CN110003016A - A kind of method that hydrogenation of chloronitrobenzene prepares aniline - Google Patents
A kind of method that hydrogenation of chloronitrobenzene prepares aniline Download PDFInfo
- Publication number
- CN110003016A CN110003016A CN201910284973.5A CN201910284973A CN110003016A CN 110003016 A CN110003016 A CN 110003016A CN 201910284973 A CN201910284973 A CN 201910284973A CN 110003016 A CN110003016 A CN 110003016A
- Authority
- CN
- China
- Prior art keywords
- sio
- catalyst
- added
- hydrogenation
- chloronitrobenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 37
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 74
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 74
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 74
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- BYIMSFXYUSZVLI-UHFFFAOYSA-N 3-methoxysilylpropan-1-amine Chemical class CO[SiH2]CCCN BYIMSFXYUSZVLI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001944 prunus armeniaca kernel oil Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to aniline preparation technical fields, disclose a kind of method that hydrogenation of chloronitrobenzene prepares aniline.This method is in aqueous solution, with amphipathic magnetic Nano material supported palladium active particle Fe3O4@SiO2@C12@NH2/ Pd is catalyst, and catalysis hydrogenation of chloronitrobenzene prepares aniline.The catalyst that this method is prepared can p-nitrophenyl catalytic efficiency with higher in a mild condition, selectivity preferably, and catalyst can be easily separated, separate in externally-applied magnetic field after can reuse.
Description
Technical field
The present invention relates to a kind of methods that hydrogenation of chloronitrobenzene prepares aniline.
Background technique
Nitrobenzene is commonly called as artificial almond oil, and sterling is colourless or flaxen oily liquids, there is the special of apricot kernel oil
Smell, it is not soluble in water, it can be with the immiscible organic solvents such as ethyl alcohol, ether or benzene;Aniline is commonly called as A Jilin oil, usually with nitre
Base benzene is made for raw material deep processing, is widely used in the production technologies such as dyestuff, pesticide, medicine, rubber chemicals and isocyanates neck
Several hundred kinds of products and intermediate, the industrial production technology of the aniline in China and developed country can be made by raw material of aniline in domain
It compares, there is also very big gaps, probe into the highly selective method for preparing aniline of Catalytic Hydrogenation of Nitrobenzene with critically important
Meaning.
The early stage production most common method of aniline is metal deoxidization, but this method is serious there is also environment is polluted,
The problems such as equipment easily corrodes, and operating cost is high is not consistent, so gradually being washed in a pan by market with the green chemical industry advocated now
It eliminates.In recent years, excessively high in order to solve reaction temperature, the problems such as pressure is big, environmental pollution, each research institution is to its process route
It is researched and developed;Chinese patent CN106242977A discloses a kind of method that catalysis hydrogenation of chloronitrobenzene prepares aniline,
Using the technique of ionic liquid concerted catalysis synthesizing amino benzene by hydrogenation of nitrobenzene, the double alkyl chain polyethers octadecylamines of double polyether chains are used
Ionic liquid stable Metal Palladium (Pd) nanoparticle prepares aniline as catalyst hydrogenation of chloronitrobenzene;Such ionic liquid
With metal nanoparticle adsorption site abundant and good electrostatic steric hindrance Dual Stabilization effect, have to metal Pd nanoparticle
There is good stabilization.Catalytic reaction condition is mild, and product can be separated by simple extraction, and catalyst is reusable, but
It is that catalyst separation is difficult, reaction temperature is larger with pressure.Chinese patent CN106975505A discloses a kind of nitrating carbon material
For Pt-supported catalyst and the preparation method and application thereof in Catalytic Hydrogenation of Nitrobenzene reaction, which is used for hydrogenation of chloronitrobenzene table
Reveal excellent catalytic activity, and has the advantages that easy preparation, Yi Huishou, easy to operate and production cost are low etc., but catalysis
Agent preparation process is complicated, severe reaction conditions.
In conclusion the present invention provides a kind of segregative method for preparing catalyst of high catalytic efficiency in a mild condition,
It is of great significance.
Summary of the invention
In view of this, the magnetism being prepared is amphipathic negative the present invention provides the method that hydrogenation of chloronitrobenzene prepares aniline
Carry Pd nanoparticle can p-nitrophenyl catalytic efficiency with higher in a mild condition, selectivity preferably, and catalyst
Can reuse after can be easily separated, separating in externally-applied magnetic field.
In order to achieve the above object of the invention, the invention adopts the following technical scheme:
A kind of method that hydrogenation of chloronitrobenzene prepares aniline, it is in aqueous solution, living with amphipathic magnetic Nano material supported palladium
Property particle Fe3O4@SiO2@C12@NH2/ Pd is catalyst, and catalysis hydrogenation of chloronitrobenzene prepares aniline;The nitrobenzene and the catalysis
Agent Fe3O4@SiO2@C12@NH2The mass ratio of/Pd is 2000.
Further, the reaction temperature of the catalysis nitrobenzene hydrogenation is 40 DEG C, reaction time 1h, reaction process
Hydrogen Vapor Pressure be 1MPa.
Preferably, in the aqueous solution, the catalyst Fe3O4@SiO2@C12@NH2/ Pd, the nitrobenzene and institute
The mass ratio for stating water is 1:60:2000.
Further, after the catalysis nitrobenzene hydrogenation, externally-applied magnetic field is by the catalyst and the aniline
Separation.
Preferably, the method that hydrogenation of chloronitrobenzene provided by the invention prepares aniline, specifically, weighing the addition of 1g nitrobenzene
Into stainless steel machinery stirred tank, 20ml water is then added, weighs 20mg catalyst Fe3O4@SiO2@C12@NH2/ Pd mixing is equal
It is even, with 1MPa hydrogen by gas displacement 4 times in kettle, 1MPa hydrogen is then poured, the mechanic whirl-nett reaction 1h at 40 DEG C, reaction knot
Shu Hou separates catalyst with product under externally-applied magnetic field.
The catalyst Fe provided by the invention3O4@SiO2@C12@NH2The preparation method of/Pd is, using Fe3O4Nanoparticle
Son prepares magnetic carrier Fe3O4@SiO2, and magnetism is carried with dodecyltrimethoxysilane and three aminopropyl methoxysilanes
Body Fe3O4@SiO2It is modified, amphipathic magnetic composite nano material Fe is prepared3O4@SiO2@C12@NH2, finally by palladium
Salt reduction plus hydrogen are supported on palladium particle on the amphipathic magnetic composite nano material, form stable catalyst Fe3O4@
SiO2@C12@NH2/Pd。
Preferably, the catalyst Fe3O4@SiO2@C12@NH2The preparation method of/Pd is specific as follows:
S1, preparation Fe3O4Nanoparticle is respectively by 3.4g FeCl3·6H2O and 1.25g FeCl2·4H2O is added to three mouthfuls
In flask, the rear ammonium hydroxide that 100ml water and 6ml 25% is added is stirred 40min at 60 DEG C, is separated using externally-applied magnetic field, pure water
Washing for several times, is dried in vacuo 4h at 60 DEG C, obtains Fe3O4Nanoparticle;
S2, prepare magnetic carrier Fe3O4@SiO2 is by 1.4g Fe3O4Nanoparticle is added in three-necked flask, is then added
5ml25% ammonium hydroxide and 70ml water, 280ml ethyl alcohol are added dropwise 1mlTEOS (ethyl orthosilicate), and mechanical stirring 8h, additional at room temperature
Magnetic field is separated, and respectively three times with water and ethanol washing, 50 DEG C of vacuum dry 8h obtain magnetic carrier Fe3O4@SiO2;
S3, prepare magnetic amphiphilic nano molecular sieve Fe3O4@SiO2@C12@NH2By 0.25g magnetic carrier Fe3O4@SiO2Add
Enter into three-necked flask, 0.88g CTAB (cetyl trimethylammonium bromide) and 125ml formaldehyde, 100ml water, 625 μ l are added
Concentration is the NaOH mechanical stirring 1h of 1mol/L, and 162 μ l dodecyl trimethoxy silanes are added, and continues to stir two hours
After be added dropwise 358 μ l TMOS (methyl orthosilicate) and 322 μ l APTS (3- aminopropyl trimethoxysilane), continue mechanical stirring
12h, still aging crystallization 12h, externally-applied magnetic field are separated, and use ethyl alcohol and water washing 3 times respectively, in 50 DEG C of vacuum drying 4h,
Obtain amphipathic magnetic nanomolecules sieve Fe3O4@SiO2@C12@NH2;
S4、Fe3O4@SiO2@C12@NH2The preparation of/Pd weighs the amphipathic magnetic nanomolecules sieve Fe of 200mg3O4@SiO2@
C12@NH2It is added in three-necked flask, ultrasonic disperse adds 50mg PdCl in ethanol solution at room temperature2, continue dispersion 10
Minute, then weigh 30mg NaBH4It is added in three-necked flask, after 40 DEG C of mechanical stirring 2h, obtains stable catalyst Fe3O4@
SiO2@C12@NH2/Pd。
Obtained amphipathic magnetic loading Pd nano-particle catalyst produced according to the present invention forms, function is as follows:
In ethanol medium, with Fe3O4@SiO2@C12@NH2The nano particle of formation is stabilizer, is added by palladium salt reduction
Hydrogen principle is supported on palladium particle on magnetic amphiphilic nanoparticles, forms the nanoparticle sphere catalyst with catalytic property
Fe3O4@SiO2@C12@NH2/ Pd, in this catalyst system, Fe3O4@SiO2@C12@NH2Act not only as " amphipathic micro- reaction
Device " makes catalysis reaction in the progress for forming microenvironment promotion reaction, plays to the raising of selectivity and catalytic efficiency key
Effect, while magnetism can also be provided, it is most important for the separation of catalyst;The work of Metal Palladium (Pd) in catalyst system
With also most important, Fe3O4@SiO2@C12@NH2Only carried metal palladium (Pd) could reach catalytic effect most preferably, final to make
The catalyst Fe obtained3O4@SiO2@C12@NH2/ Pd is added in reaction kettle, and a certain amount of nitrobenzene is then added, and is filled with a level pressure
The H of power2Hydrogenation reaction is carried out, in hydrogenation reaction, solid catalyst-nitrobenzene oil phase-hydrogen forms three phase boundary, reduces and passes
Matter resistance is conducive to reaction and carries out, carries out catalytic hydrogenation reaction in a mild condition, p-nitrophenyl is with higher to urge
Change efficiency, selectivity preferably, after reaction, separates catalyst in externally-applied magnetic field, catalyst can reuse.
Magnetic carrier Fe3O4Addition, catalyst can be separated in externally-applied magnetic field, but it is anti-to will affect catalysis
The catalytic efficiency answered, originally inventor once abandons is added magnetic material Fe3O4Initial effort, with the progress of test, system
Standby magnetic carrier Fe3O4@SiO2In the process, the dosage and reaction condition of optimization reaction supplementary material, collaboration hydrogenation of chloronitrobenzene prepare benzene
Reaction condition during amine, hydrogenation of chloronitrobenzene provided by the invention prepares the catalyst of the method preparation of aniline, in addition magnetic
Property material early period under, still can make catalysis react catalytic efficiency obtain a degree of raising.
Technical solution provided by the invention has the advantage that
(1) the present invention provides a kind of method for preparing the reaction of nitrobenzene stable hydrogenation as medium using water, catalyst separation
Simply, cleaning is cheap;
(2) catalysis hydrogenation of chloronitrobenzene method provided by the invention has very high catalytic activity and Aniline product selectivity;
(3) catalysis hydrogenation of chloronitrobenzene method provided by the invention is not required to any organic solvent, and reaction condition is mild, environment
It is friendly;
(4) in catalysis hydrogenation of chloronitrobenzene method provided by the invention, catalyst separation is simple and repeatability is good, and it is urged
It is sufficiently stable to change performance.
Detailed description of the invention
Fig. 1 is the Fe that embodiment 1 provides3O4, Fe3O4@SiO2, Fe3O4@SiO2@C12@NH2MPMS magnetic measurement figure;
Fig. 2 is the catalyst Fe that embodiment 1 provides3O4@SiO2@C12@NH2The SEM scanning figure (a) and TEM perspective view of/Pd
(b);
Fig. 3 is the catalyst Fe that embodiment 1 provides3O4@SiO2@C12@NH2The particle diameter distribution picture of/Pd;
Fig. 4 is the catalyst Fe that embodiment 1 provides3O4@SiO2@C12@NH2The mapping spectrogram of/Pd.
Specific embodiment
The invention discloses a kind of method that hydrogenation of chloronitrobenzene prepares aniline, those skilled in the art can be used for reference in this paper
Hold, is suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications are to those skilled in the art
For be it will be apparent that they are considered as including in the present invention.Method and application of the invention has passed through preferably
Embodiment is described, related personnel obviously can not depart from the content of present invention, in spirit and scope to side as described herein
Method and application are modified or appropriate changes and combinations, carry out implementation and application the technology of the present invention.
In order to enable those skilled in the art to better understand the present invention, With reference to embodiment to the present invention
It is described in further detail.
1 catalyst Fe of embodiment3O4@SiO2@C12@NH2The preparation of/Pd
S1Prepare Fe3O4Nanoparticle
3.4g FeCl is weighed respectively3·6H2O and 1.25g FeCl2·4H2O is added in three-necked flask, rear to be added
The ammonium hydroxide of 100ml water and 6ml25% is stirred 40min at 60 DEG C, is separated using externally-applied magnetic field, pure water for several times, at 60 DEG C
Lower vacuum drying 4h;
S2Prepare magnetic carrier Fe3O4@SiO2
Weigh 1.4g Fe3O4Be added in 500ml three-necked flask, then be added 5ml 25% ammonium hydroxide and 70ml water,
280ml ethyl alcohol is added dropwise 1mlTEOS (ethyl orthosilicate), and mechanical stirring 8h, externally-applied magnetic field are separated at room temperature, are used respectively
Water and ethanol washing three times, 50 DEG C of vacuum dry 8h;
S3Prepare Fe3O4@SiO2@C12@NH2
Weigh the magnetic carrier Fe of 0.25g preparation3O4@SiO2It is added in 500ml three-necked flask, 0.88g CTAB is added
(cetyl trimethylammonium bromide) and 125ml formaldehyde, 100ml water, 625ul NaOH (1mol/L) mechanical stirring 1h are added
162ul C12(dodecyl trimethoxy silane), continue two hours of stirring be added dropwise 358ul TMOS (methyl orthosilicate) and
322ul APTS (3- aminopropyl trimethoxysilane), continues mechanical stirring 12h, still aging crystallization 12h, and externally-applied magnetic field carries out
Separation uses ethyl alcohol and water washing 3 times, in 50 DEG C of vacuum drying 4h respectively;
S4Fe3O4@SiO2@C12@NH2The preparation of/Pd
Weigh the amphipathic magnetic nanomolecules sieve Fe of 200mg3O4@SiO2@C12@NH2It is added in three-necked flask, at room temperature
Ultrasonic disperse adds 50mg PdCl in ethanol solution2, continue dispersion 10 minutes, then weigh 30mg NaBH4It is added to three
In mouth flask, after 40 DEG C of mechanical stirring 2h, stable catalyst Fe is obtained3O4@SiO2@C12@NH2/Pd。
By Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2@C12@NH2MPMS magnetic measurement, measurement result is shown in that Fig. 1, Fig. 1 are shown
The size of each its magnetic intensity of material out, therefore can easily be separated catalyst with substrate very much under externally-applied magnetic field.
Fig. 2 is catalyst Fe3O4@SiO2@C12@NH2The SEM scanning figure (a) of/Pd and TEM perspective view (b), from Fig. 2 (a) and
(b) display in shows the catalysis that the present invention is prepared by the ball-type magnetic nanoparticle for the uniform rule that crystallization is formed
Agent size particles are uniform, and specific surface area is bigger, increase the contact area of substrate and catalyst, and reaction is promoted to carry out.
Fig. 3 is catalyst Fe3O4@SiO2@C12@NH2The particle diameter distribution picture of/Pd, Fig. 3 show, Malvern grain size analysis
Instrument analysis, the average particle size of synthetic material are 325nm and epigranular, and 300nm to the particle between 350nm accounts for sum
70%.
Fig. 4 is Fe3O4@SiO2@C12@NH2The mapping spectrogram of/Pd, from fig. 4, it can be seen that SiO2Layer is very well by Fe3O4
It is wrapped in inside, Pd is uniformly dispersed in Fe3O4@SiO2@C12@NH2Outside;Because of Fe3O4It is easily corroded in air with solution,
Wrap up one layer of SiO in outside2It can prevent Fe3O4It is corroded, such amphipathic magnetic Fe3O4@SiO2@C12@NH2The magnetic ratio of/Pd
More stable, therefore, the catalyst of preparation method preparation provided by the invention is not easy demagnetization in use, in acid-base solution
Middle recycling is magnetic also more stable.
2 hydrogenation of chloronitrobenzene of embodiment prepares aniline
It weighs 1g nitrobenzene to be added in stainless steel machinery stirred tank, 20ml water is then added, weigh the system of 20mg embodiment 1
The standby amphipathic catalyst Fe of magnetism3O4@SiO2@C12@NH2/ Pd is uniformly mixed, with 1MPa hydrogen by gas displacement 4 times in kettle,
Then 1MPa hydrogen is poured, the mechanic whirl-nett reaction 1h at 40 DEG C, after reaction, by catalyst and product under externally-applied magnetic field
Separation after extracting product with normal heptane, collects upper layer product and chromatography is mutually used to carry out quantitative analysis, nitrobenzene conversion rate is
99.6%, the selectivity of aniline is 98.5%.
The recycling test of 3 catalyst of embodiment
It weighs 1g nitrobenzene to be added in stainless steel machinery stirred tank, 20ml water is then added, weigh the system of 20mg embodiment 1
The standby amphipathic catalyst Fe of magnetism3O4@SiO2@C12@NH2/ Pd is uniformly mixed, with 1MPa hydrogen by gas displacement 4 times in kettle,
Then 1MPa hydrogen is poured, the mechanic whirl-nett reaction 1h at 40 DEG C, after reaction, by catalyst and product under externally-applied magnetic field
Separation, the catalyst recycling after separation, repeats above-mentioned experimental procedure.
Catalyst Fe3O4@SiO2@C12@NH2/ Pd is reused 7 times, and nitrobenzene conversion rate reaches 95.2%, the choosing of aniline
Selecting property reaches 98.5%, and catalyst is reused 8 times, and nitrobenzene conversion rate reaches 85.2%, and the selectivity of aniline reaches
95.7%.Above-mentioned test result shows, catalyst Fe3O4@SiO2@C12@NH2/ Pd recycling is high.
4 hydrogenation of chloronitrobenzene of embodiment prepares the selection of temperature in the method for aniline
It weighs 1g nitrobenzene to be added in stainless steel machinery reaction kettle, 20ml water is then added, weighs 20mg magnetism amphiphilic
Property catalyst Fe3O4@SiO2@C12@NH2/ Pd is uniformly mixed, and with 1MPa hydrogen by gas displacement 4 times in kettle, then pours 1MPa
Hydrogen, the mechanic whirl-nett reaction 1h at 120 DEG C after reaction separate catalyst with product under externally-applied magnetic field, with positive heptan
After alkane extraction, collects upper layer product and chromatography is mutually used to carry out quantitative analysis, nitrobenzene conversion rate 76.39% is selectively
92.5%;Therefore the too high catalytic efficiency of temperature declines instead, the effective catalytic temperature of the catalyst is 40 DEG C -100 DEG C.
Comparative example 1
By 250mg Fe3O4@SiO2It is added in three-necked flask with 0.3ml APTS, 140ml isopropanol, 70 DEG C of machinery
8h is stirred, Fe is obtained3O4@SiO2@NH2, then weigh 20mg Fe3O4@SiO2@NH2With 10mg PdCl2It is made in alcohol solvent
Standby Pd nano-particle catalyst, obtains catalyst Fe3O4@SiO2@NH2/Pd;1g nitrobenzene and 20ml water and 20mg are catalyzed
Agent Fe3O4@SiO2@NH2/ Pd is added in stainless steel machinery reaction kettle and is uniformly mixed, and is replaced 4 times with 1MPa hydrogen, then pour
1MPa hydrogen, mechanic whirl-nett reaction 1h at 40 DEG C utilize magnet separating catalyst and substrate after reaction, are extracted with normal heptane
Product phase, using chromatography to progress product quantitative analysis, the selectivity of nitrobenzene conversion rate 52.4%, aniline is
85.4%.
Comparative example 2
A certain amount of stabilizer PVA and 3mL water are added in 75ml autoclave, stirring 1h is equal to mixing under greenhouse
It is even, Pd metal precursor 0.0001mol is added, 1h is sufficiently stirred;First air displacement 4 times in kettle are re-filled with 1MP hydrogen
1MPa H2, 1h is reacted under the conditions of 50 DEG C, obtains the P123-Pd nanocatalyst of black even.
2.462g nitrobenzene is added in above-mentioned P123-Pd nanocatalyst reaction kettle, 1MPa H is first used2By reaction kettle
Do not have air displacement 4 times, is re-filled with 1MPa H2, 1h is reacted at 40 DEG C, is centrifugated after reaction, is extracted using normal heptane
Product, using chromatography to product quantitative analysis, nitrobenzene conversion rate 42.8%, the selectivity of aniline is 94.8%.It is magnetic
Amphipathic catalyst is higher compared to P123-Pd catalyst activity, and reaction condition is more mild.
Comparative example 3
Amphipathic magnetic catalyst in table 1 is prepared using the method for embodiment 1,1 nitrobenzene is weighed and is added to stainless steel machine
In tool stirred tank, 20ml water is then added, weigh the amphipathic catalyst of magnetism in 20mg table 1 respectively and is uniformly mixed, uses
Then gas displacement 4 times in kettle are poured 1MPa hydrogen by 1MPa hydrogen, the mechanic whirl-nett reaction 1h at 40 DEG C, after reaction,
Catalyst is separated with product under externally-applied magnetic field, after being extracted with normal heptane, upper layer product is collected and mutually chromatography is used to be determined
The selectivity of amount analysis, nitrobenzene conversion rate and aniline is as shown in table 1.
Influence of the different amphipathic magnetic catalyst of table 1 to conversion ratio and selectivity
1 data of table show that the modifying agent and metal in catalyst system play pass to the raising of selectivity and catalytic efficiency
The effect of keyness, the method that hydrogenation of chloronitrobenzene provided by the invention prepares aniline, under the early period of addition magnetic material, catalyst
Fe3O4@SiO2@C12@NH2/ Pd still can p-nitrophenyl catalytic efficiency with higher, selectivity preferably, after reaction,
Catalyst is separated in externally-applied magnetic field, catalyst can reuse.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of method that hydrogenation of chloronitrobenzene prepares aniline, which is characterized in that in aqueous solution, with amphipathic magnetic Nano material
Supported palladium active particle Fe3O4@SiO2@C12@NH2/ Pd is catalyst, and catalysis hydrogenation of chloronitrobenzene prepares aniline;The nitrobenzene with
The catalyst Fe3O4@SiO2@C12@NH2The mass ratio of/Pd is 2000.
2. the method that hydrogenation of chloronitrobenzene as described in claim 1 prepares aniline, it is characterised in that: the catalysis hydrogenation of chloronitrobenzene
The reaction temperature of reaction is 40 DEG C, reaction time 1h, and the Hydrogen Vapor Pressure of reaction process is 1MPa.
3. the method that hydrogenation of chloronitrobenzene as described in claim 1 prepares aniline, which is characterized in that in the aqueous solution, institute
State catalyst Fe3O4@SiO2@C12@NH2The mass ratio of/Pd, the nitrobenzene and the water are 1:60:2000.
4. the method that hydrogenation of chloronitrobenzene as described in claim 1 prepares aniline, which is characterized in that the catalysis hydrogenation of chloronitrobenzene
After reaction, externally-applied magnetic field separates the catalyst and the aniline.
5. the method that hydrogenation of chloronitrobenzene as described in claim 1 prepares aniline, which is characterized in that specifically, weighing 1g nitro
Benzene is added in stainless steel machinery stirred tank, and 20ml water is then added, weighs 20mg catalyst Fe3O4@SiO2@C12@NH2/ Pd is mixed
It closes uniformly, with 1MPa hydrogen by gas displacement 4 times in kettle, then pours 1MPa hydrogen, the mechanic whirl-nett reaction 1h at 40 DEG C, instead
After answering, catalyst is separated with product under externally-applied magnetic field.
6. the method that hydrogenation of chloronitrobenzene as described in claim 1 prepares aniline, which is characterized in that the catalyst Fe3O4@
SiO2@C12@NH2The preparation method of/Pd is, using Fe3O4Nanoparticle prepares magnetic carrier Fe3O4@SiO2, and with dodecyl
Trimethoxy silane and three aminopropyl methoxysilanes are to magnetic carrier Fe3O4@SiO2It is modified, amphipathic magnetic is prepared
Property composite nano materials Fe3O4@SiO2@C12@NH2, so that palladium particle is supported on the amphipathic magnetic finally by palladium salt reduction plus hydrogen
On property composite nano materials, stable catalyst Fe is formed3O4@SiO2@C12@NH2/Pd。
7. the method that hydrogenation of chloronitrobenzene as described in claim 1 or 6 prepares aniline, which is characterized in that the catalyst Fe3O4@
SiO2@C12@NH2The preparation method of/Pd is specific as follows:
S1, preparation Fe3O4Nanoparticle is respectively by 3.4g FeCl3·6H2O and 1.25g FeCl2·4H2O is added to three-necked flask
In, the rear ammonium hydroxide that 100ml water and 6ml25% is added is stirred 40min at 60 DEG C, is separated using externally-applied magnetic field, pure water number
It is secondary, it is dried in vacuo 4h at 60 DEG C, obtains Fe3O4Nanoparticle;
S2, prepare magnetic carrier Fe3O4@SiO2By 1.4gFe3O4Nanoparticle is added in three-necked flask, is then added
5ml25% ammonium hydroxide and 70ml water, 280ml ethyl alcohol are added dropwise 1ml TEOS (ethyl orthosilicate), at room temperature mechanical stirring 8h, outside
Magnetic field is added to be separated, respectively three times with water and ethanol washing, 50 DEG C of vacuum dry 8h obtain magnetic carrier Fe3O4@SiO2;
S3, prepare magnetic amphiphilic nano molecular sieve Fe3O4@SiO2@C12@NH2By 0.25g magnetic carrier Fe3O4@SiO2It is added to
In three-necked flask, 0.88g CTAB (cetyl trimethylammonium bromide) and 125ml formaldehyde, 100ml water, 625 μ l are added
162 μ l dodecyl trimethoxy silanes are added in the NaOH mechanical stirring 1h of 1mol/L, continue to be added dropwise after stirring two hours
358 μ l TMOS (methyl orthosilicate) and 322 μ l APTS (3- aminopropyl trimethoxysilane) continue mechanical stirring 12h, stand
Aging crystallization 12h, externally-applied magnetic field are separated, and obtain amphiphilic in 50 DEG C of vacuum drying 4h with ethyl alcohol and water washing 3 times respectively
Property magnetic nanomolecules sieve Fe3O4@SiO2@C12@NH2;
S4、Fe3O4@SiO2@C12@NH2The preparation of/Pd weighs the amphipathic magnetic nanomolecules sieve Fe of 200mg3O4@SiO2@C12@NH2
It is added in three-necked flask, ultrasonic disperse adds 50mg PdCl in ethanol solution at room temperature2, continue dispersion 10 minutes,
30mgNaBH is weighed again4It is added in three-necked flask, after 40 DEG C of mechanical stirring 2h, obtains stable catalyst Fe3O4@SiO2@
C12@NH2/Pd。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910284973.5A CN110003016B (en) | 2019-04-10 | 2019-04-10 | Method for preparing aniline by nitrobenzene hydrogenation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910284973.5A CN110003016B (en) | 2019-04-10 | 2019-04-10 | Method for preparing aniline by nitrobenzene hydrogenation |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110003016A true CN110003016A (en) | 2019-07-12 |
CN110003016B CN110003016B (en) | 2022-02-11 |
Family
ID=67170775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910284973.5A Active CN110003016B (en) | 2019-04-10 | 2019-04-10 | Method for preparing aniline by nitrobenzene hydrogenation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110003016B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111871441A (en) * | 2020-07-23 | 2020-11-03 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
CN111871440A (en) * | 2020-07-23 | 2020-11-03 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103586048A (en) * | 2013-11-27 | 2014-02-19 | 北京化工大学 | Nano-Pd magnetic catalyst, its preparation method, and its use in liquid phase catalysis reaction |
CN104084240A (en) * | 2014-07-08 | 2014-10-08 | 大连理工大学 | Magnetic core/shell/shell triple structure material with noble metal nano particles being at double-shell interlayer and preparation method of material |
CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Preparation of supported palladium catalyst Fe3O4/SiO2/Pd and application of supported palladium catalyst Fe3O4/SiO2/Pd in Suzuki reaction |
CN105664887A (en) * | 2016-03-14 | 2016-06-15 | 中国地质大学(武汉) | Preparation method of functional magnetic silicon balls |
CN108451910A (en) * | 2018-02-09 | 2018-08-28 | 山西医科大学 | A kind of mesoporous magnetic Fe3O4Nanocomposite and preparation method thereof |
-
2019
- 2019-04-10 CN CN201910284973.5A patent/CN110003016B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103586048A (en) * | 2013-11-27 | 2014-02-19 | 北京化工大学 | Nano-Pd magnetic catalyst, its preparation method, and its use in liquid phase catalysis reaction |
CN104084240A (en) * | 2014-07-08 | 2014-10-08 | 大连理工大学 | Magnetic core/shell/shell triple structure material with noble metal nano particles being at double-shell interlayer and preparation method of material |
CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Preparation of supported palladium catalyst Fe3O4/SiO2/Pd and application of supported palladium catalyst Fe3O4/SiO2/Pd in Suzuki reaction |
CN105664887A (en) * | 2016-03-14 | 2016-06-15 | 中国地质大学(武汉) | Preparation method of functional magnetic silicon balls |
CN108451910A (en) * | 2018-02-09 | 2018-08-28 | 山西医科大学 | A kind of mesoporous magnetic Fe3O4Nanocomposite and preparation method thereof |
Non-Patent Citations (4)
Title |
---|
PENG WANG ETAL: "Entangled Pd complexes over Fe3O4@SiO2 as supported catalysts for hydrogenation and Suzuki reactions", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
PENG WANG ETAL: "Stabilizing Pd on the surface of amine functionalized hollow Fe3O4 spheres: a highly active and recyclable catalyst for Suzuki crosscoupling and hydrogenation reactions", 《RSC ADV.》 * |
PENG WANG ETAL: "Stabilizing Pd on the surface of hollow magnetic mesoporous spheres: a highly active and recyclable catalyst for hydrogenation and Suzuki coupling reactions", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
王鹏: "磁性Pd纳米催化剂的合成及其对有机反应中的应用", 《兰州大学博士学位论文》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111871441A (en) * | 2020-07-23 | 2020-11-03 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
CN111871440A (en) * | 2020-07-23 | 2020-11-03 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
CN111871441B (en) * | 2020-07-23 | 2022-05-10 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
CN111871440B (en) * | 2020-07-23 | 2022-05-13 | 青岛科技大学 | Method for preparing hydrogenated rosin by rosin hydrogenation and catalyst thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110003016B (en) | 2022-02-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Veerakumar et al. | Nickel nanoparticle-decorated porous carbons for highly active catalytic reduction of organic dyes and sensitive detection of Hg (II) ions | |
Parida et al. | Adsorption of copper (II) on NH2-MCM-41 and its application for epoxidation of styrene | |
Choi et al. | Chemical environment control and enhanced catalytic performance of platinum nanoparticles embedded in nanocrystalline metal–organic frameworks | |
Sun et al. | Multifunctional magnetic core–shell dendritic mesoporous silica nanospheres decorated with tiny Ag nanoparticles as a highly active heterogeneous catalyst | |
Zhu et al. | Amine-functionalized SBA-15 with uniform morphology and well-defined mesostructure for highly sensitive chemosensors to detect formaldehyde vapor | |
Wang et al. | Ag NPs supported on the magnetic Al-MOF/PDA as nanocatalyst for the removal of organic pollutants in water | |
Miao et al. | Catalytic liquid marbles: Ag nanowire-based miniature reactors for highly efficient degradation of methylene blue | |
Sadjadi et al. | Pd supported on magnetic carbon coated halloysite as hydrogenation catalyst: Study of the contribution of carbon layer and magnetization to the catalytic activity | |
CN107478635A (en) | A kind of MOF noble metals composite S ERS substrates and preparation method thereof | |
Wu et al. | Fe 3 O 4@ SiO 2@ Pd-Au: a highly efficient and magnetically separable catalyst for liquid-phase hydrodechlorination of 4-chlorophenol | |
CN110003016A (en) | A kind of method that hydrogenation of chloronitrobenzene prepares aniline | |
CN105964273B (en) | A kind of high-activity composite photocatalyst α-Fe2O3/Ag6Si2O7Preparation method | |
CN105344325B (en) | A kind of preparation method of the Nanoscale Iron for the treatment of of heavy metal polluted water body/mesoporous silicon composite | |
Zhao et al. | Controlled synthesis of metal-organic frameworks coated with noble metal nanoparticles and conducting polymer for enhanced catalysis | |
Mirbagheri et al. | Magnetic ethyl-based organosilica supported Schiff-base/indium: A very efficient and highly durable nanocatalyst | |
CN106622303B (en) | It is a kind of be catalyzed nitrophenol hydro-reduction catalyst and its application | |
Liu et al. | Catalysis of the hydro-dechlorination of 4-chlorophenol and the reduction of 4-nitrophenol by Pd/Fe 3 O 4@ SiO 2@ m-SiO 2 | |
Sun et al. | Multifunctional dendritic mesoporous silica nanospheres loaded with silver nanoparticles as a highly active and recyclable heterogeneous catalyst | |
CN109912374A (en) | A kind of method that australene adds hydrogen to prepare cis-pinane | |
CN105798289A (en) | Preparation method and application of carbon shell isolated noble metal nanoparticles | |
CN107999019B (en) | Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof | |
CN107774246A (en) | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core | |
Gil et al. | Facile fabrication of functionalized core-shell Fe3O4@ SiO2@ Pd microspheres by urea-assisted hydrothermal route and their application in the reduction of nitro compounds | |
An et al. | A facile method to synthesize water-soluble Pd 8 nanoclusters unraveling the catalytic mechanism of p-nitrophenol to p-aminophenol | |
Saman et al. | Cetyltrimethylammonium bromide functionalized silica nanoparticles (MSN) synthesis using a combined sol-gel and adsorption steps with enhanced adsorption performance of oxytetracycline in aqueous solution |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |