CN113648994B - Fixed bed type benzyl alcohol aldehyde preparation catalyst with basalt fiber carrier and preparation method thereof - Google Patents
Fixed bed type benzyl alcohol aldehyde preparation catalyst with basalt fiber carrier and preparation method thereof Download PDFInfo
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- CN113648994B CN113648994B CN202110954747.0A CN202110954747A CN113648994B CN 113648994 B CN113648994 B CN 113648994B CN 202110954747 A CN202110954747 A CN 202110954747A CN 113648994 B CN113648994 B CN 113648994B
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- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 benzyl alcohol aldehyde Chemical class 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000004927 clay Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000012279 sodium borohydride Substances 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 15
- 238000005491 wire drawing Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- 229910000629 Rh alloy Inorganic materials 0.000 claims description 7
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 7
- 229910000271 hectorite Inorganic materials 0.000 claims description 7
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012784 inorganic fiber Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000002522 swelling effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229940088594 vitamin Drugs 0.000 claims 1
- 229930003231 vitamin Natural products 0.000 claims 1
- 235000013343 vitamin Nutrition 0.000 claims 1
- 239000011782 vitamin Substances 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- 238000009941 weaving Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000009987 spinning Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000080 wetting agent Substances 0.000 abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B01J35/23—
-
- B01J35/394—
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/06—Manufacture of glass fibres or filaments by blasting or blowing molten glass, e.g. for making staple fibres
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
- C03C25/16—Dipping
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
Abstract
The invention discloses a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier and a preparation method thereof. The catalytic material takes fiber as a carrier, the clay material loaded Pd dispersion liquid with catalytic activity is directly grafted on the surface of the fiber in the form of a wetting agent in the production process, and a three-dimensional reticular material with both catalytic performance and fixed bed function is formed by spinning, so that a reaction device is simplified, the number of catalytic activity sites of more Pd is exposed, and the accessibility of a catalyst and a reaction substance is improved; meanwhile, the inorganic impregnating compound coating coated on the fiber surface effectively improves the corrosion resistance of the catalytic net, and provides a novel material which is more efficient, stable in property, easy to recover, stronger in impact resistance, low in manufacturing cost, simple in production process and integrated with a catalyst and a catalytic bed for the catalytic oxidation of industrial benzyl alcohol.
Description
Technical Field
The invention discloses a fixed bed type catalyst for preparing aldehyde from benzyl alcohol by using a basalt fiber carrier and a preparation method thereof, which are a catalytic material for preparing benzaldehyde by oxidizing benzyl alcohol and a preparation method thereof, and belong to the technical field of chemical materials.
Background
The aldehydes have high value as high-value components in the flavor industry such as food, medicine, and dye. It is usually prepared by hydrolysis of benzyl chloride or oxidation of toluene. But chlorine contamination or more by-products limit its application. Therefore, in order to meet the environmental requirements, the catalytic oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) by taking oxygen or hydrogen peroxide as a green oxidant in the presence of a catalyst draws wide attention in laboratories and chemical industries. Noble metal Nanoparticles (NPs) such as Pt, pd, ru, au, etc. have high catalytic activity due to incomplete coordination of surface atoms and size effect. However, since noble metal nanoparticles tend to grow gradually into inactive large particles due to the surface energy, pd nanoparticles need to be supported on a suitable support. The prior researchers usually load the catalyst on metal oxide, glass fiber or clay (CN 107042108B; CN107519932A; CN101596454A; zhang, A fixed-bed phosphor using a jointed nano porous polymer-coated glass fibers for visible light-treated connected phosphor reactions, 2017), although the selectivity and conversion rate are improved to different degrees by the invented material, the active site exposure is insufficient and the product and the catalyst are difficult to separate because of the agglomeration effect of the powder catalyst, while the glass fiber can lose the carrier skeleton effect in a strong oxidation environment and is difficult to be industrially used for catalyzing and oxidizing the benzyl alcohol by using hydrogen peroxide as an oxidant.
Compared with the carrier, the basalt fiber has extremely high corrosion resistance, impact resistance, heat resistance and the like under the continuous strong oxidizing fluid environment, and has incomparable advantages compared with glass fiber. The weavability of the basalt fiber enables the basalt fiber to be prepared into a three-dimensional network microstructure, and provides possibility for preparing fixing devices such as a thin folded sheet structure and a packed bed with catalytic performance. Considering the technical problem that the mechanical property of the heterogeneous catalyst is reduced due to oxidation corrosion to cause structural damage, the inorganic wetting agent with stronger corrosion resistance is adopted as the modified coating, so that the advantage is obvious. The clay particles can form a continuous network structure through crosslinking in an aqueous medium, can form a uniform film due to good thixotropy and swelling property, react with silicon hydroxyl on the surface of the fiber to form a new-Si-O-Si-bond to be coated on the surface of the fiber to form a coating layer, and can haveThe surface erosion effect of the medium is effectively resisted or slowed down, and the possibility is provided for using the fiber modified impregnating compound in the production process. In addition, the clay particles have ion exchange characteristics and surface electronegativity, and Pd is adsorbed on the surface of montmorillonite in situ through static electricity under the action of a reducing agent 2+ Reduction to Pd 0 The dispersibility of the metal nanoparticles is increased, thereby exposing more active sites to be in full contact with the reactant benzyl alcohol. Therefore, the clay also provides a bridge for loading the noble metal nanoparticles on the fiber. To the best of our knowledge, few reports have been made on the use of basalt fibers modified with inorganic wetting agents as a fixed bed in the field of catalysis or to focus on solving the problem of catalyst/solvent separation. Therefore, the main materials of the clay-loaded Pd inorganic impregnating compound modified basalt fiber catalytic mesh disclosed by the invention all utilize economic, non-toxic and harmless inorganic materials, and the pressure drop is controlled in a beneficial way different from that of other traditional catalysts, so that the catalyst/solvent separation problem is solved, and the contact efficiency is improved.
In conclusion, the fixed bed type benzyl alcohol aldehyde preparation catalyst with the basalt fiber carrier is an environment-friendly material which is high in catalytic activity, good in mechanical stability, strong in corrosion resistance, simple in reaction process and low in manufacturing cost, and has good economic benefits and social benefits.
Disclosure of Invention
Technical problem to be solved
1. The invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier, which aims to further improve the catalytic oxidation efficiency of benzyl alcohol.
2. The invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier, which aims to further improve the corrosion resistance of a catalyst bed under the action of continuous corrosive fluid.
3. The invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier, and aims to further solve the problem of separation of a liquid product of benzyl alcohol oxidation from a traditional powder catalyst.
4. The invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier, and aims to further optimize the technical problem that a catalytic bed is required to be arranged in the traditional powdery catalyst.
The technical scheme is as follows:
in order to meet the technical requirements, the invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst with a basalt fiber carrier and a preparation method thereof, which can replace the traditional reaction mode of a powdery catalyst and a catalytic bed, and have the advantages of simplified reaction device, high catalytic activity, good mechanical stability, strong corrosion resistance, simple production process, low manufacturing cost and the like. The material is realized by the following technical scheme:
a fixed bed type benzyl alcohol aldehyde preparation catalyst of a basalt fiber carrier is composed of the following raw materials: basalt fiber carrier and catalytic impregnating compound
1. Preferably, the basalt fiber carrier is an inorganic fiber which is prepared from preferably basalt according to a proportion and is formed by drawing and has a diameter of 8-15 mu m.
2. Preferably, the catalytic impregnating compound is prepared by proportionally mixing clay, noble metal precursor solution, sodium borohydride and deionized water
3. Preferably, the clay can be montmorillonite, hectorite and other clay materials with electrostatic adsorption capacity, ion exchange capacity and swelling surface.
4. Preferably, the concentration of the sodium tetrachloropalladate is 0.025mol/L-0.01mol/L,
5. preferably, the mass ratio of the raw material components is as follows: 3-5 parts of clay, 15-45 parts of precursor solution, 0.04-0.2 part of sodium borohydride and 50-82 parts of deionized water.
The preparation method comprises the following steps:
according to the technical scheme of the fixed bed type benzyl alcohol aldehyde preparation catalyst with the basalt fiber carrier, the specific implementation steps are as follows:
(1) Uniformly dispersing a certain amount of weighed clay nanoparticles in deionized water, stirring for 2-3h by using a magnetic stirrer, carrying out ultrasonic treatment for 5-10min, and then stirring for 0.5-1h again for later use;
(2) Weighing a proper amount of precursor solution, adding the precursor solution into the dispersion liquid obtained in the step (1), magnetically stirring for 1-2h, performing ultrasonic treatment for 10min, uniformly stirring, centrifuging for 5-10min, and drying in a vacuum drying oven at 60-80 ℃ for 10h for later use;
(3) Dispersing the solid sample obtained in the step (2) in deionized water, weighing a proper amount of sodium borohydride particles, dissolving the sodium borohydride particles in 5-15ml of deionized water, slowly adding the sodium borohydride particles into the dispersion, and continuously stirring for 1-2 hours to obtain a catalytic impregnating compound for later use;
(4) Melting basalt raw materials at a high temperature of 1400-1550 ℃, drawing wires through a platinum-rhodium alloy bushing, and simultaneously uniformly infiltrating the catalytic impregnating agent obtained in the step (3) to the surface of a fiber filament through an infiltrator at a certain speed to obtain a micron-sized basalt catalytic fiber with the linear density of 180-220g/m 2 Standby;
(5) And (5) plying the basalt fiber filaments obtained in the step (4) by a plying machine, and then spinning to form basalt fiber cloth to obtain a basalt fiber catalytic net with the thickness of 2-5mm, so as to obtain the Pd @ CLAY/BFCN material with both the fixed bed function and the catalytic performance.
The invention has the following positive effects:
compared with the prior art, the invention provides a fixed bed type benzyl alcohol aldehyde preparation catalyst of a basalt fiber carrier and a preparation method thereof, and the positive effects are as follows:
1. the clay is used as a bridge, and the metal Pd nano particles loaded on the three-dimensional basalt fiber mesh structure obtain higher dispersity and expose more active sites;
2. the three-dimensional basalt fiber mesh structure increases the accessibility of the reactant benzyl alcohol and the active sites, thereby increasing the conversion efficiency;
3. the clay is used as an inorganic modified impregnating compound to wrap the basalt fiber, so that the corrosion resistance of the fiber catalytic mesh in a strong oxidation medium is improved;
4. the basalt fiber three-dimensional net is taken as a fixed catalytic bed structure of the reactor, and has very good fluid impact resistance in continuous fluid
5. The clay-loaded Pd inorganic impregnating compound modified basalt fiber catalytic net is used as a reactor fixed catalytic bed structure, so that the problem of separation of a fluid medium and a catalyst can be effectively solved. The oxidation reaction steps are simplified.
Drawings
FIG. 1 is a surface topography of basalt fiber filaments and fabrics after the impregnation of a catalytic coating according to the present invention;
FIG. 2 is a graph of the conversion and strength of the catalytic web of example 2 of the present invention over four cycles;
FIG. 3 is a graph of the change in tensile strength and mass loss of the catalytic web at different impact times for example 2 of the present invention;
FIG. 4 is a graph showing the effect of the catalytic gauze on the conversion and selectivity of the reaction for producing aldehyde from benzyl alcohol under different impact times in example 2 of the present invention;
FIG. 5 is a graph of the change in catalytic web tensile strength and mass loss for different fluid velocities according to example 2 of the present invention;
FIG. 6 is a graph showing the effect of catalytic gauze on the conversion and selectivity of the reaction for producing aldehyde from benzyl alcohol at different fluid velocities in example 2 of the present invention.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which do not limit the present invention in any way, and any modifications or changes that can be easily made by a person skilled in the art to the present invention will fall within the scope of the claims of the present invention without departing from the technical solution of the present invention.
Example 1:
weighing 3 parts of montmorillonite sample, dissolving in 82 parts of deionized water, fully stirring for 2 hours, then carrying out ultrasonic treatment for 10 minutes, and stirring again for 30 minutes to form montmorillonite dispersion liquid; then adding 15 parts of 0.025mol/L sodium tetrachloropalladate solution, fully stirring for 1.5h and carrying out ultrasonic treatment for 10min; then 0.1 part of sodium borohydride is weighed and dissolved in 8ml of deionized water, and the mixture is slowly added into the dispersion liquid and stirred for 1 hour to obtain an inorganic impregnating compound; the basalt raw materials are uniformly mixed and then placed into a wire drawing machine, wire drawing is carried out through platinum-rhodium alloy at 1500 ℃, meanwhile, inorganic impregnating compound is poured into an impregnating compound container, the impregnating compound is dripped on the surface of the fiber at a constant speed while wire drawing is carried out, and the prepared fiber bundle is woven into basalt fiber cloth through a strander and a loom.
Example 2:
weighing 5 parts of montmorillonite sample, dissolving in 50 parts of deionized water, fully stirring for 2 hours, performing ultrasonic treatment for 10 minutes, and stirring again for 30 minutes to form montmorillonite dispersion liquid; then adding 45 parts of 0.025mol/L sodium tetrachloropalladate solution, fully stirring for 1.5h and carrying out ultrasonic treatment for 10min; then 0.1 part of sodium borohydride is weighed and dissolved in 8ml of deionized water, and the mixture is slowly added into the dispersion liquid and stirred for 1 hour to obtain an inorganic impregnating compound; the basalt raw materials are uniformly mixed and then placed into a wire drawing machine, wire drawing is carried out through platinum-rhodium alloy at 1500 ℃, meanwhile, inorganic impregnating compound is poured into an impregnating compound container, the impregnating compound is dripped on the surface of the fiber at a constant speed while wire drawing is carried out, and the prepared fiber bundle is woven into basalt fiber cloth through a strander and a loom.
Example 3:
weighing 3 parts of a hectorite sample, dissolving the hectorite sample in 67 parts of deionized water, fully stirring for 2 hours, performing ultrasonic treatment for 10min, and stirring again for 30min to form a hectorite dispersion liquid; then adding 30 parts of 0.025mol/L sodium tetrachloropalladate solution, fully stirring for 1.5h and carrying out ultrasonic treatment for 10min; then 0.2 part of sodium borohydride is weighed and dissolved in 8ml of deionized water, and is slowly added into the dispersion liquid to be stirred for 1 hour, so as to obtain the inorganic impregnating compound; the basalt raw materials are uniformly mixed and then placed into a wire drawing machine, wire drawing is carried out through platinum-rhodium alloy at 1500 ℃, meanwhile, inorganic impregnating compound is poured into an impregnating compound container, the impregnating compound is dripped on the surface of the fiber at a constant speed while wire drawing is carried out, and the prepared fiber bundle is woven into basalt fiber cloth through a strander and a loom.
Example 4:
weighing 5 parts of montmorillonite sample, dissolving in 80 parts of deionized water, fully stirring for 2 hours, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes again to form montmorillonite dispersion liquid; then adding 15 parts of 0.025mol/L sodium tetrachloropalladate solution, fully stirring for 1.5h and carrying out ultrasonic treatment for 10min; then 0.2 part of sodium borohydride is weighed and dissolved in 8ml of deionized water, and is slowly added into the dispersion liquid to be stirred for 1 hour, so as to obtain the inorganic impregnating compound; the preparation method comprises the steps of uniformly mixing basalt raw materials, putting the mixture into a wire drawing machine, drawing wires through platinum-rhodium alloy at 1500 ℃, pouring an inorganic impregnating compound into an impregnating compound container, dripping the impregnating compound on the surface of fibers at a constant speed while drawing the wires, and spinning fiber bundles into basalt fiber cloth through a stranding machine and a loom.
Example 5:
weighing 4 parts of hectorite sample, dissolving in 66 parts of deionized water, fully stirring for 2 hours, performing ultrasonic treatment for 10min, and stirring again for 30min to form a hectorite dispersion liquid; then 30 parts of 0.025mol/L sodium tetrachloropalladate solution is added to be fully stirred for 1.5h and subjected to ultrasonic treatment for 10min; then 0.1 part of sodium borohydride is weighed and dissolved in 8ml of deionized water, and is slowly added into the dispersion liquid to be stirred for 1 hour, so as to obtain the inorganic impregnating compound; the basalt raw materials are uniformly mixed and then placed into a wire drawing machine, wire drawing is carried out through platinum-rhodium alloy at 1500 ℃, meanwhile, inorganic impregnating compound is poured into an impregnating compound container, the impregnating compound is dripped on the surface of the fiber at a constant speed while wire drawing is carried out, and the prepared fiber bundle is woven into basalt fiber cloth through a strander and a loom.
Test example:
a performance experiment was conducted on the fixed bed type benzyl alcohol to aldehyde catalysts of basalt fiber supports prepared in examples 1 to 5. The tensile strength test is carried out according to national standards GB/T3354 and GB/T21490-2008; the catalytic activity test is carried out on the conversion efficiency of oxidizing the benzyl alcohol into the benzaldehyde after 5 hours of reaction when hydrogen peroxide is used as an oxidant through gas chromatography under the condition of condensation reflux; the fluid impact resistance test measures the change of tensile strength and mass loss of the catalytic net impacting for 1-24h when the water flow rate is 0.1-0.6m/s through a laboratory self-made device.
Table 1 catalytic activity testing of catalytic nets
| Serial number | Conversion (%) | Selectivity (%) | TOF(h -1 ) | Reaction temperature (. Degree. C.) |
| Example 1 | 54 | 99 | 12.72 | 40 |
| Example 2 | 96 | 90 | 22.61 | 80 |
| Example 3 | 86 | 88 | 20.64 | 80 |
| Example 4 | 90 | 91 | 21.2 | 80 |
| Example 5 | 87 | 84 | 20.49 | 80 |
。
Claims (4)
1. A fixed bed type benzyl alcohol aldehyde preparation catalyst of basalt fiber carrier is characterized in that: the catalyst consists of the following raw materials: a basalt fiber carrier component and a catalytic impregnating compound component;
the catalytic impregnating compound is prepared by mixing clay, a sodium tetrachloropalladate solution, sodium borohydride and deionized water in proportion; wherein the clay is montmorillonite or hectorite which has electrostatic adsorption capacity, ion exchange capacity and swelling property, and the mass ratio is as follows: 3-5 parts of clay, 15-45 parts of sodium tetrachloropalladate solution, 0.04-0.2 part of sodium borohydride and 50-82 parts of deionized water.
2. The fixed bed type benzyl alcohol aldehyde catalyst of basalt fiber carrier according to claim 1, characterized in that: the basalt fiber carrier is an inorganic fiber which is prepared from basalt in proportion and has a micron-sized diameter through wire drawing.
3. The fixed bed type benzyl alcohol aldehyde catalyst of basalt fiber carrier according to claim 1, characterized in that: the concentration of the sodium tetrachloropalladate solution is 0.025mol/L-0.01 mol/L.
4. The preparation method of the basalt fiber-supported fixed bed type catalyst for preparing aldehyde from benzyl alcohol according to any one of claims 1 to 3, wherein the fixed bed type catalyst comprises: the specific implementation steps are as follows:
(1) Uniformly dispersing a certain amount of weighed clay nanoparticles in deionized water, stirring for 2-3h by using a magnetic stirrer, performing ultrasonic treatment for 5-10min, and then stirring for 0.5-1h again for later use;
(2) Weighing a proper amount of sodium tetrachloropalladate solution, adding the sodium tetrachloropalladate solution into the dispersion liquid obtained in the step (1), magnetically stirring for 1-2 hours, ultrasonically treating for 10-20 minutes, uniformly stirring, centrifuging for 5-10 minutes, and drying in a vacuum drying oven at 60-80 ℃ for 10 hours for later use;
(3) Dispersing the solid sample obtained in the step (2) in deionized water, weighing a proper amount of sodium borohydride particles, dissolving the sodium borohydride particles in 5-15ml of deionized water, slowly adding the sodium borohydride particles into the dispersion liquid, and continuously stirring for 1-2 hours to obtain a catalytic impregnating compound for later use;
(4) Melting basalt raw materials at a high temperature of 1400-1550 ℃, drawing the basalt raw materials into filaments through a platinum-rhodium alloy bushing, drawing the filaments, and simultaneously uniformly infiltrating the catalytic impregnating compound obtained in the step (3) onto the surface of the filaments through an infiltrator at a certain speed to obtain the micron-sized basalt catalytic fibersThe linear density of the vitamin is 180 to 220g/m 2 Standby;
(5) And (4) stranding the basalt catalytic fiber obtained in the step (4) through a stranding machine, and then weaving to form basalt fiber cloth to obtain a basalt fiber catalytic net with the thickness of 2-5mm, so as to obtain the material with both fixed bed and catalytic performance.
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