CN108579781A - A kind of phenol hydrogenation catalyst and preparation method thereof - Google Patents
A kind of phenol hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN108579781A CN108579781A CN201810081264.2A CN201810081264A CN108579781A CN 108579781 A CN108579781 A CN 108579781A CN 201810081264 A CN201810081264 A CN 201810081264A CN 108579781 A CN108579781 A CN 108579781A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 10
- 238000005554 pickling Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
Abstract
The present invention relates to a kind of phenol hydrogenation catalyst and preparation method thereof, belong to catalysis technical field.The catalyst is with 67 TiO of ZIF2For presoma, using the method for slow temperature programming by 67 TiO of ZIF2Calcining generates Co/CN TiO2Then CN TiO are prepared by the method for pickling in material2Carrier, then through active component salt stirring dipping, H2Catalyst is made in reduction.The advantages of the invention, is, passes through a small amount of Detitanium-ore-type TiO2Modified ZIF 67 can obviously increase the specific surface area of carrier, and enhance electron transport ability, and the catalytic performance of phenol hydrogenation preparing cyclohexanone is made to be obviously improved, and catalyst obtained has good catalytic stability.
Description
Technical field
The present invention relates to a kind of phenol hydrogenation catalyst and preparation method thereof, belong to catalysis technical field.
Background technology
Cyclohexanone is a kind of important industrial chemicals, is the important intermediate for producing nylon 6 and nylon66 fiber, industrial at present
Main preparation path is cyclohexane oxidation process.But the cyclohexane oxidation process carried out under high temperature, high pressure can generate many by-products
Object is a kind of disagreeableness production technology of environment.In recent years, the work of the low and environmentally friendly phenol direct hydrogenation preparing cyclohexanone of energy consumption
Skill has been to be concerned by more and more people.
In recent years, carbon-nitrogen material oneself widely paid close attention to through causing researcher, N element introducing can not only change carbon material
Acid-base property, electric conductivity, parent/hydrophobicity, can equally basic sites be used as to adsorb specific substrate, such as phenol hydrogenation preparing cyclohexanone
When, phenol is chemisorbed on carrier surface, and carrying out reaction by the hydrogen activated by active component on carrier generates cyclohexanone.Carbon
N in nitrogen material has the function of selective absorption for phenol, but weaker for the adsorption capacity of cyclohexanone, therefore can be with
Improve the selectivity of cyclohexanone in product.Such as Pd@mpg-C3N4Very high selectivity is achieved in this reaction（99 %）.But
It is to synthesize mpg-C3N4Complex process and condition it is more difficult to control.Therefore, a kind of synthesis of simple and effective carbon nitrogen carriers is found
Method is particularly important.
Class zeolite imidazole skeleton ester material（Zeolitic Imidazolate Frameworks, ZIFs）It is a kind of research
Compare extensive metal-organic framework（Metal-Organic Frameworks, MOFs）Material, by metal node zinc or
Cobalt is synthesized with imidazoles or imidazate by way of self assembly.ZIFs material pore passage structures are orderly, and imidazoles and imidazoles
Contain a large amount of carbon nitrogen in derivative, therefore the method that can be pyrolyzed by a step prepares CN carriers.
Research shows that metal can effectively enhance the phenol hydrogenation performance of catalyst with the direct heterojunction structure of semiconductor.
Titanium dioxide（TiO2）It is used for catalyst or catalyst carrier as a kind of environmental-friendly semi-conducting material, particularly,
Detitanium-ore-type TiO2Under lower temperature hydrogen reducing（Less than 300 DEG C）There are strong interactions with metal, can improve catalysis
Performance.So introducing TiO in CN materials2, the interaction of carrier and active component can be improved, to improve the benzene of catalyst
Phenol Hydrogenation.
Invention content
The purpose of the invention is to provide a kind of high performance phenol hydrogenation to prepare cyclohexanone catalyst；In synthesis ZIF-
Detitanium-ore-type TiO is added during 672, CN-TiO is prepared by high-temperature calcination, pickling2Carrier, and load Pd nano particle systems
Standby Pd@CN-TiO2Catalyst.
The technical scheme is that：
A kind of phenol hydrogenation catalyst and preparation method thereof, is as follows：
Step 1：Using 2-methylimidazole as solute, methanol is solvent solution-forming I；Using cabaltous nitrate hexahydrate as solute, methanol is
Solvent solution-forming II；By two kinds of solution, ultrasound is to clear respectively, for use；
Step 2：By anatase TiO2It is scattered in the methanol solution of polyvinylpyrrolidone, stirring a period of time obtains poly- second
The TiO that alkene pyrrolidone is stablized2Soliquid；
Step 3：The solution I that step 1 is configured, is added in suspension, and solution II is added in stirring a period of time afterwards again, continues to stir
It is stood after mixing a period of time；Mixed liquor after standing is centrifuged into out deposit, is used in combination methanol or ethyl alcohol to wash, baking oven is dry
It is dry, obtain ZIF-67-TiO2；
Step 4：The ZIF-67-TiO that step 3 is obtained2It is placed in tube furnace, is roasted under nitrogen or indifferent gas atmosphere
It burns, obtained sample is named as Co/CN-TiO2；
Step 5：The Co/CN-TiO that step 4 obtains2It flows back in the acid solution under a certain concentration and under water bath condition and washes
A period of time is washed, is then washed with deionized, is placed in oven drying, obtained sample is denoted as CN-TiO2；
Step 6：Sample is impregnated into palladium chloride aqueous solution obtained by step 5, after stirring dipping, centrifugation, and oven drying；
Step 7：Sample obtained by step 6 is restored under an atmosphere of hydrogen, natural cooling obtains Pd@CN-TiO2。
A concentration of 0.4 ~ 1.6 mol/L for the 2-methylimidazole solution that preferred steps one are configured；Cabaltous nitrate hexahydrate
Solution concentration is respectively 0.05 ~ 0.2 mol/L.
The mass concentration of polyvinylpyrrolidone methanol solution described in preferred steps two is 10 ~ 40 g/L, TiO2
The 0 ~ 1/4 of a concentration of cabaltous nitrate hexahydrate solution concentration, mixing time are 10 ~ 30 min.
I, II and TiO of solution described in preferred steps three2The volume ratio of soliquid is 1:1:1, I He of solution is added
Mixing time is respectively 10 ~ 30 min and 8 ~ 20 h after II, and time of repose is 0 ~ 5 h；Washing times are 2 ~ 5 times；
Drying temperature is 50 ~ 80oC, 6 ~ 24 h of drying time.
Inert gas described in preferred steps four is helium or argon gas；Calcination temperature is 550 ~ 800oC, calcination time
4 ~ 8 h, heating rate are 1 ~ 4 oC/min。
Acid solution described in preferred steps five is nitric acid or hydrochloric acid, and mass concentration is 20 ~ 40%；2 ~ 5 h of return time；
Deionized water washing times are 3 ~ 6 times；Oven drying temperature is 80 ~ 120oC, 6 ~ 10 h of drying time.
A concentration of 0.45 ~ 1.2 g/L of palladium bichloride dipping solution described in preferred steps six, dip time are 4 ~ 12 h.
Hydrogen reducing temperature described in preferred steps seven is 150 ~ 300oC, 3 ~ 6 h of recovery time, heating rate are
1 ~ 4 oC/min。
The present invention uses phenol selectivity Hydrogenation cyclohexanone for the catalytic performance of model reaction evaluation prepared catalyst.
Detailed process is as follows：
The reaction unit that this reaction uses is the Schlenk pipe of 25 mL.First by 0.10 g Pd@CN-TiO2Catalyst is added to
Guan Zhong is subsequently added into the phenol solution of 5 mL 1wt %.Reaction temperature control is 80oC, reaction pressure are 1 bar.Reaction
Time is 70 min.Take reaction product centrifugation, filtering after use gas chromatographic analysis, according to standard curve calculate feed stock conversion and
Selectivity of product.
Advantageous effect：
Detitanium-ore-type TiO is added during synthesizing ZIF-672, high-specific surface area can be prepared by calcining, pickling
CN-TiO2Carrier, and the electron transport ability enhancing between carrier and metal active centres Pd nano particles, improve catalyst
Phenol hydrogenation performance.
Description of the drawings
Fig. 1 is CN-TiO in embodiment 12- 0.01 be not added with TiO2The CN-TiO of preparation2The N of -0 carrier2Adsorption/desorption figure,
Wherein a is to be not added with TiO2The CN-TiO of preparation2The adsorption section of -0 carrier, a ' are CN-TiO2The desorption section of -0 carrier.B is to implement
CN-TiO in example 12The adsorption section of -0.01 carrier, b ' are CN-TiO2The desorption section of -0.01 carrier.
Fig. 2 is Pd@CN-TiO in embodiment 12- 0.01 be not added with TiO2The Pd@CN-TiO of preparation2The N 1s of -0 catalyst
XPS is characterized, wherein (a) Pd@CN-TiO2- 0, (b) Pd@CN-TiO2-0.01。
Specific implementation mode
The method of the present invention and the using effect of catalyst are illustrated below by embodiment, the following example is only used for
The bright present invention, but be not used to limit the practical range of the present invention.
Embodiment 1
(1) ZIF-67-TiO2Preparation
The 0.1 mol/L cabaltous nitrate hexahydrates of 2-methylimidazole methanol solution and 50 mL of 50 mL, 0.8 mol/L are configured first
Methanol solution.By 0.01 g TiO2It is scattered in the polyvinylpyrrolidone methanol solution of 50 mL, 20 g/L, stirring 10
2-methylimidazole solution is placed in after min, continues to stir 10 min, Co (NO is added3)2·6H2O methanol solutions are mixed 10
Stop stirring after h, mixed liquor is stood to 1 h at ambient temperature.Product is detached by way of centrifugation after standing
Out, it is used in combination methanol to wash 3 times, finally 80oDry 6 h, sample are denoted as ZIF-67-TiO in the baking oven of C2-0.01。
(2) CN-TiO2The preparation of carrier
The ZIF-67-TiO for taking 0.5 g to be prepared2- 0.01 in tube furnace, and calcination atmosphere is argon gas, calcination temperature 600oC, calcination time are 5 h.Temperature rises to target temperature, heating rate 1 from room temperatureoC/min.Sample after calcining is denoted as Co/
CN-TiO2-0.01.The Co/CN-TiO being prepared2- 0.01 sample is in the salpeter solution of 34 %, in 60oC, lasting stirring
Under conditions of 5 h of pickling, be washed with deionized water after pickling 4 times, finally by sample 80o10 h are dried in C baking ovens, are obtained
Sample be denoted as CN-TiO2-0.01。
(3) Pd@CN-TiO2The preparation of catalyst
Take 0.2 g CN-TiO2Stirring 12 h of dipping in the palladium chloride aqueous solution of -0.01 15 mL of dispersion, 0.89 g/L, centrifugation,
8 h of oven drying.The sample being dried to obtain is placed in tube furnace, in atmosphere of hydrogen, heating rate 2oIt heats up under C/min
To 250o6 h are restored under C, obtain Pd@CN-TiO2- 0.01 catalyst.
With Pd@CN-TiO2- 0.01 preparation method is identical, is not added with TiO2The catalyst being prepared is denoted as Pd@CN-TiO2-
0.Fig. 1 is CN-TiO2- 0.01 and CN-TiO2- 0 N2Isothermal adsorption desorption figure, it can be seen that it is lower in relative pressure,
Adsorbance occurs hysteresis loop when relative pressure is higher, illustrates CN-TiO there are one the process uprushed2- 0.01 and CN-
TiO2- 0 all has micro--meso-hole structure；By the height of adsorbance, it can be found that having added TiO2CN-TiO2- 0.01 specific surface
Product significantly increases.Fig. 2 is Pd@CN-TiO2- 0.01 and Pd@CN-TiO2N 1s XPS swarming figures in -0 catalyst, it can be found that system
Graphite nitrogen is existed simultaneously with pyridine nitrogen in standby catalyst, and Pd@CN-TiO2- 0.01 graphite nitrogen content dramatically increases, and carries
Body electron transport ability enhances.
By catalyst Pd@CN-TiO2- 0.01 applies in the experiment of phenol hydrogenation preparing cyclohexanone, is converted after reacting 70 min
Rate is 98.0 %, and selectivity is 98.0 %.It is not added with TiO2The catalyst Pd@CN-TiO of preparation2- 0 applies to phenol hydrogenation hexamethylene
In ketone experiment, conversion ratio is 72.3% after reacting 70 min, and selectivity is 98.3%.
Embodiment 2
(1) ZIF-67-TiO2Preparation
The 0.05 mol/L cabaltous nitrate hexahydrates of 2-methylimidazole methanol solution and 50 mL of 50 mL, 1.6 mol/L are configured first
Methanol solution.By 0.05 g TiO2It is scattered in the polyvinylpyrrolidone methanol solution of 50 mL, 10 g/L, stirring 30
2-methylimidazole solution is placed in after min, continues to stir 10 min, Co (NO is added3)2·6H2O methanol solutions are mixed 8
Stop stirring after h, mixed liquor is stood to 5 h at ambient temperature.Product is detached by way of centrifugation after standing
Out, it is used in combination methanol to wash 5 times, finally 50oDry 24 h, sample are denoted as ZIF-67-TiO in the baking oven of C2-0.05。
(2) CN-TiO2The preparation of carrier
The ZIF-67-TiO for taking 0.5 g to be prepared2- 0.05 in tube furnace, and calcination atmosphere is helium, calcination temperature 550oC, calcination time are 8 h.Temperature rises to target temperature, heating rate 2 from room temperatureoC/min.Sample after calcining is denoted as Co/
CN-TiO2-0.05.The Co/CN-TiO being prepared2- 0.05 sample is in the salpeter solution of 40 %, in 60oC, lasting stirring
Under conditions of 2 h of pickling, be washed with deionized water after pickling 6 times, finally by sample 100o8 h are dried in C baking ovens, are obtained
Sample be denoted as CN-TiO2-0.05。
(3) Pd@CN-TiO2The preparation of catalyst
Take 0.2 g CN-TiO2- 0.05 is scattered in 8 h of stirring dipping in the palladium chloride aqueous solution of 12 mL, 0.45 g/L, centrifuges,
8 h of oven drying.The sample being dried to obtain is placed in tube furnace, in atmosphere of hydrogen, heating rate 1oIt heats up under C/min
To 300oC restores 4 h, obtains Pd@CN-TiO2- 0.05 catalyst.
By catalyst Pd@CN-TiO2- 0.05 applies in the experiment of phenol hydrogenation preparing cyclohexanone, is converted after reacting 70 min
Rate is 42.3 %, and selectivity is 99.4 %.
Embodiment 3
(1) ZIF-67-TiO2Preparation
The 0.2 mol/L cabaltous nitrate hexahydrates of 2-methylimidazole methanol solution and 50 mL of 50 mL, 0.4 mol/L are configured first
Methanol solution.By 0.1 g TiO2It is scattered in the polyvinylpyrrolidone methanol solution of 50 mL, 40 g/L, stirs 20 min
2-methylimidazole solution is placed in afterwards, continues to stir 30 min, Co (NO is added3)2·6H220 h are mixed in O methanol solutions
Stop stirring later, mixed liquor is directly separated product by way of centrifugation, is used in combination ethyl alcohol to wash 2 times, finally 70oDry 12 h, sample are denoted as ZIF-67-TiO in the baking oven of C2-0.1。
(2) CN-TiO2The preparation of carrier
The ZIF-67-TiO for taking 0.5 g to be prepared2- 0.1 in tube furnace, and calcination atmosphere is nitrogen, calcination temperature 800oC, calcination time are 4 h.Temperature rises to target temperature, heating rate 4 from room temperatureoC/min.Sample after calcining is denoted as Co/
CN-TiO2-0.1.The Co/CN-TiO being prepared2- 0.1 sample is in the hydrochloric acid solution of 20 %, in 60oC, it persistently stirs
Under the conditions of 2 h of pickling, be washed with deionized water after pickling 3 times, finally by sample 120o6 h are dried in C baking ovens, are obtained
Sample is denoted as CN-TiO2-0.1。
(3) Pd@CN-TiO2The preparation of catalyst
Take 0.2 g CN-TiO2- 0.1 is scattered in 4 h of stirring dipping in the palladium chloride aqueous solution of 14 mL, 1.2 g/L, centrifuges, dries
Case dries 8 h.The sample being dried to obtain is placed in tube furnace, in atmosphere of hydrogen, heating rate 4oIt is warming up under C/min
150 o3 h are restored under C, obtain Pd@CN-TiO2- 0.1 catalyst.
By catalyst Pd@CN-TiO2- 0.1 applies in the experiment of phenol hydrogenation preparing cyclohexanone, reacts conversion ratio after 70 min
For 50.7 %, selectivity is 99.2 %.
Claims (8)
1. a kind of phenol hydrogenation catalyst and preparation method thereof, which is characterized in that be related to being as follows：
Step 1：Using 2-methylimidazole as solute, methanol is solvent solution-forming I；Using cabaltous nitrate hexahydrate as solute, methanol is
Solvent solution-forming II；By two kinds of solution, ultrasound is to clear respectively, for use；
Step 2：By anatase TiO2It is scattered in the methanol solution of polyvinylpyrrolidone, stirring a period of time obtains polyethylene
The TiO that pyrrolidones is stablized2Soliquid；
Step 3：The solution I that step 1 configures is added to the TiO of step 2 configuration2In soliquid, stirring a period of time is again
Solution II is added afterwards, continues to stand after stirring a period of time；Mixed liquor after standing is centrifuged into out deposit, first is used in combination
Alcohol or ethyl alcohol washing, oven drying obtain ZIF-67-TiO2；
Step 4：The ZIF-67-TiO that step 3 is obtained2It is placed in tube furnace, is roasted under nitrogen or indifferent gas atmosphere,
Obtained sample is named as Co/CN-TiO2；
Step 5：The Co/CN-TiO that step 4 is obtained2It is placed in certain density acid solution and flows back under water bath condition
For a period of time, it is then washed with deionized, is placed in oven drying, obtained sample is denoted as CN-TiO2；
Step 6：Sample obtained by step 5 is impregnated into palladium chloride aqueous solution, after stirring dipping, centrifugation, oven drying；
Step 7：Sample obtained by step 6 is restored under an atmosphere of hydrogen, natural cooling obtains Pd@CN-TiO2。
2. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that step 1 was configured
A concentration of 0.4 ~ 1.6 mol/L of 2-methylimidazole solution；A concentration of 0.05 ~ 0.2 mol/ of cabaltous nitrate hexahydrate solution
L。
3. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that described in step 2
The mass concentration of polyvinylpyrrolidone methanol solution is 10 ~ 40 g/L, TiO2A concentration of cabaltous nitrate hexahydrate solution concentration
0 ~ 1/4, mixing time be 10 ~ 30 min.
4. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that described in step 3
I, II and TiO of solution2The volume ratio of soliquid is 1:1:1, mixing time is respectively 10 ~ 30 after solution I and II is added
Min and 8 ~ 20 h, time of repose are 0 ~ 5 h；Washing times are 2 ~ 5 times；Drying temperature is 50 ~ 80oC, when dry
Between 6 ~ 24 h.
5. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that described in step 4
Inert gas is helium or argon gas；Calcination temperature is 550 ~ 800oC, 4 ~ 8 h of calcination time, heating rate are 1 ~ 4 oC/
min。
6. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that acid described in step 5 is molten
Liquid is nitric acid or hydrochloric acid, and mass concentration is 20 ~ 40%；2 ~ 5 h of return time；Deionized water washing times are 3 ~ 6 times；
Oven drying temperature is 80 ~ 120oC, 6 ~ 10 h of drying time.
7. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that chlorine described in step 6
Change a concentration of 0.45 ~ 1.2 g/L of palladium dipping solution, dip time is 4 ~ 12 h.
8. phenol hydrogenation catalyst according to claim 1 and preparation method thereof, which is characterized in that described in step 7
Hydrogen reducing temperature is 150 ~ 300oC, 3 ~ 6 h of recovery time, heating rate are 1 ~ 4oC/min。
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