CN104557485B - 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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- 238000005727 Friedel-Crafts reaction Methods 0.000 title claims abstract description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000002105 nanoparticle Substances 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 21
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [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
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012346 acetyl chloride Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 42
- 239000003054 catalyst Substances 0.000 description 17
- 239000013558 reference substance Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 235000013339 cereals Nutrition 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 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
- 238000005917 acylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- -1 iron oxide series compound Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000013049 sediment 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
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003905 agrochemical 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
- 125000003118 aryl group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014121 butter Nutrition 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion 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
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000001023 inorganic pigment 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
- 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
- 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
- 230000001590 oxidative effect Effects 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
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling 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
- 239000000243 solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses application of a micro-flow field reactor in Friedel-Crafts reaction, wherein nano iron oxide particles are filled in an immobilized microchannel reactor and used for catalyzing Friedel-Crafts acylation reaction of aromatic hydrocarbon and acetyl chloride. Wherein, the nano iron oxide particles are prepared by the following method: dissolving the inorganic substance containing iron with distilled water, pumping the aqueous solution of inorganic base and the aqueous solution of the inorganic substance containing iron into a microchannel modular reaction device respectively and simultaneously, keeping the residence time for 30s-1min, reacting at room temperature, centrifuging the reaction product, washing and drying the precipitate, and roasting for 2h at 500 ℃ in a muffle furnace. The invention fills the prepared nano iron oxide particles in an immobilized microchannel reactor for catalyzing Friedel-Crafts reaction of aromatic hydrocarbon and acetyl chloride, and the conversion rate of the raw material reaches 100 percent.
Description
Technical field
The present invention relates to a kind of immobilized miniflow field reactor that has a nano-sized iron oxide in Friedel-Crafts reactionApplication, belongs to field of fine chemical.
Background technology
Nano material is because it is small-sized, and electronics is limited in a space that volume is very little, causes electronics transportBe restricted, make electron mean free path very short, electronic coherence and limitation strengthen. Therefore, nano material occurs differentIn some special natures of conventional material. Nano material mainly comprises four large feature, 1. skin effects. 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 property are abundant. Transition metal oxide is wherein to attach most importance toThe one of wanting. Nano transition metal oxides is the specific type in nano material, and its size is in elementide and macroscopical thingThe transition region of body interfaces, its structure had both been different from solid matter, was also different from single atom. Conventionally people are by the oxidation of ironThing and light base oxide thereof all belong to iron oxide series compound. Can be divided into by the difference of its crystal formation, valence state and structureα, β and γ type Fe2O3, α, β and γ type FeOOH, FeO, Fe3O4Deng. Studying more iron oxide is mainly α-Fe2O3、γ-Fe2O3And Fe3O4. Iron oxide pigment is the important raw and processed materials of coatings industry, worldwide, and the volume of production and marketing of iron oxide pigment, onlyInferior to titanium dioxide, be second inorganic pigment that amount is large and wide. Transparent Fe2O3The simple particle diameter of pigment has 10nm, thereby hasHigh chroma, the high grade of transparency and high tinting strength, tinting power, its surface has good dispersiveness after special processing. Add it fineThe excellent performance such as heatproof, weather-proof, resistance to acids and bases, make transparent Fe2O3At high-grade automobile finish, building coating, anti-corrosion material etc.Be used widely in many fields such as powder coating and nylon, rubber, plastics and ink. Nano-sized iron oxide exists a large amount of brilliant simultaneouslyVolume defect, and Fe (III) in fault location easily absorption there is electron rich material or form complex with it and stablize. HaveThe nanometer Fe of semiconductor property2O3Can also serve as photochemical catalyst, nano material is made to hollow bead, can float over to contain hasOn the waste water surface of machine thing, utilize sunshine to degrade to accelerate wastewater treatment process. In addition nanometer Fe,2O3Composite also canPrepare the catalyst of the even phthalein of benzene as Oxybenzene acyloin. Magnetic nano-particle is due to its special superparamagnetism, thereby at huge magnetoelectricityThe aspects such as resistance, magnetic recording and magnetic liquid, permanent magnetism, soft magnetism, magnetic cooling, giant magnetoimpedance material and magnetic detector, magnetic-optic devicesAll have broad application prospects. Nano-sized iron oxide also has and widely should aspect biomedical and sensor material simultaneouslyWith.
The preparation of alpha-iron oxide nano-powder comprises that hydro-thermal method, sol-gel process, the precipitation method, forced hydrolysis method, electrochemistry closesEstablished law, thermal decomposition method, reverse microemulsion process. In addition, also have some as template, sonochemical method, spoke beta radiation method, skyGas oxidizing process and colloid chemistry method etc. CN200410023302.7 disclose a kind of ultra-fine/the preparation side of nano-sized iron oxide/iron powderMethod, is that iron salt solutions and aqueous slkali are carried out to complex reaction under the condition of supersonic oscillations, obtains transparent colloid, after being dried,At 350-700 DEG C of temperature, calcine, obtain nanometer/superfine nano croci. The method products therefrom powder sizeCarefully, purity is high, but product bad dispersibility, particle diameter is inhomogeneous. CN1817801A discloses a kind of alpha-ferric oxide of American football shape and has receivedThe synthetic method of rice grain, the method is taking ferric nitrate, ethylene glycol, ammoniacal liquor as raw material, preparation comprises ferric nitrate, ethylene glycolWater-ammonia water mixed solution, is positioned over this mixed solution in reactor, little 150～200 DEG C of temperature range heating 10～48Time, then through deionized water and absolute ethanol washing, put into drying box and be dried, obtain the alpha-ferric oxide of American football shapeNano particle.
Be one of effective means realizing carbon carbon Cheng Jian due to friedel-crafts acylation reaction, and be the various aryl of preparationKetone, the important means of heterocyclic arene ketone etc., so that it has in the industrial production such as medicine, agricultural chemicals, dyestuff, spices is very extensiveApplication, therefore chemists nourish very high interest to friedel-crafts acylation reaction always. In general, Fu-Ke acyl groupization is anti-What should use is lewis acid, as zinc chloride, aluminium chloride, iron chloride, butter of tin, titanium tetrachloride etc. or very strong protonAcid, as hydrofluoric acid, sulfuric acid etc. After reaction finishes, thereby these lewis acids and product coordination are deposited with the form of complex, so just can obtain target product after hydrolysis, this will cause the pollution of environment. So, in the past few decades in,Friedel-crafts acylation reaction is made great efforts the future development towards Green Chemistry always. By more effectively catalyst of exploitation, make anti-Answer efficiency to be improved, or optimize reaction condition, under microwave condition, the friedel-crafts acylation reaction in ionic liquid, realizesThe recycling of catalyst; Or be to use graphite as solid catalyst, and the development of various different-phase catalysts all makeObtaining friedel-crafts acylation reaction constantly pushes ahead. HashemSharghi etc. use through ultrasonic nano-sized iron oxide after treatmentCatalysis Friedel-Crafts acylation reaction, products collection efficiency can reach more than 90%, but catalysts reclaims difficulty, and heavyUtilize again rate variance. TaoLin etc. prepare composite catalyst FeOx/HZSM-5 and are applied in the acylation reaction of benzene, formerMaterial conversion ratio is up to 100%.
Summary of the invention
High for technological process complexity, cost in nowadays nano-sized iron oxide production process, particle is easily reunited, particle diameter dividesThe defects such as the shortcomings such as cloth is inhomogeneous and catalyst recovery difficulty, technical problem to be solved by this invention is to provide immobilized receivingThe application of the miniflow field reactor of rice iron oxide in Friedel-Crafts reaction, the method technique is simple, post-processing operationSimply, the reaction time is short, is suitable for suitability for industrialized production; Gained ferric oxide particles is little, be evenly distributed, good crystallinity, good stabilityHigh with transparency; In addition can not cause stopping up 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 solidSurely change in micro passage reaction, for the Friedel-Crafts acylation reaction of catalysis aromatic hydrocarbon and chloroacetic chloride.
Described nano-sized iron oxide particle prepares as follows: the inorganic matter of iron content distilled water dissolved, thenThe aqueous solution of the aqueous solution of inorganic base and iron content inorganic matter is pumped in microchannel module reaction unit respectively simultaneously, keep stoppingStay time 30s-1min, under room temperature, react, product is centrifugal, precipitate through washing, dry, then in Muffle furnace400～700 DEG C of roasting 1～3h (preferably 500 DEG C of roasting 2h), obtain nano-sized iron oxide particle.
Wherein, the inorganic matter of described iron content be in ferric nitrate, ferric sulfate and iron chloride any one or several. ExcellentSelect ferric nitrate or ferric sulfate.
Wherein, described inorganic base be in NaOH, potassium hydroxide, ammoniacal liquor, urea and six methine four ammoniums arbitrarilyOne or several. Preferably ammoniacal liquor or urea.
Wherein, the solute concentration of described inorganic base aqueous solution is 3～20wt%, the solute of the aqueous solution of iron content inorganic matterConcentration is 3～20wt%; The mol ratio of described inorganic base and iron content inorganic matter is 3～8:1, preferably 3～6:1.
Wherein, described microchannel module reaction unit is that valve formula blender is (purchased from EhrfeldMikrotechnikBTSGmbH, model is 0111-2-0014-F).
Wherein, nano-sized iron oxide is filled in immobilization micro passage reaction, reaction temperature be 30～120 DEG C (preferably40～100 DEG C, most preferably 100 DEG C), pressure is 8.0～25.0bar (preferably 8.0～20.0bar, most preferably 20.0bar), excellentThe mol ratio of selecting aromatic hydrocarbon and chloroacetic chloride is 1:1～6 (preferably 1:1～4, most preferably 1:4), and the reaction time is that 10～30min is (excellentSelect 10～25min, most preferably 25min).
Wherein, described immobilization micro passage reaction is purchased from Bayer, and model is fixedbedmeanderReactorHC. When use, only catalyst need be filled out in the filling slot of reactor and realize and fixing.
Wherein, described aromatic hydrocarbon is methyl phenyl ethers anisole, toluene, chlorobenzene, bromobenzene, nitrobenzene, ortho-xylene, anthracene or biphenyl.
Beneficial effect: the present invention compared with prior art, has following advantage:
1. the nano-sized iron oxide particle preparation process reaction time of the present invention short, whole generated time is 30s-1min. Pass throughChange process conditions, as the parameter such as time, pH, can autotelic course of reaction be realized accurately and being controlled.
2. the coarse iron oxide product postprocessing that the present invention obtains is simple, obtains nano-sized iron oxide particle.
3. the present invention is filled in nano-sized iron oxide in immobilization micro passage reaction, for catalysis aromatic hydrocarbon and chloroacetic chlorideFriedel-Crafts acylation reaction, reaction efficiency is high, feed stock conversion is up to 100%, and recovery place of catalystManage very convenient.
Brief description of the drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the powder diagram of the nano-sized iron oxide particle prepared of the present invention.
Detailed description of the invention
According to following embodiment, the present invention may be better understood. But, those skilled in the art will readily understand, realExecute routine described content only for the present invention is described, and should also can not limit in claims described in detailInvention.
Embodiment 1
Be 1:3 pump by the aqueous solution of 3wt% ferric sulfate and 5wt% ammoniacal liquor according to the mol ratio of inorganic base and iron content inorganic matterIn path modular reaction unit, keep time of staying 30s in a subtle way, under room temperature, react, product is centrifugal, precipitationWith distilled water washing 3 times, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then 500 DEG C of roastings in Muffle furnaceBurn 2h, obtain final products nano-sized iron oxide, average grain diameter 20nm.
Embodiment 2
Be 1:4 by the aqueous solution of 10wt% ferric sulfate and 15wt% ammoniacal liquor according to the mol ratio of inorganic base and iron content inorganic matterPump in microchannel module reaction unit, keep time of staying 1min, under room temperature, react, product is centrifugal,Distilled water washing 3 times for precipitation, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace 500DEG C roasting 2h, obtains final products nano-sized iron oxide, average grain diameter 30nm.
Embodiment 3
Be 1:6 by the aqueous solution of 20wt% ferric sulfate and 20wt% ammoniacal liquor according to the mol ratio of inorganic base and iron content inorganic matterPump in microchannel module reaction unit, keep time of staying 1min, under room temperature, react, product is centrifugal,Distilled water washing 3 times for precipitation, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace 500DEG C roasting 2h, obtains final products nano-sized iron oxide, average grain diameter 100nm.
Embodiment 4
Be 1:3 by the aqueous solution of 5wt% ferric sulfate and 10wt% ammoniacal liquor according to the mol ratio of inorganic base and iron content inorganic matterPump in microchannel module reaction unit, keep time of staying 30s, under room temperature, react, product is centrifugal, heavyDistilled water washing 3 times for forming sediment, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace 500 DEG CRoasting 2h, obtains final products nano-sized iron oxide, average grain diameter 10nm.
Embodiment 5
Be 1:3 by the aqueous solution of 5wt% ferric nitrate and 10wt% urea according to the mol ratio of inorganic base and iron content inorganic matterPump in microchannel module reaction unit, keep time of staying 30s, under room temperature, react, product is centrifugal, heavyDistilled water washing 3 times for forming sediment, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace 500 DEG CRoasting 2h, obtains final products nano-sized iron oxide, average grain diameter 15nm.
Embodiment 6
By the aqueous solution of 5wt% iron chloride and 10wt% NaOH according to the mol ratio of inorganic base and iron content inorganic matter be1:3 pumps in microchannel module reaction unit, keep time of staying 30s, under room temperature, react, by product fromThe heart, distilled water washing 3 times for precipitation, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace500 DEG C of roasting 2h, obtain final products nano-sized iron oxide, average grain diameter 200nm.
Embodiment 7
By the aqueous solution of 5wt% ferric sulfate and 10wt% six methine four ammoniums according to inorganic base and iron content inorganic matter moleThan pumping in microchannel module reaction unit for 1:3, keep time of staying 30s, under room temperature, react, by productCentrifugal, distilled water washing 3 times for precipitation, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then at Muffle furnaceIn 500 DEG C of roasting 2h, obtain final products nano-sized iron oxide, average grain diameter 60nm.
Embodiment 8
By the aqueous solution of 5wt% ferric sulfate and 10wt% potassium hydroxide according to the mol ratio of inorganic base and iron content inorganic matter be1:3 pumps in microchannel module reaction unit, keep time of staying 30s, under room temperature, react, by product fromThe heart, distilled water washing 3 times for precipitation, then use absolute ethanol washing 1 time, and dry in vacuum desiccator, then in Muffle furnace500 DEG C of roasting 2h, obtain final products nano-sized iron oxide, average grain diameter 200nm.
Embodiment 9
By the nano-sized iron oxide particle of preparing in embodiment 1-4 and reference substance, (reference substance is purchased from receiving in AladdinRice iron oxide, particle diameter 30nm) to react with the Friedel-Crafts of chloroacetic chloride for catalysis methyl phenyl ethers anisole, described method will be for receivingRice iron oxide is filled in immobilization micro passage reaction, and reaction temperature is 40 DEG C, and pressure is 8.0bar, methyl phenyl ethers anisole and chloroacetic chlorideMol ratio be 1:1, the reaction time is 10min. The Friedel-Crafts of different catalysts catalysis methyl phenyl ethers anisole and chloroacetic chloride is anti-The reaction result of answering is in table 1.
Table 1
| Catalyst | 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 of preparing in embodiment 1-4 and reference substance, (reference substance is purchased from receiving in AladdinRice iron oxide, particle diameter 30nm) to react with the Friedel-Crafts of chloroacetic chloride for catalysis methyl phenyl ethers anisole, described method will be for receivingRice iron oxide is filled in immobilization micro passage reaction, and reaction temperature is 90 DEG C, and pressure is 12.0bar, methyl phenyl ethers anisole and acetylThe mol ratio of chlorine is 1:3, and the reaction time is 20min. The Friedel-Crafts of different catalysts catalysis methyl phenyl ethers anisole and chloroacetic chlorideThe reaction result of reaction is in table 2.
Table 2
| Catalyst | 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 of preparing in embodiment 1-4 and reference substance, (reference substance is purchased from receiving in AladdinRice iron oxide, particle diameter 30nm) to react with the Friedel-Crafts of chloroacetic chloride for catalysis methyl phenyl ethers anisole, described method will be for receivingRice iron oxide is filled in immobilization micro passage reaction, and reaction temperature is 100 DEG C, and pressure is 20.0bar, methyl phenyl ethers anisole and acetylThe mol ratio of chlorine is 1:4, and the reaction time is 25min. The Friedel-Crafts of different catalysts catalysis methyl phenyl ethers anisole and chloroacetic chlorideThe reaction result of reaction is in table 3.
Table 3
| Catalyst | 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 of preparing in embodiment 1-4 and reference substance, (reference substance is purchased from receiving in AladdinRice iron oxide, particle diameter 30nm) to react with the Friedel-Crafts of chloroacetic chloride for catalysis methyl phenyl ethers anisole, described method will be for receivingRice iron oxide is filled in immobilization micro passage reaction, and reaction temperature is 120 DEG C, and pressure is 25.0bar, methyl phenyl ethers anisole and acetylThe mol ratio of chlorine is 1:4, and the reaction time is 25min. The Friedel-Crafts of different catalysts catalysis methyl phenyl ethers anisole and chloroacetic chlorideThe reaction result of reaction is in table 4.
Table 4
| Catalyst | 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
Friedel-Crafts by the nano-sized iron oxide particle of preparation in embodiment 4 for catalysis substituted benzene and chloroacetic chlorideReaction, described method is for to be filled in nano-sized iron oxide in immobilization micro passage reaction, and reaction temperature is 100 DEG C, pressureFor 20.0bar, the mol ratio of methyl phenyl ethers anisole and chloroacetic chloride is 1:4, different material and excess acetyl chloride the results are shown in Table 5.
Table 5
Claims (7)
1. the application of miniflow field reactor in Friedel-Crafts reaction, is characterized in that, nano-sized iron oxide particle is filled outFill in immobilization micro passage reaction, for the Friedel-Crafts acylation reaction of catalysis aromatic hydrocarbon and chloroacetic chloride;
Wherein, described nano-sized iron oxide particle prepares as follows: the inorganic matter of iron content distilled water is dissolved, thenThe aqueous solution of the aqueous solution of inorganic base and iron content inorganic matter is pumped in microchannel module reaction unit respectively simultaneously, keep stoppingStay time 30s-1min, under room temperature, react, product is centrifugal, precipitate through washing, dry, then in Muffle furnace400～700 DEG C of roasting 1～3h, obtain nano-sized iron oxide particle.
2. application according to claim 1, is characterized in that, the inorganic matter of described iron content be ferric nitrate, ferric sulfate andAny one in iron chloride or several.
3. application according to claim 1, is characterized in that, described inorganic base is NaOH, potassium hydroxide and ammoniaAny one in water or several.
4. application according to claim 1, is characterized in that, the solute concentration of described inorganic base aqueous solution is 3～20wt%, the solute concentration of the aqueous solution of iron content inorganic matter is 3～20wt%; Described inorganic base and iron content inorganic matter moleThan being 3～8:1.
5. application according to claim 1, is characterized in that, described microchannel module reaction unit is that valve formula is mixedDevice.
6. application according to claim 1, is characterized in that, nano-sized iron oxide is filled in to immobilization micro passage reactionIn, reaction temperature is 30～120 DEG C, and pressure is 8.0～25.0bar, and the mol ratio of aromatic hydrocarbon and chloroacetic chloride is 1:1～6, reactionTime is 10～30min.
7. application according to claim 1, is characterized in that, described aromatic hydrocarbon be methyl phenyl ethers anisole, toluene, chlorobenzene, bromobenzene,Nitrobenzene, ortho-xylene, anthracene or biphenyl.
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