by batch reaction, and the specific procedure was as in example 2.
The reaction result shows that the conversion rate of guaiacol is 90% and the selectivity of cyclohexanol is 58% under the action of the catalyst. Under the condition of the same ratio, the Co/rGO catalyst can completely convert guaiacol, and the cyclohexanol yield reaches 95%.
Comparative example 2 Fe/rGO batch reaction
1. And (3) preparing a catalyst: preparing the Fe/rGO catalyst by adopting an impregnation-roasting method, wherein the preparation of the salt solution in the step (2) is specifically performed: 101mg of Fe (NO 3)3·9H2 O, dissolved in deionized water to form a salt solution;
the remaining preparation steps were the same as in examples 1-3.
2. Reaction test: the performance of the Fe/rGO catalyst for catalyzing the guaiacol hydrogenation reaction is tested by adopting a batch reaction, and the specific steps are as in example 2.
The reaction result shows that the conversion rate of guaiacol is 4.5% and the cyclohexanol selectivity is 12% under the action of the catalyst. Under the condition of the same ratio, the Co/rGO catalyst can completely convert guaiacol, and the cyclohexanol yield reaches 95%.
Comparative examples 3-5 batch reactions of different Supported catalysts
1. And (3) preparing a catalyst: preparing Co/Al 2O3, co/HY and Co/AC catalysts by adopting an impregnation-roasting method, wherein the specific steps are as follows except for the impregnation in the step (3): the prepared salt solution was placed in a beaker. 100mgAl 2O3, HY, and AC were weighed separately, added to a beaker, and stirred continuously with a glass rod. Standing the sample at room temperature for 3 hours;
the remaining preparation steps were the same as in examples 1-3.
2. Reaction test: the performance of the Co/Al 2O3, co/HY and Co/AC catalysts for catalyzing the hydrogenation reaction of guaiacol was tested by batch reaction, and the specific procedure is as in example 2.
3. The reaction results are shown in Table 4.
TABLE 4 results for different Supported catalysts
As can be seen from comparative examples 3 to 5, co supported on Al 2O3、HY、SiO2 carrier could not obtain good catalytic activity without reduction pretreatment. Transition metal catalysis in the literature generally requires a reductive pretreatment. The pretreatment process not only complicates the catalyst preparation and maintenance process and increases energy consumption, but also some reduced catalysts may lose activity due to oxidation. The Co/rGO catalyst of the invention is directly used after N 2 is calcined and is directly operated in an air atmosphere. Therefore, the catalyst disclosed by the invention is energy-saving and efficient and has the characteristic of oxidation resistance and deactivation.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The application of the cobalt-reduced graphene oxide Co/rGO catalyst is characterized by comprising the following specific steps of: n-dodecane is used as a solvent, and guaiacol reacts with H 2 under the action of a Co/rGO catalyst to obtain cyclohexanol;
the preparation method of the cobalt-reduced graphene oxide Co/rGO catalyst is characterized by comprising the following specific steps:
(1) Preparation of a graphene carrier: taking 230mL of concentrated sulfuric acid and 5.0gNaNO 3, stirring, adding 10g of natural crystalline flake graphite powder, stirring for 2.5 hours, adding 30g of KMnO 4, transferring to 35 ℃ constant-temperature water bath for reaction for 2 hours, adding 460mL of deionized water, stirring for 15 minutes in 98 ℃ oil bath, finally adding 1.4L of deionized water for terminating reaction, simultaneously adding 25mL of 30% H 2O2, cooling to room temperature, centrifugally washing deionized water, washing to neutrality, taking the prepared GO paste with the dry content of 1g, dispersing in 1000mL of deionized water, performing ultrasonic treatment for 30 minutes, standing and ageing, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing for 3 hours in 95 ℃ oil bath, adding 4mL of 80% hydrazine hydrate for reaction for 30 minutes, adding 4% hydrochloric acid solution, filtering while hot, and freeze-drying to obtain a rGO carrier for standby;
(2) Preparation of salt solution: putting Co (NO 3)2·6H2 O into a beaker, dissolving with deionized water to prepare a salt solution, adding absolute ethyl alcohol, and shaking uniformly for later use;
(3) Dipping: weighing the rGO carrier prepared in the step (1), adding the rGO carrier into the beaker in the step (2), continuously stirring the rGO carrier with a glass rod, and standing the sample at room temperature;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12 hours, and grinding the sample into powder by an agate mortar;
(5) Roasting: placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by a program of 10 ℃/min under nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 1-4h, cooling the quartz tube to room temperature, taking out the quartz tube, and sealing and storing the quartz tube.
2. The use of the cobalt-reduced graphene oxide Co/rGO catalyst according to claim 1, wherein the sample of step (3) is left to stand at room temperature for 2-5h.
3. The use of the cobalt-reduced graphene oxide Co/rGO catalyst according to claim 1, wherein the sample of step (4) is in the form of a 80-100 mesh powder.
4. The application of the cobalt-reduced graphene oxide Co/rGO catalyst according to claim 1, wherein the ratio of Co (NO 3)2·6H2 O to carrier rGO) in the step (2) and the step (3) is 0.5-3.0 mmol/g, the volume ratio of water to ethanol is 10:1-5:5, and the salt solution prepared in the step (2) can be just absorbed by rGO weighed in the step (3).
5. The application of the cobalt-reduced graphene oxide Co/rGO catalyst according to claim 1, wherein the reaction temperature for preparing cyclohexanol by catalytic hydrogenation of guaiacol is 180-220 ℃, the hydrogen pressure is 1-4 MPa, and the reaction time is 0.25-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111143175.4A CN113731441B (en) | 2021-09-28 | 2021-09-28 | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111143175.4A CN113731441B (en) | 2021-09-28 | 2021-09-28 | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113731441A CN113731441A (en) | 2021-12-03 |
| CN113731441B true CN113731441B (en) | 2024-05-03 |
Family
ID=78741495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111143175.4A Active CN113731441B (en) | 2021-09-28 | 2021-09-28 | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731441B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478198B (en) * | 2022-01-27 | 2023-07-21 | 大连大学 | Method for preparing phenol by catalytic hydrogenation of guaiacol |
| CN116764629B (en) * | 2023-08-25 | 2023-10-20 | 内蒙古瑞翔拓创新材料有限公司 | Cyclohexene ruthenium-based catalyst prepared by benzene partial hydrogenation and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422739A (en) * | 2008-11-03 | 2009-05-06 | 大连大学 | Diatomic alcohol load type catalyst by glycerol hydrogenolysis and preparation method thereof |
| CN101774534A (en) * | 2009-11-04 | 2010-07-14 | 中国科学院上海硅酸盐研究所 | B2O3/Al2O3 composite powder with double-pore-canal nano-pore structure and preparation method thereof |
| CN109384750A (en) * | 2018-12-26 | 2019-02-26 | 大连大学 | A kind of method that catalytic hydrogenation 5 hydroxymethyl furfural prepares 2,5- dimethyl furan |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101558735B1 (en) * | 2014-02-13 | 2015-10-08 | 포항공과대학교 산학협력단 | Inorganic nanoparticle deposited catalyst for hydrogenation and manufacturing method of the same, and hydrogenation for biomass derived hydrocarbon compounds |
-
2021
- 2021-09-28 CN CN202111143175.4A patent/CN113731441B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422739A (en) * | 2008-11-03 | 2009-05-06 | 大连大学 | Diatomic alcohol load type catalyst by glycerol hydrogenolysis and preparation method thereof |
| CN101774534A (en) * | 2009-11-04 | 2010-07-14 | 中国科学院上海硅酸盐研究所 | B2O3/Al2O3 composite powder with double-pore-canal nano-pore structure and preparation method thereof |
| CN109384750A (en) * | 2018-12-26 | 2019-02-26 | 大连大学 | A kind of method that catalytic hydrogenation 5 hydroxymethyl furfural prepares 2,5- dimethyl furan |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113731441A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109174085B (en) | Atomic-level dispersed palladium-based nano-diamond/graphene composite material catalyst and preparation method and application thereof | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN113101933B (en) | Supported nickel-cobalt bimetallic nano catalyst and application thereof in catalyzing selective hydrogenation reaction of vanillin | |
| CN110327962B (en) | Nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, and preparation method and application thereof | |
| CN111153768B (en) | Synthesis method of isohexide | |
| CN112138698B (en) | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction | |
| CN108623436B (en) | Method for converting cellulose into bioethanol by one-pot method | |
| CN114656337A (en) | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin | |
| CN114471540A (en) | Sub-nano Pt selective hydrogenation catalyst, preparation method and application thereof | |
| CN110339852B (en) | CoO @ nitrogen and sulfur co-doped carbon material/CdS composite photocatalytic material, and preparation method and application thereof | |
| CN112191252B (en) | Tubular cobaltosic oxide catalyst modified by dispersing nano nickel particles in cerium dioxide and preparation method and application thereof | |
| CN112778243A (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN107442134B (en) | Rhodium/nickel alloy nano catalyst and preparation method and application thereof | |
| CN114588940B (en) | Nickel-based catalyst for hydrogenation of phenolic compounds, and preparation method and application thereof | |
| CN113304756B (en) | Ni-Mo bimetal alloy catalyst and preparation method and application thereof | |
| CN114054023B (en) | Preparation method and application of alloy monoatomic catalyst | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN111097497B (en) | Method for producing hydrogen by catalyzing direct conversion of methane, catalyst and preparation method thereof | |
| CN107952439B (en) | Catalyst for catalyzing methanol carbonylation, preparation method thereof, and method for preparing acetic acid and methyl acetate by methanol carbonylation | |
| CN114478198B (en) | Method for preparing phenol by catalytic hydrogenation of guaiacol | |
| CN102029155B (en) | Hydrogen producing catalyst | |
| CN115715982B (en) | Catalyst suitable for preparing VA and MMP, catalyst preparation method and catalysis method | |
| CN115197280B (en) | Metal cobalt complex with photocatalytic carbon dioxide reduction activity and preparation method and application thereof | |
| CN112791735A (en) | Cadmium sulfide material for anaerobic dehydrogenation of photocatalytic alcohol, and preparation and application thereof | |
| CN112774662A (en) | Monoatomic catalyst, preparation method and application thereof |
Legal Events
| 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 |