CN104557485A - Application of micro-flow field reactor in Friedel-Crafts reaction - Google Patents
Application of micro-flow field reactor in Friedel-Crafts reaction Download PDFInfo
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- CN104557485A CN104557485A CN201510016104.6A CN201510016104A CN104557485A CN 104557485 A CN104557485 A CN 104557485A CN 201510016104 A CN201510016104 A CN 201510016104A CN 104557485 A CN104557485 A CN 104557485A
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- friedel
- iron oxide
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- 238000005727 Friedel-Crafts reaction Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 24
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 40
- 239000002105 nanoparticle Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 15
- 239000011707 mineral Substances 0.000 claims description 15
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 235000010755 mineral Nutrition 0.000 description 12
- 239000013558 reference substance Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- -1 ferric oxide series compound Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses an application of a micro-flow field reactor in Friedel-Crafts reaction. An immobilized microchannel reactor is filled with nano iron oxide particles for catalysis of Friedel-Crafts acylation reaction of aromatic hydrocarbon and acetyl chloride, wherein the nano iron oxide particles are prepared by the following methods: dissolving an iron-containing inorganic matter with distilled water, respectively and simultaneously pumping a water solution of inorganic alkali and a water solution of the iron-containing inorganic matter into the immobilized microchannel reaction device; standing for 30 seconds to 1 minute, reacting at a room temperature, and centrifuging the reaction product; and washing and drying sediments, and then sintering in a muffle furnace at 500 DEG C for 2 hours. The immobilized microchannel reactor is filled with the nano iron oxide particles prepared by the method for catalysis of Friedel-Crafts acylation reaction of the aromatic hydrocarbon and acetyl chloride.
Description
Technical field
The present invention relates to a kind of immobilized have the miniflow field reactor of nano-sized iron oxide Friedel-Crafts reaction in application, belong to field of fine chemical.
Background technology
Nano material is small-sized due to it, and electronics is limited in the very little space of a volume, causes electronics to transport and is restricted, make electron mean free path very short, and electronic coherence and limitation strengthen.Therefore, there are some special propertys being different from conventional material in nano material.Nano material mainly comprises four large feature, 1. surface effectss.2. small-size effect.3. interfacial effect.4. quantum effect.5. macro quanta tunnel effect.
Metal oxide materials is of a great variety, and chemistry and physical properties are enriched.Transition metal oxide is the one of wherein outbalance.Nano transition metal oxides is the specific type in nano material, and its size is in the zone of transition of elementide and macro object interfaces, and its structure was both different from solid matter, is also different from single atom.The oxide compound of iron and light base oxide thereof are all belonged to ferric oxide series compound by usual people.α, β and γ type Fe can be divided into by the difference of its crystal formation, valence state and structure
2o
3, α, β and γ type FeOOH, FeO, Fe
3o
4deng.Study more ferric oxide mainly α-Fe
2o
3, γ-Fe
2o
3and Fe
3o
4.Iron oxide pigment is the important raw and processed materials of coatings industry, and worldwide, the volume of production and marketing of iron oxide pigment, is only second to titanium dioxide, is the mineral dye that second amount is large and wide.Transparent Fe
2o
3the simple particle diameter of pigment has 10nm, and thus have high chroma, high-clarity and high tinting strength, namely its surface has good dispersiveness after special process.Add the excellent performance such as its good heatproof, weather-proof, resistance to acids and bases, make transparent Fe
2o
3be used widely in many fields such as the powder coatings such as superior automobile finish paint, building coating, impregnating material and nylon, rubber, plastics and ink.There is a large amount of lattice defect in nano-sized iron oxide simultaneously, and the easy absorption of the Fe (III) being in fault location has electron rich material or forms title complex with it and stablize.There is the nanometer Fe of semiconductor property
2o
3as photocatalyst, nano material can also be made hollow beads, can float over containing on organic wastewater surface, utilize sunlight to degrade to accelerate wastewater treatment process.In addition, nanometer Fe
2o
3matrix material also can be used as the catalyzer that Oxybenzene acyloin prepares the even phthalein of benzene.Magnetic nano-particle, due to its special superparamagnetism, thus all has broad application prospects in giant magnetoresistance, magnetic recording and magnetic liquid, permanent magnetism, soft magnetism, magnetic cooling, giant magnetoimpedance material and magnetic detector, magnetic-optic devices etc.Nano-sized iron oxide also has a wide range of applications in biomedicine and sensor material simultaneously.
The preparation of alpha-iron oxide nano-powder comprises hydrothermal method, sol-gel method, the precipitator method, forced hydrolysis method, electrochemical synthesis, thermal decomposition method, reverse microemulsion process.In addition, some are also had as template, sonochemical method, spoke beta radiation method, air oxidation process and colloid chemistry methods etc.CN200410023302.7 disclose a kind of ultra-fine/preparation method of nano-sized iron oxide/iron powder, that iron salt solutions and alkaline solution are carried out complex reaction under the condition of ultra-sonic oscillation, obtain transparent colloid, after drying, calcine at 350-700 DEG C of temperature, obtain nanometer/superfine nano croci.The method products therefrom powder size is thin, and purity is high, but product bad dispersibility, particle diameter is uneven.CN1817801A discloses a kind of synthetic method of alpha-ferric oxide nano particle of American football shape, the method is for raw material with iron nitrate, ethylene glycol, ammoniacal liquor, preparation comprises the water-ammonia water mixed solution of iron nitrate, ethylene glycol, this mixing solutions is positioned in reactor, 150 ~ 200 DEG C of temperature range heating 10 ~ 48 hours, then through deionized water and absolute ethanol washing, put into loft drier and carry out drying, namely obtain the alpha-ferric oxide nano particle of American football shape.
Because friedel-crafts acylation reaction is one of most effective means realizing carbon carbon Cheng Jian; and be the various aryl ketones of preparation; the important means of heterocyclic arene ketone etc.; so it has application widely in the industrial production such as medicine, agricultural chemicals, dyestuff, spices, therefore chemists nourish very high interest to friedel-crafts acylation reaction always.In general, friedel-crafts acylation reaction uses Lewis acid, as zinc chloride, aluminum chloride, iron(ic) chloride, tin tetrachloride, titanium tetrachloride etc. or very strong protonic acid, as hydrofluoric acid, sulfuric acid etc.After reaction terminates, these Lewis acids and product coordination thus exist with the form of title complex, so just can obtain target product after hydrolyzing, this will cause the pollution of environment.So in the past few decades, friedel-crafts acylation reaction makes great efforts the future development towards Green Chemistry always.By the more effective catalyzer of exploitation, reaction efficiency is improved, or Optimal reaction conditions, as under microwave condition, the friedel-crafts acylation reaction in ionic liquid, realizes the recycling of catalyzer; Or be use graphite as solid catalyst, and the development of various different-phase catalyst all make friedel-crafts acylation reaction constantly push ahead.HashemSharghi etc. use the butylphenol Catalyzed by Nano-ferric Oxide Friedel-Crafts acylation reaction after supersound process, and products collection efficiency can reach more than 90%, but catalysts reclaims difficulty, recycling rate variance.Tao Lin etc. prepares composite catalyst FeOx/HZSM-5 and is applied in the acylation reaction of benzene, and feed stock conversion is up to 100%.
Summary of the invention
The defect such as shortcoming and catalyst recovery difficulty such as complicated for the technical process in nowadays nano-sized iron oxide production process, cost is high, particle is easily reunited, size distribution is uneven, technical problem to be solved by this invention be to provide immobilized have the miniflow field reactor of nano-sized iron oxide Friedel-Crafts reaction in application, the method technique is simple, post-processing operation is simple, reaction times is short, is suitable for suitability for industrialized production; Gained ferric oxide particles is little, be evenly distributed, good crystallinity, good stability and transparency are high; In addition blocking can not be caused to microreactor.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
The application of miniflow field reactor in Friedel-Crafts reaction, by nano oxidized iron particles filled in immobilization micro passage reaction, for the Friedel-Crafts acylation reaction of catalysis aromatic hydrocarbon and Acetyl Chloride 98Min..
Described nano-sized iron oxide particle prepares as follows: dissolved by the inorganics distilled water of iron content, again the aqueous solution of the aqueous solution of mineral alkali and iron content inorganics is pumped in microchannel module reaction unit respectively simultaneously, keep residence time 30s-1min, react under room temperature, reaction product is centrifugal, precipitate through washing, dry, then in retort furnace 400 ~ 700 DEG C of roasting 1 ~ 3h (preferably 500 DEG C of roasting 2h), obtain nano-sized iron oxide particle.
Wherein, the inorganics of described iron content be in iron nitrate, ferric sulfate and iron(ic) chloride any one or several.Preferred iron nitrate or ferric sulfate.
Wherein, described mineral alkali be in sodium hydroxide, potassium hydroxide, ammoniacal liquor, urea and six methyne four ammoniums any one or several.Preferred ammoniacal liquor or urea.
Wherein, the solute concentration of described inorganic base aqueous solution is 3 ~ 20wt%, and the solute concentration of the aqueous solution of iron content inorganics is 3 ~ 20wt%; The mol ratio of described mineral alkali and iron content inorganics is 3 ~ 8:1, preferably 3 ~ 6:1.
Wherein, described microchannel module reaction unit is valve type mixing tank (purchased from Ehrfeld MikrotechnikBTS GmbH, model is 0111-2-0014-F).
Wherein, nano-sized iron oxide is filled in immobilization micro passage reaction, temperature of reaction is 30 ~ 120 DEG C (preferably 40 ~ 100 DEG C, most preferably 100 DEG C), pressure is 8.0 ~ 25.0bar (preferably 8.0 ~ 20.0bar, most preferably 20.0bar), the mol ratio of preferred aromatic hydrocarbon and Acetyl Chloride 98Min. is (preferred 1:1 ~ 4,1:1 ~ 6, most preferably 1:4), the reaction times is 10 ~ 30min (preferably 10 ~ 25min, most preferably 25min).
Wherein, described immobilization micro passage reaction is purchased from Bayer, and model is fixed bed meander reactor HC.Only catalyzer need be filled out during use and realize fixing in the filling slot of reactor.
Wherein, described aromatic hydrocarbon is methyl-phenoxide, toluene, chlorobenzene, bromobenzene, oil of mirbane, o-Xylol, anthracene or biphenyl.
Beneficial effect: the present invention compared with prior art, has following advantage:
1. the nano-sized iron oxide particulate production reaction times of the present invention is short, and whole generated time is 30s-1min.By changing processing condition, as the parameter such as time, pH, can autotelicly realize accurately controlling to reaction process.
2. the coarse iron oxide product postprocessing that obtains of the present invention is simple, namely obtains nano-sized iron oxide particle.
3. nano-sized iron oxide is filled in immobilization micro passage reaction by the present invention, and for the Friedel-Crafts acylation reaction of catalysis aromatic hydrocarbon and Acetyl Chloride 98Min., reaction efficiency is high, and feed stock conversion is up to 100%, and the recycling of catalyzer is very convenient.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the powder diagram of nano-sized iron oxide particle prepared by the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 3wt% ferric sulfate and 5wt% ammoniacal liquor according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 20nm again.
Embodiment 2
Be that 1:4 pumps in microchannel module reaction unit by the aqueous solution of 10wt% ferric sulfate and 15wt% ammoniacal liquor according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 1min, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 30nm again.
Embodiment 3
Be that 1:6 pumps in microchannel module reaction unit by the aqueous solution of 20wt% ferric sulfate and 20wt% ammoniacal liquor according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 1min, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 100nm again.
Embodiment 4
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 5wt% ferric sulfate and 10wt% ammoniacal liquor according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 10nm again.
Embodiment 5
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 5wt% iron nitrate and 10wt% urea according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 15nm again.
Embodiment 6
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 5wt% iron(ic) chloride and 10wt% sodium hydroxide according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 200nm again.
Embodiment 7
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 5wt% ferric sulfate and 10wt% six methyne four ammonium according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 60nm again.
Embodiment 8
Be that 1:3 pumps in microchannel module reaction unit by the aqueous solution of 5wt% ferric sulfate and 10wt% potassium hydroxide according to the mol ratio of mineral alkali and iron content inorganics, keep residence time 30s, react under room temperature, reaction product is centrifugal, precipitation distilled water wash 3 times, then use absolute ethanol washing 1 time, and it is dry in vacuum drier, 500 DEG C of roasting 2h in retort furnace, obtain the finished product nano-sized iron oxide, median size 200nm again.
Embodiment 9
By the nano-sized iron oxide particle prepared in embodiment 1-4 and reference substance, (reference substance is purchased from the nano-sized iron oxide in Aladdin, particle diameter 30nm) react for the Friedel-Crafts of catalysis methyl-phenoxide and Acetyl Chloride 98Min., described method is for be filled in immobilization micro passage reaction by nano-sized iron oxide, temperature of reaction is 40 DEG C, pressure is 8.0bar, the mol ratio of methyl-phenoxide and Acetyl Chloride 98Min. is 1:1, and the reaction times is 10min.The reaction result that the Friedel-Crafts of different catalysts catalysis methyl-phenoxide and Acetyl Chloride 98Min. reacts is in table 1.
Table 1
| Catalyzer | Feed stock conversion |
| Embodiment 1 | 81.12％ |
| Embodiment 2 | 83.23％ |
| Embodiment 3 | 79.34％ |
| Embodiment 4 | 84.23％ |
| Reference substance | 71.23％ |
Embodiment 10
By the nano-sized iron oxide particle prepared in embodiment 1-4 and reference substance, (reference substance is purchased from the nano-sized iron oxide in Aladdin, particle diameter 30nm) react for the Friedel-Crafts of catalysis methyl-phenoxide and Acetyl Chloride 98Min., described method is for be filled in immobilization micro passage reaction by nano-sized iron oxide, temperature of reaction is 90 DEG C, pressure is 12.0bar, the mol ratio of methyl-phenoxide and Acetyl Chloride 98Min. is 1:3, and the reaction times is 20min.The reaction result that the Friedel-Crafts of different catalysts catalysis methyl-phenoxide and Acetyl Chloride 98Min. reacts is in table 2.
Table 2
| Catalyzer | Feed stock conversion |
| Embodiment 1 | 92.12％ |
| Embodiment 2 | 93.12％ |
| Embodiment 3 | 87.45％ |
| Embodiment 4 | 94.17％ |
| Reference substance | 82.23％ |
Embodiment 11
By the nano-sized iron oxide particle prepared in embodiment 1-4 and reference substance, (reference substance is purchased from the nano-sized iron oxide in Aladdin, particle diameter 30nm) react for the Friedel-Crafts of catalysis methyl-phenoxide and Acetyl Chloride 98Min., described method is for be filled in immobilization micro passage reaction by nano-sized iron oxide, temperature of reaction is 100 DEG C, pressure is 20.0bar, the mol ratio of methyl-phenoxide and Acetyl Chloride 98Min. is 1:4, and the reaction times is 25min.The reaction result that the Friedel-Crafts of different catalysts catalysis methyl-phenoxide and Acetyl Chloride 98Min. reacts is in table 3.
Table 3
| Catalyzer | Feed stock conversion |
| Embodiment 1 | 95.18％ |
| Embodiment 2 | 94.67％ |
| Embodiment 3 | 89.34％ |
| Embodiment 4 | 100.00％ |
| Reference substance | 83.12％ |
Embodiment 12
By the nano-sized iron oxide particle prepared in embodiment 1-4 and reference substance, (reference substance is purchased from the nano-sized iron oxide in Aladdin, particle diameter 30nm) react for the Friedel-Crafts of catalysis methyl-phenoxide and Acetyl Chloride 98Min., described method is for be filled in immobilization micro passage reaction by nano-sized iron oxide, temperature of reaction is 120 DEG C, pressure is 25.0bar, the mol ratio of methyl-phenoxide and Acetyl Chloride 98Min. is 1:4, and the reaction times is 25min.The reaction result that the Friedel-Crafts of different catalysts catalysis methyl-phenoxide and Acetyl Chloride 98Min. reacts is in table 4.
Table 4
| Catalyzer | Feed stock conversion |
| Embodiment 1 | 94.38％ |
| Embodiment 2 | 96.45％ |
| Embodiment 3 | 89.34％ |
| Embodiment 4 | 96.57％ |
| Reference substance | 82.89％ |
Embodiment 13
The Friedel-Crafts that the nano-sized iron oxide particle of preparation in embodiment 4 is used for catalysis substituted benzene and Acetyl Chloride 98Min. is reacted, described method is for be filled in immobilization micro passage reaction by nano-sized iron oxide, temperature of reaction is 100 DEG C, pressure is 20.0bar, the mol ratio of methyl-phenoxide and Acetyl Chloride 98Min. is 1:4, different material and excess acetyl chloride the results are shown in Table 5.
Table 5
Claims (8)
1. the application of miniflow field reactor in Friedel-Crafts reaction, is characterized in that, by nano oxidized iron particles filled in immobilization micro passage reaction, for the Friedel-Crafts acylation reaction of catalysis aromatic hydrocarbon and Acetyl Chloride 98Min..
2. application according to claim 1, it is characterized in that, described nano-sized iron oxide particle prepares as follows: dissolved by the inorganics distilled water of iron content, again the aqueous solution of the aqueous solution of mineral alkali and iron content inorganics is pumped in microchannel module reaction unit respectively simultaneously, keep residence time 30s-1min, react under room temperature, reaction product is centrifugal, precipitate through washing, dry, then in retort furnace 400 ~ 700 DEG C of roasting 1 ~ 3h, obtain nano-sized iron oxide particle.
3. application according to claim 2, is characterized in that, the inorganics of described iron content be in iron nitrate, ferric sulfate and iron(ic) chloride any one or several.
4. application according to claim 2, is characterized in that, described mineral alkali be in sodium hydroxide, potassium hydroxide, ammoniacal liquor, urea and six methyne four ammoniums any one or several.
5. application according to claim 2, is characterized in that, the solute concentration of described inorganic base aqueous solution is 3 ~ 20wt%, and the solute concentration of the aqueous solution of iron content inorganics is 3 ~ 20wt%; The mol ratio of described mineral alkali and iron content inorganics is 3 ~ 8:1.
6. application according to claim 2, is characterized in that, described microchannel module reaction unit is valve type mixing tank.
7. application according to claim 1, is characterized in that, is filled in by nano-sized iron oxide in immobilization micro passage reaction, temperature of reaction is 30 ~ 120 DEG C, pressure is 8.0 ~ 25.0bar, and the mol ratio of aromatic hydrocarbon and Acetyl Chloride 98Min. is 1:1 ~ 6, and the reaction times is 10 ~ 30min.
8. application according to claim 1, is characterized in that, described aromatic hydrocarbon is methyl-phenoxide, toluene, chlorobenzene, bromobenzene, oil of mirbane, o-Xylol, anthracene or biphenyl.
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