CN115282982B - CoAg/SiO 2 Bimetallic catalyst and preparation method and application thereof - Google Patents
CoAg/SiO 2 Bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 claims abstract description 54
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005770 Eugenol Substances 0.000 claims abstract description 6
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960002217 eugenol Drugs 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- LUOAEJWSKPQLJD-UHFFFAOYSA-N syringyl alcohol Chemical compound COC1=CC(CO)=CC(OC)=C1O LUOAEJWSKPQLJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 229940094933 n-dodecane Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000011521 glass Substances 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
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229920005610 lignin Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QSZCGGBDNYTQHH-UHFFFAOYSA-N 2,3-dimethoxyphenol Chemical compound COC1=CC=CC(O)=C1OC QSZCGGBDNYTQHH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001971 elastomer Polymers 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
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KJNDNYDBXVVIKZ-UHFFFAOYSA-N 1,2,3-trimethoxycyclohexane Chemical compound COC1CCCC(OC)C1OC KJNDNYDBXVVIKZ-UHFFFAOYSA-N 0.000 description 1
- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention belongs to the technical field of cyclohexanol preparation, and discloses a CoAg/SiO2 bimetallic catalyst, and a preparation method and application thereof, namely, eugenol in CoAg and SiO 2 And (3) carrying out selective hydrogenation reaction under the action of a composite material catalyst to generate cyclohexanol. CoAg/SiO 2 The catalyst is not required to be subjected to high-temperature pre-reduction treatment before use, and reacts for 2 hours under the conditions of 280 ℃ and 3MPa of hydrogen pressure, the conversion rate of the syringol is 100%, and the yield and the selectivity of the cyclohexanol can reach 94%. The catalyst has simple preparation and maintenance process, high reaction activity, good selectivity and industrial application value.
Description
Technical Field
The invention belongs to the technical field of cyclohexanol preparation, and relates to a CoAg/SiO 2 Bimetallic catalyst and preparation method and application thereof, in particular to CoAg/SiO 2 A method for preparing cyclohexanol by catalyzing selective hydrogenation of syringyl alcohol by a bimetallic catalyst.
Background
At present, the global energy consumption is continuously increased, the fossil energy reserves are limited, and the requirement of sustainable development cannot be met; meanwhile, the large consumption of energy sources also causes the problems of environmental pollution, climate warming and the like. Therefore, it is necessary to quickly find an environmentally friendly renewable resource. Biomass energy is paid attention to due to the characteristics of low carbon emission, abundant storage capacity, wide distribution and the like, and is the only carbon-based renewable resource in nature. Lignin is one of the main components of biomass, and the structure of lignin is rich in benzene rings, so that the lignin can be refined to obtain rich six-membered ring hydrocarbon compounds, such as cyclohexanol. Cyclohexanol is an industrial raw material with wide application, and can be used as a solvent for substances such as fiber, rubber, paint and the like; a stabilizer for the water-soluble latex; resin stabilizers such as monomers for polymerization, plasticizers, and PVC; petroleum processing aids, rubber additives, pharmaceuticals, and the like. In addition, cyclohexanol is also an important chemical for the preparation of nylon, caprolactam and adipic acid. The key to lignin conversion is the development of efficient catalysts. Since lignin is a high molecular polymer, a model compound is often used as a raw material in the search of a catalyst. The syringyl alcohol structure can more represent a typical structural unit of lignin, but has larger steric hindrance, low reaction activity and poor selectivity, and the research of using the syringyl alcohol structure as a model compound to explore lignin hydrogenation to prepare chemicals is less.
Shu R,Zhang Q,Xu Y,et al.Hydrogenation of lignin-derived phenolic compounds over step by step precipitated Ni/SiO 2 [J]RSC extensions, 2016,6 (7): 5214-5222. Ni/SiO is prepared by a distributed precipitation method 2 -Al 2 O 3 The catalyst is pretreated by hydrogen reduction at 550 ℃ before use. The reaction is carried out for 2 hours under the hydrogen pressure of 2MPa at 200 ℃, the conversion rate of the syringol reaches 100 percent, and the selectivity of the product is 97.8 percent because of transitional hydrogenation and the cyclohexane is the main product. The catalyst is repeatedly used for three times under the reaction condition, the activity of the catalyst and the selectivity of cyclohexane as a product are reduced, and the coking of the catalyst is a main cause of the deactivation of the catalyst. Szczyglewska P, feliczak-Guzik A, jaroniec M, et al Catalytic role of metals supported on SBA-16 in hydrodeoxygenation of chemical compounds derived from biomass processing[J]RSC Advances,2021,11 (16): 9505-9517. 3% Ir/SBA-16, 3% Ru/SBA-16, 3% Pd/SBA-16, 3% Pt/SBA-16 catalysts were pretreated by reduction at 400 ℃, 250 ℃, 350 ℃, 250 ℃ respectively, then syringol was catalyzed by them, and reacted for 4 hours under 6MPa hydrogen pressure at 130 ℃, 3% Ir/SBA-16 and 3% Pt/SBA-16 catalysts were used, the reactivity was poor, and the syringol conversion was 5%, 2%, respectively; when using 3% Ru/SBA-16 and 3% Pd/SBA-16 catalysts, the conversion rate of syringol is 100% and 48% respectively, and the main products are 1,2, 3-trimethoxycyclohexane. Liu Xiaohao cobalt-based catalyst catalyzed lignin phenols hydrodeoxygenation [ D ]]University of science and technology, 2017 CoN was prepared in an in situ co-pyrolysis method X N.sub.NC catalyst, n-dodecane as solvent, 6.53wt% CoN X 76mg of @ NC catalyst and 1mmol of syringol were placed in a Parr kettle at 200℃under 2MPa of hydrogenThe reaction is carried out for 2 hours under pressure, the conversion rate of the syringol is 43.4%, the cyclohexane yield is 9.1%, the dimethoxy phenol yield is 9.7%, when the reaction time is prolonged for 12 hours, the conversion rate of the syringol is 100%, and the product is cyclohexane due to transitional hydrogenation, and the yield is close to 100%. In addition, 10wt% Co/TiO was prepared by impregnation 2 The catalyst reacts for 6 hours under the hydrogen pressure of 1MPa at 200 ℃, the conversion rate of the syringol is 100 percent, the yield of the cyclohexanol reaches 99.9 percent, which is a catalyst with the less cyclohexanol yield reaching more than 90 percent at present, and the defect that the catalyst needs to be used at 600 ℃ and H before being used is that 2 In addition, the cyclic experiment finds that the metal loss and agglomeration are easy to cause in the catalytic reaction process, so that the catalyst is deactivated. Ishikawa M, tamura M, nakagawa Y, et al Demethox of guaiacol and methoxybenzenes over carbon-supported Ru-Mn catalyst [ J ]]Applied Catalysis B Environmental,2016, 182:193-203A 5wt% Ru-MnOx/C catalyst was prepared by impregnation, in which Ru and Mn were reacted in a ratio of 1:1, violet eugenol at 160℃and a hydrogen pressure of 1.5MPa for 4h with a conversion of approximately 100% and a cyclohexanol selectivity of 70% due to the formation of cyclohexane by transient hydrogenation.
At present, the related researches on preparing cyclohexanol by selective hydrogenation of syringol are few, and a plurality of catalyst systems used in the literature need reduction pretreatment before being put into a reaction system, so that the catalyst preparation and maintenance process is complicated, the operation cost is increased, in addition, the catalyst activity is low, the reaction time is long, and the catalyst activity is high, but the selectivity to cyclohexanol is low, and the cyclohexane is easy to be subjected to transitional hydrogenation. Therefore, for this reaction, there is a need to develop a catalyst which does not require a reduction pretreatment, has high reactivity, and has good selectivity to cyclohexanol.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, the present invention provides a CoAg/SiO 2 Bimetallic catalyst and its preparation method and application.
The invention is characterized in that: the catalyst takes cheap transition metal Co as a hydrogenation active component, precious metal Ag as an auxiliary agent and silicon dioxide (SiO) 2 ) Is a carrierThe catalyst is prepared by adopting an impregnation method, the preparation process is simple, the catalyst does not need to be subjected to high-temperature reduction pretreatment under the action of Ag auxiliary agent, and high catalytic activity and product selectivity are generated under mild conditions, so that the novel high-efficiency catalyst is provided for preparing cyclohexanol by selective hydrogenation of syringol.
The invention aims at realizing the following technical scheme:
CoAg/SiO 2 The preparation method of the bimetallic catalyst adopts an impregnation-roasting method, and comprises the following steps:
(1) Preparation of salt solution: taking a certain amount of Co (NO) 3 ) 2 ·6H 2 O and AgNO 3 Placing in a beaker, and dissolving with deionized water to prepare a salt solution;
(2) Dipping: weighing SiO 2 The carrier is added into the salt solution prepared in the step (1) at one time, a glass rod is used for continuous stirring, and the sample is placed at room temperature for standing for 2-5 h;
(3) And (3) drying: placing the sample after standing in the step (2) in a blast drying oven to be dried for 8-12 hours at 50-80 ℃, and grinding the sample into powder by using a mortar;
(4) Roasting: placing the powdery sample prepared in the step (3) into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ from room temperature through a programming temperature of 1-10 ℃/min, roasting the crucible at the constant temperature of 500 ℃ for 1-3 hours, and taking out the sample and storing the sample in a sealing way when the temperature is reduced to the room temperature;
further, co (NO) is disposed in the step (1) 3 ) 2 ·6H 2 O and AgNO 3 In the case of salt solutions, the molar ratio of Co to Ag is 1:0.05-1:0.5, preferably 1:0.25, co (NO 3 ) 2 ·6H 2 O and carrier SiO 2 The proportion relation of (2) is SiO per g 2 The carrier supported 2.0mmol of Co.
CoAg/SiO 2 Bimetallic catalysts were prepared as described above.
CoAg/SiO 2 The application of the bimetallic catalyst is used for catalyzing selective hydrogenation of syringyl alcohol to prepare cyclohexanol.
Further, the catalytic syringol selectionThe method for preparing cyclohexanol by hydrogenation comprises the following steps: n-dodecane is used as solvent, and the eugenol is used in CoAg/SiO 2 Under the action of catalyst and H 2 The catalyst is used in the amount of 5-30% of the material syringol, the reaction temperature is 250-310 ℃, the hydrogen pressure is 1-4 MPa, and the reaction time is 1-4 h, so as to obtain cyclohexanol.
Further, the selective hydrogenation reaction temperature of syringyl alcohol is preferably 280 ℃, and the hydrogen pressure is preferably 3MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1)Co/SiO 2 a small amount of noble metal Ag is introduced into the catalyst as an auxiliary agent, so that the conversion rate of syringol and the selectivity of cyclohexanol are both improved. The catalyst does not need to be subjected to high-temperature pre-reduction treatment and is not deactivated by oxidation.
(2)CoAg/SiO 2 The catalyst is prepared by adopting an impregnation-roasting method, the preparation method is simple, and the catalyst is suitable for large-scale industrial preparation. At 280 ℃ and 3MPa H 2 Under the condition of 2 hours, the yield of the cyclohexanol can reach 94 percent, and the cyclohexanol has high selectivity.
In conclusion, coAg/SiO 2 The catalyst has the characteristics of high reaction activity, high selectivity and the like when catalyzing selective hydrogenation reaction of syringol, the conversion rate of the reaction syringol can reach 100%, the selectivity of cyclohexanol can reach 94%, the catalyst does not need to be subjected to high-temperature prereduction in the reaction process, and the preparation method is simple, is suitable for industrialized mass preparation, and has obvious advantages and industrial application value.
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.
Examples 1-3 batch reactions at different reaction temperatures
1. And (3) preparing a catalyst: preparation of CoAg/SiO by impregnation-roasting 2 The catalyst comprises the following specific steps:
(1)preparation of salt solution: 0.5821gCo (NO) 3 ) 2 ·6H 2 O and 0.0849gAgNO 3 Placing in a beaker, and dissolving with 1.8mL of deionized water to prepare a salt solution;
(2) Dipping: 1.0000g of SiO was weighed out 2 The carrier is added into the salt solution prepared in the step (1) at one time, a glass rod is used for continuous stirring, and the sample is placed at room temperature for standing for 2-5 h;
(3) And (3) drying: placing the sample after standing in the step (2) in a forced air drying oven for drying at 50-80 ℃ for 8-12 h, and grinding the sample into powder by using a mortar;
(4) Roasting: and (3) placing the powdery sample prepared in the step (3) into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ from room temperature through a programming temperature of 1-10 ℃/min, roasting the crucible at the constant temperature of 500 ℃ for 1-3 hours, and taking out the sample when the temperature is reduced to the room temperature, and sealing and storing the sample.
2. Reaction test: testing of CoAg/SiO Using batch reaction 2 The catalyst has the performance of catalyzing selective hydrogenation reaction of syringol, and comprises the following specific steps:
(1) Taking a mechanically-stirred high-pressure reaction kettle, adding 500.0mg of eugenol, 10mlL n-dodecane, 120mg of internal standard tetradecane and 50mg of CoAg/SiO 2 The catalyst is used for screwing the reaction kettle and checking the air tightness of the device, so that the 3MPaH is introduced after the device is airtight 2 The stirring rate was 700rpm, and the designated temperature was set 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 syringol= (amount of syringol substance at the beginning of reaction-amount of syringol substance at the end of reaction)/amount of syringol substance at the beginning of reaction x 100%
Yield of cyclohexanol = amount of cyclohexanol material at the end of reaction/amount of syringol material at the start of reaction x 100%
Selectivity of cyclohexanol = yield of cyclohexanol/conversion of syringol x 100%
The chromatographic conditions were: hydrogen flame detector (FID), hydrogen as carrier gas, internal standard method, tetradecane as internal standard.
3. The reaction results are shown in Table 1
TABLE 1 results for different reaction temperatures
As can be seen from examples 1-3, the conversion of syringol was 73% at a reaction temperature of 250℃but the cyclohexanol selectivity was lower, and 100% conversion and 94% yield of cyclohexanol was achieved with syringol when the reaction temperature reached 280 ℃. When the temperature is 310 ℃, the cyclohexanol selectivity is slightly reduced, which indicates that the catalyst is continuously hydrogenated to form cyclohexane at high temperature.
Examples 2,4-6 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 the same as in examples 1-3 for the reaction test procedure, the specific reaction conditions: ensuring that the device is airtight and then is supplied with a specified pressure H 2 The reaction was carried out at a stirring rate of 700rpm at a set temperature of 280℃for 2 hours.
3. The reaction results are shown in Table 2.
TABLE 2 results for different reaction pressures
As can be seen from examples 2,4-6, the conversion of syringyl alcohol increases with increasing reaction pressure when the reaction is carried out for 2 hours under a hydrogen pressure of 1MPa to 4MPa and a temperature of 280 ℃. When the hydrogen pressure was 3.0MPa, the syringyl alcohol was completely converted and the cyclohexanol selectivity was 94%. When H is 2 At a pressure of 4.0MPa, the cyclohexanol yield was reduced, indicating excess H 2 The pressure causes the cyclohexanol to continue to hydrogenate to form cyclohexane.
Examples 2,7-8 batch reactions at different reaction times
2. 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: ensuring that the device is air-tight and then is introduced with 3MPaH 2 The stirring rate was 700rpm, and the reaction was set at 280℃for the indicated time.
3. The reaction results are shown in Table 3.
TABLE 3 results for different reaction times
As can be seen from examples 2,7-8, 280℃and 3MPaH 2 When the reaction time is 2h, the conversion of the purple eugenol can be 100%, the yield of the cyclohexanol is 94%, the reaction time is prolonged continuously, and the yield of the cyclohexanol is not changed greatly, so that the cyclohexanol is stable in the reaction system.
Comparative example 1Co/SiO 2 Batch reaction of catalyst
1. And (3) preparing a catalyst: preparation of Co/SiO by impregnation-roasting 2 The catalyst comprises the following specific steps:
except for the preparation of the salt solution in the step (1): 0.5821g of Co (NO) 3 ) 2 ·6H 2 O, dissolving with 1.8mL of deionized water to prepare a salt solution; the remaining preparation steps were the same as in examples 1-3.
2. Reaction test: co/SiO testing Using batch reaction 2 The catalyst catalyzes the selective hydrogenation reaction of syringol, and the specific steps are the same as in examples 1-3.
The reaction result shows that the conversion rate of the syringyl alcohol is 12% and the cyclohexanol selectivity is 28% under the action of the catalyst. Under the condition of the same ratio, the CoAg/SiO of the invention 2 The catalyst can completely convert syringyl alcohol, and the yield of cyclohexanol reaches 94%.
Comparative example 2Ag/SiO 2 Batch reaction of catalyst
1. And (3) preparing a catalyst: preparation of Ag/SiO by impregnation-roasting method 2 The catalyst comprises the following specific steps:
except for the preparation of the salt solution in the step (1): 0.0849g of AgNO was weighed out 3 Dissolving with 1.8mL of ionized water to prepare a salt solution; the remaining preparation steps were the same as in examples 1-3.
2. Reaction test: testing Ag/SiO Using intermittent reaction 2 The catalyst catalyzes the selective hydrogenation reaction of syringol, and the specific steps are the same as in examples 1-3.
The reaction results showed that the conversion of syringol was 4% with the catalyst and that no cyclohexanol was detected in the product. Under the condition of the same ratio, the CoAg/SiO of the invention 2 The catalyst can completely convert syringyl alcohol, and the yield of cyclohexanol reaches 94%.
Co/SiO 2 Catalyst and Ag/SiO 2 The sum of the yields of cyclohexanol obtained by the catalyst reaction is far lower than CoAg/SiO 2 The yield of cyclohexanol obtained by the catalyst reaction shows that SiO is simultaneously supported 2 The surface coags are not simply physical stacks but rather form a synergistic effect, resulting in excellent catalysis.
The catalysts mentioned in the literature generally require a reductive pretreatment which not only complicates the catalyst preparation and maintenance process and increases the energy consumption, but also some reduced catalysts may lose activity due to oxidation. CoAg/SiO according to the invention 2 The catalyst can generate catalytic activity without hydrogen reduction pretreatment, is directly used after roasting in a muffle furnace, and can be directly operated in an air atmosphere without a glove box in the weighing process. 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. CoAg/SiO 2 The application of the bimetallic catalyst is characterized in that the bimetallic catalyst is used for catalyzing selective hydrogenation of syringyl alcohol to prepare cyclohexanol, and the CoAg/SiO is prepared by 2 The bimetallic catalyst is prepared by adopting a dipping-roasting method and comprises the following steps:
(1) Preparation of salt solution: taking a certain amount of Co (NO) 3 ) 2 ·6H 2 O and AgNO 3 Placing in a beaker, and dissolving with deionized water to prepare a salt solution;
(2) Dipping: weighing SiO 2 The carrier is added into the salt solution prepared in the step (1) at one time, a glass rod is used for continuously stirring, and the sample is placed at room temperature for standing for 2-5 hours;
(3) And (3) drying: placing the sample subjected to standing in the step (2) in a forced air drying oven, drying at 50-80 ℃ for 8-12 hours, and grinding the sample into powder by using a mortar;
(4) Roasting: and (3) placing the powdery sample prepared in the step (3) into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ from room temperature through a programming temperature of 1-10 ℃/min, roasting the crucible at the constant temperature of 500 ℃ for 1-3 hours, and taking out the sample when the temperature is reduced to the room temperature, and sealing and storing the sample.
2. A CoAg/SiO as claimed in claim 1 2 The application of the bimetallic catalyst is characterized in that,
the Co (NO) is configured in the step (1) 3 ) 2 ·6H 2 O and AgNO 3 In the salt solution, the molar ratio of Co to Ag is 1:0.05-1:0.5.
3. A CoAg/SiO as claimed in claim 1 2 The application of the bimetallic catalyst is characterized in that,
the Co (NO) is configured in the step (1) 3 ) 2 ·6H 2 O and AgNO 3 In the case of salt solutions, the molar ratio of Co to Ag was 1:0.25.
4. A CoAg/SiO as claimed in claim 1 2 The application of the bimetallic catalyst is characterized in that the method for preparing cyclohexanol by catalyzing selective hydrogenation of syringol comprises the following steps: n-dodecane is used as solvent, and the eugenol is used in CoAg/SiO 2 Under the action of catalyst and H 2 The reaction is carried out, and the dosage of the catalyst is raw material purple5-30% of eugenol by mass, wherein the reaction temperature is 250-310 ℃, the hydrogen pressure is 1-4 MPa, and the reaction time is 1-4 h, so as to obtain cyclohexanol.
5. A CoAg/SiO as claimed in claim 4 2 The application of the bimetallic catalyst is characterized in that the reaction temperature is 280 ℃ and the hydrogen pressure is 3MPa.
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| CN105582956A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method |
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| CN105582956A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method |
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