CN104069892A - Preparation method for magnetic microsphere supported high-molecular catalyst - Google Patents
Preparation method for magnetic microsphere supported high-molecular catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method for a magnetic microsphere supported high-molecular catalyst and belongs to the technical field of preparation process of chemical catalysts. The high-molecular catalyst is a novel core/shell type heterogeneous catalyst and has the following characteristics that an inorganic magnetic material is adopted as an inner core, a high-molecular material is adopted as a shell, a catalytic center is supported by the covalent bonds and coordinate bonds on the high-molecular surface, certain magnetism is achieved, and the catalyst can be conveniently separated, recycled and applied from a reaction system. The catalytic center with diversified functions is supported by modifying the high-molecular surface, and the adaptability to various different application occasions can be achieved. The process is simple in process, is environmentally friendly and conforms to the trend of green chemistry.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic microsphere carried polymer catalyst, belong to chemical catalyst fabricating technology field.
Background technology
Magnetic microsphere carried polymer catalyst refers to that organic high molecular polymer wraps up inorganic magnetic material, has certain magnetic and special construction, in chemical reaction, plays the composite of heterogeneous catalysis effect.Inorganic magnetic material comprises that iron, cobalt, nickel simple substance and oxide, alloy etc. can directly or indirectly produce the material of magnetic, macromolecular material comprises various natural polymers (as shitosan, gelatin, fibroin albumen, liposome, poly-polysaccharide etc.) and manually synthesizes macromolecule (as polystyrene, polyethylene, polypropylene, polyacrylamide, polyacrylic acid, polyacrylate etc.), and the catalytic center of its load comprises the materials such as various metal simple-substances (as palladium, platinum, ruthenium, osmium, copper, cobalt, nickel, zinc, iron) and salt thereof, part and various phosphorous, nitrogen, sulphur, boron.Magnetic microsphere carried polymer catalyst has numerous characteristics of magnetic and macromolecular material simultaneously: can not only add surface active groups by methods such as copolymerization and surface modifications, also have magnetic responsiveness, can under additional magnetic fields, carry out separation and control.
In numerous organic chemical reactionses, as reactions such as Heck, Susuki, Appel, Knoevenagel, Wittig, often adopt the materials such as metal and salt thereof, part and various phosphorous, nitrogen, sulphur, boron to make catalyst.The catalyst of this class reaction of developing is the earliest all micromolecule catalyst, participates in reaction greatly mainly with homogeneous phase form.Although this class catalyst has active high, the feature such as be swift in response, also exist expensive, be difficult for recovery, complex operation, easily sneak in product, the shortcoming such as contaminated environment.
Take magnetic inorganic particle (comprising the magnetisable materials such as iron, cobalt, nickel simple substance and oxide thereof) as core, take high molecular polymer as shell, there is following characteristics at the various catalytic centers of high molecular polymer area load, the magnetic microsphere carried polymer catalyst that forms core/shell type structure:
One, magnetic microsphere carried polymer catalyst can be separated from reaction system with form very easily---and under additional magnetic fields, catalyst is fixed on ad-hoc location in reactor, and reactant liquor can be discharged at the bottom of still, very simple and convenient.Hereby to illustrate the convenience of this operation: commonly use the catalyst that highly active palladium carbon is done hydro-reduction in Chemical Manufacture; after reaction completes, palladium carbon is separated with reactant liquor; conventionally way is suction filtration; and under the state of inflated with nitrogen protection in closed container, carry out; but also can not take out too dry; otherwise the easy spontaneous combustion of catalyst, this will produce very seriously even catastrophic consequence.The catalyst separation mode of this routine need to be used professional pumping and filtering device, high to equipment requirement, complex operation, and to be equipped with special operating personnel in the explosion-proof Venue Operations of special use, to enterprise, cause certain financial burden and great security hidden danger.Use magnetic microsphere carried polymer catalyst can address this problem well, easy and simple to handle, without security risks, do not need special operating personnel.
Two, magnetic microsphere carried polymer catalyst can polluted product---the catalytic center of magnetic microsphere carried polymer catalyst be by loading on macromolecule surface with high polymer monomer copolymerization or coordinate bond, there is very high stability, be not easy disengaging and enter in reaction system, can be easily separated with reaction system under the effect of externally-applied magnetic field.Conventional palladium-carbon catalyst is to adopt on active carbon, to make palladium is immobilized, its catalytic center (palladium) relies on molecular separating force to be combined between carrier (active carbon), intensity is lower, in the course of reaction of vigorous stirring, easily from carrier, depart from, thereby pollution products, and cause and reclaim not exclusively.Most of little molecule phosphorus-containing catalysts participate in reaction with homogeneous phase form, need the operations such as extraction by repeatedly, distillation, recrystallization phosphorus-containing catalyst content could be controlled to acceptable scope after having reacted.
Three, magnetic microsphere carried polymer catalyst is convenient to apply mechanically---and under additional magnetic fields, magnetic microsphere carried polymer catalyst can rest in reactor and with reactant liquor, not flow out, and can continue to produce after adding new raw material.The heterogeneous supported catalyst (as palladium carbon) that does not possess magnetic will could be separated by suction filtration after reaction completes from reactant liquor, and then puts in reactor and carry out the production of next batch, time-consuming, and effort is expensive.
Four, magnetic microsphere carried polymer catalyst is easy to reclaim---because magnetic microsphere carried polymer catalyst participates in reaction system with heterogeneous form, separated from reaction system under magnetic fields after having reacted, then pass through the means such as burning by its harmless treatment.The phosphorous ligand catalyst of homogeneous phase will be separated it by operations such as loaded down with trivial details extraction, mistake post, distillation, recrystallizations after having reacted from reaction system.Because most of phosphorous ligand catalysts have toxicity, and the easy polluted-water of P elements, in liquid waste processing, also need to increase extra operating procedure it is innoxious after discharge.
Summary of the invention
The object of the invention is to overcome the deficiency of existing catalyst system, provide a kind of environmentally friendly, operation is convenient, the heterogeneous loaded catalyst of the magnetic core/shell-type of tool, the i.e. preparation method of magnetic microsphere carried polymer catalyst.
For achieving the above object, the present invention is by the following technical solutions:
The first step: the kernel of preparing magnetic microsphere carried polymer catalyst---magnetic microsphere.
Magnetic microsphere is comprised of inorganic magnetic material, specifically refers to that iron, cobalt, nickel and oxide, alloy etc. can directly or indirectly produce the material of magnetic, and research is the most popular with Fe 3 O 4 magnetic microballoon at present.
The Fe 3 O 4 magnetic microballoon of now take is set forth technical scheme of the present invention as prototype.
Tri-iron tetroxide magnetic microsphere has following two kinds of preparation technologies:
1.1, adopt coprecipitation to prepare tri-iron tetroxide magnetic microsphere, concrete steps are as follows:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add in proportion a certain amount of Fe
3+and Fe
2+the deionized water solution of salt drips alkaline solution under high-speed stirred, controls pH value at 12-13, and now whole solution becomes black, maintains uniform temperature reaction 0.5-2 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality, constant volume, stand-by.
Shown in the following reaction equation of basic principle of the inventive method:
2Fe
3++Fe
2++8OH
-→Fe
3O
4+4H
2O
1.2, adopt local reduction way to prepare tri-iron tetroxide magnetic microsphere, concrete steps are as follows:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add a certain amount of Fe
3+salt deionized water solution, then adds a certain amount of SO
3 2-salt deionized water solution drips alkaline solution under high-speed stirred, controls pH value at 12-13, and now whole solution becomes black, maintains uniform temperature reaction 0.5-2 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality, constant volume, stand-by.
Shown in the following reaction equation of basic principle of the inventive method:
2Fe
3++SO
3 2-+H
2O→2Fe
2++SO4
2-+2H
+
H
++OH
-→H
2O
2Fe
3++Fe
2++8OH
-→Fe
3O
4+4H
2O
Second step: the shell of preparing magnetic microsphere carried polymer catalyst---magnetic macromolecular microsphere.
By some technical schemes, can be at magnetic microsphere coated outside macromolecule, form and take the magnetic polymer microsphere of core/shell-type, tool that magnetic microsphere is shell as core, the macromolecule of take.
The magnetic polymer microsphere of tool of preparing core/shell-type has following several technical scheme:
2.1, natural polymer subshell
Natural polymer contains great amount of hydroxy group and amino as shitosan, gelatin, fibroin albumen, liposome, poly-polysaccharide etc., and coated magnetic microballoon forms coordinate bond, forms firm compound.
The shitosan of now take is set forth the technology of preparing scheme of core/shell-type, the magnetic polymer microsphere of tool as prototype.
Get a certain amount of Fe 3 O 4 magnetic microballoon water liquid, drip the acetum of shitosan, high-speed stirred, maintains uniform temperature reaction 0.5-2 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality, constant volume, stand-by.
2.2, manually synthesize macromolecule shell
Artificial synthetic macromolecule, as polystyrene, polyethylene, polypropylene, polyacrylamide, polyacrylic acid, polyacrylate etc., has different structure of functional groups, can in different occasions, use as required.The own non-activity of the macromolecule functional groups such as polystyrene, polyethylene, polypropylene, to most of reaction system inertia, acid and alkali-resistance, resistance to solvent; The macromolecules such as polyacrylamide, polyacrylic, polyacrylate have a large amount of active function groups, by coordinate bond and various catalytic center (as metallic salt), form compound, have greatly enriched the selective of catalyst.
The polystyrene of now take is set forth the technology of preparing scheme of core/shell-type, the magnetic polymer microsphere of tool as prototype.
Get a certain amount of Fe 3 O 4 magnetic microballoon water liquid, drip the tetrahydrofuran solution of polystyrene, high-speed stirred, maintains uniform temperature reaction 0.5-2 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality.With absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains tri-iron tetroxide-polystyrene magnetic microsphere powder.
The 3rd step, catalytic center and magnetic macromolecular microsphere compound
Catalytic center comprises the materials such as various metal simple-substances (as palladium, platinum, ruthenium, osmium, copper, cobalt, nickel, zinc, iron) and salt thereof, part and various phosphorous, nitrogen, sulphur, boron, with the magnetic heterogeneous catalysis of the compound rear formation tool of magnetic macromolecular microsphere.This catalyst is can be easily under additional magnetic fields separated from reaction system, reclaim and apply mechanically.
Now take palladium, phosphorus sets forth catalytic center and the compound technical scheme of magnetic macromolecular microsphere as prototype.
3.1, the preparation of tri-iron tetroxide-chitose magnetic microsphere-palladium complex: get a certain amount of tri-iron tetroxide-chitose magnetic microsphere water liquid and put into reactor, add palladium salt and absolute ethyl alcohol, add thermal agitation, temperature is 60 ℃-80 ℃, reaction 6-10 hour.After completion of the reaction, naturally cool to room temperature, at reactor bottom, place magnet, strain most liquid.Use absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains the tri-iron tetroxide-chitose magnetic microsphere-palladium complex of black again.
3.2, the preparation of tri-iron tetroxide-polystyrene magnetic microsphere-phosphorus complex:
Tri-iron tetroxide-polystyrene magnetic microsphere-phosphorus complex has following two kinds of preparation technologies:
3.2.1, adopt modification legal system for tri-iron tetroxide-polystyrene magnetic microsphere-phosphorus complex, concrete steps are as follows:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add a certain amount of tri-iron tetroxide-polystyrene magnetic microsphere powder, add dry oxolane, be cooled to subzero 60 ℃-subzero 80 ℃, slowly drip butyl lithium/hexane solution, 0.5-2 as a child slowly dripped diphenyl phosphorus chloride/tetrahydrofuran solution again, continue reaction after 4-6 hour, be naturally warming up to subzero 5 ℃-0 ℃, slowly drip the shrend reaction of going out.At reactor bottom, place magnet, strain most liquid.Add weak acid scrubbing, with the deionized water rinsing flowing, slowly stir simultaneously, be washed till neutrality, then use absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine complex of black.
3.2.2, adopt one kettle way to prepare tri-iron tetroxide-polystyrene magnetic microsphere-phosphorus complex, concrete steps are as follows:
Get a certain amount of Fe 3 O 4 magnetic microballoon water liquid, drip the tetrahydrofuran solution of polystyrene-diphenylphosphine, high-speed stirred, maintains uniform temperature reaction 0.5-2 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing flowing, slowly stir simultaneously, be washed till neutrality, then use absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains tri-iron tetroxide-polystyrene magnetic microsphere-phosphorus complex of black.
The specific embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
The preparation of tri-iron tetroxide-chitose magnetic microsphere-palladium complex.
Technical process and the step of the present embodiment are as follows:
(1) preparation of tri-iron tetroxide-chitose magnetic microsphere:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add 31.46g iron chloride, 100ml deionized water, after dissolving completely, drip 2.45g sodium sulfite/20ml deionized water solution.The NaOH deionized water solution (approximately 200ml) that drips 2mol/L under high-speed stirred, to pH=13, continues reaction 2 hours.Remove nitrogen protection, take in the HAc solution that 1.0g shitosan is dissolved in 100ml1%, it is slowly dropped in magnetic microsphere solution, continue reaction 0.5 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality, be settled to 500ml, standby.
The mass ratio of the tri-iron tetroxide/shitosan in the prepared tri-iron tetroxide-chitose magnetic microsphere of above method of operating is 9/1.
(2) preparation of tri-iron tetroxide-chitose magnetic microsphere-palladium complex:
Shake up, (in this mixture, chitose magnetic microsphere quality is 1.00g to measure the chitose magnetic microsphere water liquid of 51.3ml,) to three mouthfuls of round-bottomed flasks of 100ml, add 0.027g palladium bichloride (0.15mmol) and 30ml absolute ethyl alcohol, reflux 10 hours, be cooled to room temperature, at reactor bottom, place magnet, strain most liquid.Use 50ml absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains the tri-iron tetroxide-chitose magnetic microsphere-palladium complex of black again.
After tested, in tri-iron tetroxide-chitose magnetic microsphere-palladium complex, the actual negative carrying capacity of palladium is 1.36%.
Embodiment 2
The preparation of tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine complex.
Technical process and the step of the present embodiment are as follows:
(1) preparation of tri-iron tetroxide-polystyrene magnetic microsphere:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add 7.72g frerrous chloride, 20.97g ferric trichloride, 100ml deionized water, after dissolving completely, the NaOH deionized water solution (approximately 200ml) that drips 2mol/L under high-speed stirred, to pH=13, continues reaction 2 hours.Remove nitrogen protection, take 1.0g polystyrene and be dissolved in 50ml tetrahydrofuran solution, it is slowly dropped in magnetic microsphere solution, continue reaction 0.5 hour.Standing, at reactor bottom, place magnet, strain most liquid.With the deionized water rinsing black solid flowing, slowly stir simultaneously, gained black solid is washed till to neutrality.With absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtain tri-iron tetroxide-polystyrene magnetic microsphere powder of black.
(2) preparation of tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine complex:
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add 1.0g tri-iron tetroxide-polystyrene magnetic microsphere powder, add dry oxolane 20ml, dry ice acetone is cooled to subzero 78 ℃, slowly drip 2ml1.0M butyl lithium/hexane solution, finish and continue to stir 0.5 hour, more slowly drip 0.45g diphenyl phosphorus chloride/5ml tetrahydrofuran solution, continue reaction after 4 hours, naturally be warming up to subzero 5 ℃-0 ℃, slowly drip the shrend reaction of going out.At reactor bottom, place magnet, strain most liquid.Add weak acid scrubbing, with the deionized water rinsing flowing, slowly stir simultaneously, be washed till neutrality, then use absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine complex of black.
Embodiment 3
The preparation of tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine-copper complex.
With nitrogen replacement air three times, omnidistance nitrogen protection.In reactor, add 1.0g tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine complex, 0.34g copper chloride, 50ml methyl alcohol, heating reflux reaction 10h, is cooled to room temperature, at reactor bottom, places magnet, strains most liquid.Use 50ml absolute ethanol washing 3 times, cryogenic freezing vacuum drying, obtains tri-iron tetroxide-polystyrene magnetic microsphere-diphenylphosphine-copper complex of black again.
Claims (10)
1. a preparation method for magnetic microsphere carried polymer catalyst, is characterized in that having following technical process and step:
(1), with the air in nitrogen replacement reactor, in reactor, add Fe
3+and Fe
2+salt mixed liquor or Fe
3+salt and SO
3 2-the mixed liquor of salt slowly drips alkaline solution under high-speed stirred, controls pH value at 12-13, maintains 10-30 ℃ of thermotonus 0.5-2 hour;
(2) get Fe 3 O 4 magnetic microballoon water liquid, drip high molecular solution, high-speed stirred, maintains 10-30 ℃ of thermotonus 0.5-2 hour;
(3) get magnetic macromolecular microsphere and put into reactor, add catalytic center and other reagent, through specific reaction means make catalytic center and magnetic macromolecular microsphere compound.
2. the preparation method of magnetic microsphere carried polymer catalyst according to claim 1, is characterized in that, described Fe
3+salt is: iron chloride, ferric sulfate, ferric nitrate, ferric phosphate and ferric acetate; Described Fe
2+salt is: frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous phosphate and ferrous acetate; Described SO
3 2-salt is: sodium sulfite, potassium sulfite; Alkali lye is: NaOH, potassium hydroxide, ammoniacal liquor.
3. the preparation method of magnetic microsphere carried polymer catalyst according to claim 1, is characterized in that, described
Magnetic microsphere is: tri-iron tetroxide, nitrided iron.
4. the preparation method of magnetic microsphere carried polymer catalyst according to claim 1, is characterized in that, described macromolecule is: natural polymer and artificial synthetic macromolecule.
5. the preparation method of magnetic microsphere carried polymer catalyst according to claim 4, is characterized in that, described natural polymer is: shitosan, gelatin, fibroin albumen, liposome, poly-polysaccharide and modified high-molecular thereof.
6. the preparation method of magnetic microsphere carried polymer catalyst according to claim 4, it is characterized in that, described artificial synthetic macromolecule is: polystyrene, polyethylene, polypropylene, polyacrylamide, polyacrylic acid, polyacrylate and modified high-molecular thereof.
7. the preparation method of magnetic microsphere carried polymer catalyst according to claim 1, is characterized in that, described catalytic center is: metal catalytic center and nonmetal catalytic center.
8. the preparation method of magnetic microsphere carried polymer catalyst according to claim 7, is characterized in that, described metal catalytic center is: metal simple-substance and salt thereof, part.
9. the preparation method of magnetic microsphere carried polymer catalyst according to claim 7, is characterized in that, described nonmetal catalytic center is: phosphorous, nitrogen, sulphur, boron organic compound.
10. the preparation method of magnetic microsphere carried polymer catalyst according to claim 1, is characterized in that, described specific reaction means are: metal and macromolecule form coordinate bond, macromolecule surface modification, grafting, copolymerization, block polymerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092221A (en) * | 2018-09-01 | 2018-12-28 | 兰州理工大学 | The preparation method and applications of the ferroso-ferric oxide particulate material of polyacrylamide cladding |
| CN109092219A (en) * | 2018-07-31 | 2018-12-28 | 湖南华腾制药有限公司 | A kind of magnetic macromolecular microsphere structure and its preparation |
| CN111470575A (en) * | 2019-10-30 | 2020-07-31 | 长沙凯天工研院环保服务有限公司 | Magnetic phosphorus removal agent and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053287A2 (en) * | 2001-01-05 | 2002-07-11 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Method for evaluating the efficiency of solid catalysts for a reaction network |
| CN101011669A (en) * | 2007-02-09 | 2007-08-08 | 上海大学 | Method for preparing chitose magnetic microsphere metal palladium complex catalyst |
| CN101116829A (en) * | 2007-06-29 | 2008-02-06 | 中山大学 | Nanometer high molecule magnetic microsphere of binding metalloporphyrin and method for preparing the same |
-
2014
- 2014-06-24 CN CN201410290194.3A patent/CN104069892A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053287A2 (en) * | 2001-01-05 | 2002-07-11 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Method for evaluating the efficiency of solid catalysts for a reaction network |
| CN101011669A (en) * | 2007-02-09 | 2007-08-08 | 上海大学 | Method for preparing chitose magnetic microsphere metal palladium complex catalyst |
| CN101116829A (en) * | 2007-06-29 | 2008-02-06 | 中山大学 | Nanometer high molecule magnetic microsphere of binding metalloporphyrin and method for preparing the same |
Cited By (10)
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|---|---|---|---|---|
| CN109092219A (en) * | 2018-07-31 | 2018-12-28 | 湖南华腾制药有限公司 | A kind of magnetic macromolecular microsphere structure and its preparation |
| CN109092221A (en) * | 2018-09-01 | 2018-12-28 | 兰州理工大学 | The preparation method and applications of the ferroso-ferric oxide particulate material of polyacrylamide cladding |
| CN111470575A (en) * | 2019-10-30 | 2020-07-31 | 长沙凯天工研院环保服务有限公司 | Magnetic phosphorus removal agent and preparation method thereof |
| CN111672530A (en) * | 2020-05-19 | 2020-09-18 | 江苏大学 | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN111672530B (en) * | 2020-05-19 | 2023-01-17 | 江苏大学 | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN111732179A (en) * | 2020-05-22 | 2020-10-02 | 福建工程学院 | Fenton-fluidized bed sewage treatment plant |
| CN111841660A (en) * | 2020-07-28 | 2020-10-30 | 福建省农业科学院农业工程技术研究所 | Preparation of magnetic suspension 3D ozone catalytic microspheres and application thereof in aquaculture sewage |
| CN111841660B (en) * | 2020-07-28 | 2023-03-03 | 福建省农业科学院农业工程技术研究所 | Preparation of magnetic suspension 3D ozone catalytic microspheres and application thereof in aquaculture sewage |
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