CN107954842A - A kind of method that palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis prepares hydroresorcinol - Google Patents
A kind of method that palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis prepares hydroresorcinol Download PDFInfo
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- CN107954842A CN107954842A CN201711026276.7A CN201711026276A CN107954842A CN 107954842 A CN107954842 A CN 107954842A CN 201711026276 A CN201711026276 A CN 201711026276A CN 107954842 A CN107954842 A CN 107954842A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 181
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 68
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004005 microsphere Substances 0.000 title claims abstract description 64
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 64
- 239000011733 molybdenum Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 42
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 35
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000006462 rearrangement reaction Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 85
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006197 hydroboration reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FELGMEQIXOGIFQ-CYBMUJFWSA-N (3r)-9-methyl-3-[(2-methylimidazol-1-yl)methyl]-2,3-dihydro-1h-carbazol-4-one Chemical compound CC1=NC=CN1C[C@@H]1C(=O)C(C=2C(=CC=CC=2)N2C)=C2CC1 FELGMEQIXOGIFQ-CYBMUJFWSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- NPAKNKYSJIDKMW-UHFFFAOYSA-N carvedilol Chemical compound COC1=CC=CC=C1OCCNCC(O)COC1=CC=CC2=NC3=CC=C[CH]C3=C12 NPAKNKYSJIDKMW-UHFFFAOYSA-N 0.000 description 1
- 229960004195 carvedilol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- -1 nitre sulphur ketone Chemical class 0.000 description 1
- 229960005343 ondansetron Drugs 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
Classifications
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method that palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis prepares 1,3 cyclohexanediones, concretely comprises the following steps：Precursor solution is formed by graphene is added in the precursor solution of palladium, using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected to the outer layer of coaxial endless tube micro-fluidic chip, sodium borohydride solution injection sandwich layer, coutroi velocity enters hybrid channel, ultrasonic wave added, filtering, after liquid nitrogen frozen, freeze-drying, it is impregnated in molybdate solution, obtains palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis；Resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst, is passed through hydrogen, heating pressurization carries out hydrogenating reduction, then reacts with sulfuric acid to obtain 1,3 cyclohexanediones at room temperature.The selection rate in 1,3 cyclohexanediones are prepared is high using palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis by the present invention, and high income is efficient.
Description
Technical field
The invention belongs to medicinal chemistry art, and in particular to a kind of palladium/molybdenum/graphene porous microsphere of microfluidic method synthesis
The method that catalyst prepares hydroresorcinol.
Background technology
1, hydroresorcinol is important chemical intermediate, and there is typical ketoenol tautomerization in the solution to show
As, i.e., at the same time there are enol form and keto-acid isomers, there is good amphipathic property energy, available for synthesize Carvedilol,
The medicines such as Ondansetron, synthetic polymer additive, cosmetics, herbicide sulphur humulone, nitre sulphur ketone,
At present, 1, the method for hydroresorcinol has condensation method and reduction method, wherein reduction method, be from resorcinol,
By the synthesis such as alkalization, hydrogenating reduction or hydrogen migration, esterification and rearrangement 1, hydroresorcinol, acts in Sodium Hydroxide Alkaline
Under, make a hydroxyl generation phenol sodium in resorcinol, and resorcinol and Pd/AC catalyst parallel contacts, synchronize hydrogenation
Progressively it is hydrogenated with, is further acidified, obtains 1, hydroresorcinol.A kind of 1,3- hexamethylenes disclosed in Chinese patent CN1275922C
The preparation method of diketone, salt is first neutralized into by resorcinol and inorganic strong alkali, under the modified skeletal nickel catalyst catalysis containing molybdenum,
Hydrogenating reduction is carried out, then is acidified at room temperature with Bronsted acid and rearrangement reaction, obtains 1, hydroresorcinol, this method uses
Alkali metal hydroxide replaces precious metals palladium catalyst as alkali neutralization salifying agent, and with modified skeletal nickel catalyst, realizes
High conversion and high selectivity are realized under the conditions of gentle reaction and low toxicity, and cost is greatly lowered.
Graphene has special construction, and from molecular level, graphene is made of numerous hexatomic ring, its edge hydrogen is former
Son is much smaller than phenyl ring to molecular contributions.Chemical property of the graphene with part condensed-nuclei aromatics and graphite, it is generally recognized that due to π
The presence of electron cloud causes to be easy to the graphite-structure that accumulation forms multilayer between graphene carbon skeleton, make its battery, sensor,
The field such as composite material and energy storage is all widely used.Palladium Selective graphene disclosed in Chinese patent CN 104860802B is urged
Change Hydrogenation for 1, the method for hydroresorcinol, palladium chloride solution is added by graphene oxide solution, is uniformly mixed, then slowly drop
Add in sodium borohydride aqueous solution, be freeze-dried, obtain palladium graphen catalyst, be transferred in reaction kettle, add raw material isophthalic two
Phenol is dissolved in dichloromethane solution, is passed through hydrogen, heats compressive reaction, then it is post-treated obtain 1, hydroresorcinol.By above-mentioned existing
There is technology to understand, the catalysis resorcinol selective hydrogenation of palladium graphen catalyst prepares 1, and hydroresorcinol, obtains higher choosing
Selecting property and high yield.
The content of the invention
Palladium/molybdenum/graphene porous microsphere the technical problem to be solved in the present invention is to provide a kind of synthesis of microfluidic method is urged
Agent catalysis prepares 1, and the method for hydroresorcinol is molten by the use of coaxial endless tube micro-fluidic chip as reaction unit, palladium presoma
Liquid, graphene and sodium borohydride solution are raw material, and assisting ultrasonic technology and liquid-nitrogen freeze drying technology obtain porous microsphere, then soak
Stain and molybdate solution, obtain palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis, what this method was prepared
Palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis catalytic activity in 1, hydroresorcinol preparation is high, catalytic
Can be excellent efficient, the high income of product.
In order to solve the above technical problems, the technical scheme is that：
A kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis prepares the side of hydroresorcinol
Method, comprises the following steps：
(1) graphene will be added in the precursor solution of palladium, ultrasonic disperse is formed uniformly precursor solution, with sodium borohydride
Solution is reducing agent, and using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial endless tube miniflow
Control the outer layer of chip, sodium borohydride solution injects the sandwich layer of coaxial endless tube micro-fluidic chip, control precursor solution flow velocity and
The flow velocity of sodium borohydride solution enters hybrid channel, and ultrasonic wave added reduction, collects product, filtering, obtains miniflow in channel end
The palladium/graphene porous microsphere catalyst of control method synthesis；
(2) for the palladium/graphene microballoon for preparing step (1) after liquid nitrogen frozen, freeze-drying, is impregnated in molybdate solution
In, obtain palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis；
(3) resorcinol is mixed with sodium hydroxide solution, is urged in palladium/molybdenum/graphene porous microsphere prepared by step (1)
Under the action of agent, hydrogen is passed through, heating pressurization carries out hydrogenating reduction, then carries out acidulant rearrangement reaction at room temperature with sulfuric acid
Obtain hydroresorcinol.
As the preferred of above-mentioned technical proposal, in the step (1), the precursor solution of palladium is the PbCl of 1-2mmol/L2
Solution.
As the preferred of above-mentioned technical proposal, in the step (1), the presoma of palladium and the mass ratio of graphene are 1-
1.5:1。
As the preferred of above-mentioned technical proposal, in the step (1), the concentration of sodium borohydride solution is 20-50mmol/L,
The pH value of sodium borohydride solution is 12-14.
As the preferred of above-mentioned technical proposal, in the step (1), the flow velocity of precursor solution and sodium borohydride solution
The ratio of flow velocity is 1:4-5.
As the preferred of above-mentioned technical proposal, in the step (1), the power of ultrasonic wave added is 200-300w.
As the preferred of above-mentioned technical proposal, in the step (2), the time of liquid nitrogen frozen is 5-10s.
As the preferred of above-mentioned technical proposal, in the step (2), molybdenum in palladium/molybdenum/graphene porous microsphere catalyst
Content is 7-10wt%.
As the preferred of above-mentioned technical proposal, in the step (2), the hole in palladium/molybdenum/graphene porous microsphere catalyst
Gap rate is not less than 30%.
As the preferred of above-mentioned technical proposal, in the step (3), the temperature for heating pressurization is 1-3Mpa, temperature 80-
140℃。
Compared with prior art, the invention has the advantages that：
The present invention prepares 1,3- hexamethylenes two using palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis
Ketone, catalyst are palladium/molybdenum/graphene porous microspheres of microfluidic method synthesis, and reaction is used as by the use of coaxial endless tube micro-fluidic chip
Device, palladium precursor solution, graphene and sodium borohydride solution are raw material, control the flow velocity of precursor solution and reducing agent, auxiliary
Ultrasonic technique is helped, obtains palladium/graphene microballoon, recycles liquid-nitrogen freeze drying technology to obtain porous microsphere, is impregnated in molybdate
Solution, obtains palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis, and the microfluidic method that this method is prepared is closed
Into palladium/molybdenum/graphene porous microsphere catalyst specific surface area it is big, aperture is small, and pore volume is big, and catalytic activity is big, 1,3-
Catalytic activity is high in prepared by cyclohexanedione, and catalytic performance is excellent efficiently, the high income of product.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) it is 1 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 1mmol/L2Graphite is added in solution
Alkene, ultrasonic disperse are formed uniformly precursor solution, and using the sodium borohydride solution of 20mmol/L as reducing agent, wherein sodium borohydride is molten
The pH value of liquid is 12, and using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial endless tube miniflow
Control the outer layer of chip, sodium borohydride solution injects the sandwich layer of coaxial endless tube micro-fluidic chip, control precursor solution flow velocity and
The ratio of the flow velocity of sodium borohydride solution is 1:4, into hybrid channel, ultrasonic wave added reduces under 200w, is received in channel end
Collect product, filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 5s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 7wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Hydrogen is passed through, at a temperature of 1Mpa pressure and 80 DEG C, heating pressurization carries out hydrogenating reduction 1h, then carries out acid at room temperature with sulfuric acid
Agent rearrangement reaction obtains hydroresorcinol.
Embodiment 2：
(1) it is 1.5 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 2mmol/L2Stone is added in solution
Black alkene, ultrasonic disperse are formed uniformly precursor solution, using the sodium borohydride solution of 50mmol/L as reducing agent, wherein sodium borohydride
The pH value of solution is 14, and using coaxial endless tube micro-fluidic chip as reaction unit, it is micro- that precursor solution is injected coaxial endless tube
The outer layer of fluidic chip, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control the flow velocity of precursor solution
Ratio with the flow velocity of sodium borohydride solution is 1:5, into hybrid channel, ultrasonic wave added reduces under 300w, in channel end
Product is collected, filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 10s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 10wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Hydrogen is passed through, at a temperature of 3Mpa pressure and 140 DEG C, heating pressurization carries out hydrogenating reduction 3h, then is carried out at room temperature with sulfuric acid
Acidulant rearrangement reaction obtains hydroresorcinol.
Embodiment 3：
(1) it is 1.2 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 1.5mmol/L2Added in solution
Graphene, ultrasonic disperse are formed uniformly precursor solution, using the sodium borohydride solution of 30mmol/L as reducing agent, wherein hydroboration
The pH value of sodium solution is 13, and using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial endless tube
The outer layer of micro-fluidic chip, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control the stream of precursor solution
The ratio of the flow velocity of speed and sodium borohydride solution is 1:4.5, into hybrid channel, ultrasonic wave added reduces under 250w, in passage
Product is collected in end, and filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 6s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 8wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Be passed through hydrogen, at a temperature of 1.5Mpa pressure and 100 DEG C, heating pressurization carry out hydrogenating reduction 2h, then with sulfuric acid at room temperature into
Row acidulant rearrangement reaction obtains hydroresorcinol.
Embodiment 4：
(1) it is 1.3 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 1.2mmol/L2Added in solution
Graphene, ultrasonic disperse are formed uniformly precursor solution, using the sodium borohydride solution of 2.5mmol/L as reducing agent, wherein boron hydrogen
The pH value for changing sodium solution is 12.5, using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial
The outer layer of endless tube micro-fluidic chip, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control precursor solution
Flow velocity and sodium borohydride solution flow velocity ratio be 1:5, into hybrid channel, ultrasonic wave added reduces under 230w, logical
Product is collected in road end, and filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 6s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 8wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Be passed through hydrogen, at a temperature of 2Mpa pressure and 110 DEG C, heating pressurization carry out hydrogenating reduction 2.5h, then with sulfuric acid at room temperature into
Row acidulant rearrangement reaction obtains hydroresorcinol.
Embodiment 5：
(1) it is 1.4 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 1.6mmol/L2Added in solution
Graphene, ultrasonic disperse are formed uniformly precursor solution, using the sodium borohydride solution of 35mmol/L as reducing agent, wherein hydroboration
The pH value of sodium solution is 13.5, and using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial rings
The outer layer of pipe micro-fluidic chip, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control precursor solution
The ratio of the flow velocity of flow velocity and sodium borohydride solution is 1:4.2, into hybrid channel, ultrasonic wave added reduces under 270w, logical
Product is collected in road end, and filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 9s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 8.5wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Hydrogen is passed through, at a temperature of 2.5Mpa pressure and 130 DEG C, heating pressurization carries out hydrogenating reduction 2.5h, then with sulfuric acid at room temperature
Carry out acidulant rearrangement reaction and obtain hydroresorcinol.
Embodiment 6：
(1) it is 1.2 according to the presoma of palladium and the mass ratio of graphene:1, by the PbCl of 1.8mmol/L2Added in solution
Graphene, ultrasonic disperse are formed uniformly precursor solution, using the sodium borohydride solution of 35mmol/L as reducing agent, wherein hydroboration
The pH value of sodium solution is 13.5, and using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected coaxial rings
The outer layer of pipe micro-fluidic chip, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control precursor solution
The ratio of the flow velocity of flow velocity and sodium borohydride solution is 1:4.2, into hybrid channel, ultrasonic wave added reduces under 240w, logical
Product is collected in road end, and filtering, obtains the palladium/graphene porous microsphere catalyst of microfluidic method synthesis.
(2) by palladium/graphene microballoon after liquid nitrogen frozen 10s, 12h is freeze-dried at -20 DEG C, it is molten to be impregnated in molybdate
In liquid, palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis is obtained, wherein palladium/molybdenum/graphene porous microsphere is urged
The content of molybdenum is 9wt% in agent.
(3) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphene porous microsphere catalyst,
Be passed through hydrogen, at a temperature of 1.5Mpa pressure and 100 DEG C, heating pressurization carry out hydrogenating reduction 3h, then with sulfuric acid at room temperature into
Row acidulant rearrangement reaction obtains hydroresorcinol.
Comparative example：
(1) resorcinol is mixed with sodium hydroxide solution, under the action of palladium/molybdenum/graphen catalyst, is passed through hydrogen
Gas, at a temperature of 1Mpa pressure and 80 DEG C, heating pressurization carries out hydrogenating reduction 1h, then carries out acidulant weight at room temperature with sulfuric acid
Row's reaction obtains hydroresorcinol.
After testing, the knot of the palladium/molybdenum/graphene porous microsphere catalyst for the microfluidic method synthesis that prepared by embodiment 1-6
Fruit is as follows：
After testing, the palladium/molybdenum/graphene porous microsphere catalyst and right for the microfluidic method synthesis that prepared by embodiment 1-6
The result of conversion ratio and selectivity of the ratio in hydroresorcinol preparation is as follows：
As seen from the above table, the ratio of the palladium/molybdenum synthesized by microfluidic method/graphene porous microsphere catalyst prepared by the present invention
Surface area is big, and catalytic activity is big, high conversion rate and high selectivity in 1, hydroresorcinol preparation.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of palladium/molybdenum of microfluidic method synthesis/graphene porous microsphere catalyst preparation 1, the method for hydroresorcinol,
It is characterised in that it includes following steps：
(1) graphene will be added in the precursor solution of palladium, ultrasonic disperse is formed uniformly precursor solution, with sodium borohydride solution
For reducing agent, using coaxial endless tube micro-fluidic chip as reaction unit, precursor solution is injected into the micro-fluidic core of coaxial endless tube
The outer layer of piece, sodium borohydride solution inject the sandwich layer of coaxial endless tube micro-fluidic chip, control the flow velocity and boron hydrogen of precursor solution
The flow velocity for changing sodium solution enters hybrid channel, and ultrasonic wave added reduction, collects product, filtering, obtains microfluidic method in channel end
The palladium/graphene porous microsphere catalyst of synthesis；
(2) after liquid nitrogen frozen, freeze-drying, is impregnated in molybdate solution the palladium/graphene microballoon for preparing step (1),
Obtain palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis；
(3) resorcinol is mixed with sodium hydroxide solution, in palladium/molybdenum/graphene porous microsphere catalyst prepared by step (1)
Under the action of, hydrogen is passed through, heating pressurization carries out hydrogenating reduction, then carries out acidulant rearrangement reaction at room temperature with sulfuric acid and obtain
Hydroresorcinol.
2. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (1), the precursor solution of palladium is the PbCl of 1-2mmol/L2
Solution.
3. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (1), the presoma of palladium and the mass ratio of graphene are 1-
1.5:1。
4. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (1), the concentration of sodium borohydride solution is 20-50mmol/L,
The pH value of sodium borohydride solution is 12-14.
5. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (1), the flow velocity of precursor solution and sodium borohydride solution
The ratio of flow velocity is 1:4-5.
6. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (1), the power of ultrasonic wave added is 200-300w.
7. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (2), the time of liquid nitrogen frozen is 5-10s.
8. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (2), molybdenum in palladium/molybdenum/graphene porous microsphere catalyst
Content is 7-10wt%.
9. prepared by a kind of palladium/molybdenum/graphene porous microsphere catalyst of microfluidic method synthesis according to claim 1
1, the method for hydroresorcinol, it is characterised in that：In the step (2), the hole in palladium/molybdenum/graphene porous microsphere catalyst
Gap rate is not less than 30%.
A kind of 10. palladium/molybdenum/graphene porous microsphere catalyst system of microfluidic method synthesis according to claim 1
Standby 1, the method for hydroresorcinol, it is characterised in that：In the step (3), the temperature for heating pressurization is 1-3Mpa, and temperature is
80-140℃。
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| CN111875497A (en) * | 2020-08-17 | 2020-11-03 | 万华化学集团股份有限公司 | Method for synthesizing ethyl glyoxylate by catalytic hydrogenation of diethyl maleate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108712352A (en) * | 2018-05-04 | 2018-10-26 | 上海理工大学 | Morse code conversion based on coaxial type micro-fluidic chip and visualization device |
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| CN111875497B (en) * | 2020-08-17 | 2022-11-08 | 万华化学集团股份有限公司 | Method for synthesizing ethyl glyoxylate by catalytic hydrogenation of diethyl maleate |
| CN112588331A (en) * | 2020-11-16 | 2021-04-02 | 苏州艾达仕电子科技有限公司 | Method for synthesizing composite conductive material by droplet microfluidics and microfluidic synthesis chip |
| CN113881399A (en) * | 2021-09-27 | 2022-01-04 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
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