CN115595689B - Photocatalytic CO 2 Optical fiber for preparing methanol and preparation method thereof - Google Patents

Photocatalytic CO 2 Optical fiber for preparing methanol and preparation method thereof Download PDF

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Publication number
CN115595689B
CN115595689B CN202210801392.6A CN202210801392A CN115595689B CN 115595689 B CN115595689 B CN 115595689B CN 202210801392 A CN202210801392 A CN 202210801392A CN 115595689 B CN115595689 B CN 115595689B
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light guide
layer
photocatalytic
fiber
photocatalysis
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CN115595689A (en
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刘宇清
董伊航
张叶轲
张克勤
周宁
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Suzhou Kaiqing Carbon Neutral Technology Co ltd
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Suzhou Kaiqing Carbon Neutral Technology Co ltd
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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    • 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
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
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    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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    • D01D5/34—Core-skin structure; Spinnerette packs therefor
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
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Abstract

The invention belongs to the field of photocatalysis optical fiber, and in particular relates to a photocatalysis CO 2 A guide fiber for preparing methanol and a preparation method thereof. The method is that a layer of photocatalysis layer is coated outside the prefabricated member of the light guide layer, and the functional polymer is sprayed outside the fiber by blowing and spinning under the hot stretching outlet, so as to obtain the light guide fiber. Wherein the cross section of the light guide fiber is cross-shaped, the light guide fiber has a skin-core structure, a light guide layer, a photocatalysis layer and a protective layer are sequentially arranged from inside to outside, the light guide layer is made of modified polyethylene terephthalate, and the photocatalysis layer is g-C 3 N 4 With rGO composite material, the protective layer is thermoplastic polyurethane elastomer, and the light guide fiber can be used for photocatalysis of CO 2 Reducing to methanol.

Description

Photocatalytic CO 2 Optical fiber for preparing methanol and preparation method thereof
Technical Field
The invention belongs to the field of photocatalysis optical fiber, and in particular relates to a photocatalysis CO 2 A guide fiber for preparing methanol and a preparation method thereof.
Background
With the development of industrialization, CO 2 The emission amount of (2) is continuously increasing, global warming caused by greenhouse effect is one of the problems restricting the development, and with the further emphasis of environmental problems and the proposal of carbon neutralization, CO 2 Capture, fixation and reduction of CO in air 2 Is also becoming more and more important. CO 2 There are many methods of reduction, with photocatalysis being of interest as a green, sustainable method. Different photocatalysts can convert CO 2 Reduction to a different species, methanol being a desirable product as a fuel that can be liquefied and is convenient for storage and transportation. From g-C 3 N 4 The photocatalyst formed by the rGO (reduced graphene oxide) composite material is a directional reduction CO 2 Is a photocatalyst of methanol. The optical fiber with the inside capable of transmitting light is a good photocatalysis reduction method for CO 2 Is a reactor of (a). Modified PET (polyethylene terephthalate) as a light guide material for an unconventional photocatalytic reactor has certain advantages in a reactor with low requirements for light transmission.
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalytic photolysis, light is absorbed by the adsorbed substrate. In photocatalysis, photocatalytic activity (PCA) depends on the ability of a catalyst to generate electron-hole pairs that generate free radicals (e.g., hydroxyl radicals:. OH) that are capable of undergoing secondary reactions. The discovery of electrolyzed water by titanium dioxide (TiO) makes practical use possible. Photocatalysis principle: macroscopically, i.e. the reverse reaction of photosynthesis, is a catalyst that converts organic matter to inorganic matter under the action of light. 1. On the microcosmic aspect, the titanium dioxide particles degrade organic matters after absorbing the energy of ultraviolet light, and finally carbon dioxide and water are generated without loss. Photocatalysis is the most ideal environment purification technology in the current world, and has the advantages of simple operation, low energy consumption, no secondary pollution, high efficiency and the like. Oxygen in the air is directly used as an oxidant, and can react at normal temperature and normal pressure. The organic pollutant is decomposed into inorganic micromolecules such as carbon dioxide, water and the like, and the purifying effect is thorough. The semiconductor photocatalyst has stable chemical property, strong oxidation-reduction property, low cost, no adsorption saturation phenomenon and long service life. 2. The basic principle is that under the excitation of light, electrons jump from the valence band to the conduction band position, so that the electrons form photo-generated electrons on the conduction band, and photo-generated holes are formed on the valence band. Organic pollutants in the degradable environment by the reductive oxidative nature of photogenerated electron-hole pairs, and the preparation of CO 2 . A high efficiency photocatalyst must meet the following conditions: (1) The proper conduction and valence band positions of the semiconductor must have sufficient oxidation properties for the valence band potential to be useful in contaminant decontamination applications, and in photolytic applications. (2) The effective electron-hole separation capability reduces the synthesis probability. (3) visible light response characteristics: the ultraviolet energy less than 420nm accounts for about 4% of the solar energy, and how to use the visible light and even the infrared light energy determines whether the photocatalytic material can obtain large-scale real lifePrecondition for practical application.
At present, researchers are used for photocatalysis of CO by a photocatalysis reactor 2 The reduction to methanol was investigated. As in patent CN201410446964.9, a multi-fiber reaction channel reactor with reversely arranged light sources is provided, four optical fibers are formed into an independent reaction channel, and a plurality of reaction channels are formed into the fiber reaction channel reactor, so that the photon utilization is enhanced, the reaction efficiency and the methanol product concentration are improved due to the arrangement of the multi-optical fibers, but the fiber used for transmitting light in the reactor is a common quartz fiber, the light guiding effect in the fiber is good, but the light intensity of the refracted fiber is low, and the reaction efficiency is still to be improved. Patent CN201610144691.1 provides an optical fiber type photocatalytic reactor and a method for introducing CO 2 In the method for converting the rare earth-modified titanium dioxide-loaded optical fiber into methanol, the optical fiber is arranged in a reaction barrel, the light utilization rate of the reactor is high, the specific surface area of a catalyst is large, but the reactor is a conventional optical fiber with a circular section, and the specific surface area and the refractive intensity can be further improved by changing the optical fiber into the optical fiber with other sections. In the literature 'analysis and reinforcement of photocatalytic reduction of carbon dioxide in a honeycomb optical fiber reactor', photocatalytic CO is performed by a method of dip-coating calcined photocatalyst on the outer wall of an optical fiber and the inner wall of a reaction unit and forming a reactor by a plurality of reaction units 2 Although the supported photocatalyst part of the reactor is increased, the method cannot be applied to light guide fibers which are not resistant to high temperature, and the advantages of the fibers cannot be utilized. Document "Photocatalytic CO 2 reduction using an internally illuminated monolith photoreactor "A photocatalytic reactor for photocatalytic CO is composed of a photocatalyst prepared by dip-coating and calcining a photocatalyst on the inner wall of a reactor having multiple channels, and inserting multiple PMMA (polymethyl methacrylate) into the channels 2 In this method, PMMA is used, but there is a distance between PMMA and the inner wall of the reactor, and the light reflected by the PMMA is inevitably lost when it irradiates the inner wall, and the photocatalyst used in the reactor absorbs 460nm at most.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventionThe invention provides a photocatalytic CO 2 The light guide fiber for preparing the methanol is of a skin-core structure and comprises a light guide layer, a photocatalysis layer covered on the light guide layer and a protective layer covered on the photocatalysis layer;
the light guide layer is cross-shaped and comprises a high polymer with a light guide effect; the total light transmittance of the high polymer with the light guide effect is 88% -90%, and the refractive index is 1.45-1.50;
the protective layer comprises TPU (thermoplastic polyurethane elastomer) nanofibers;
the equivalent thickness ratio of the light guide layer, the photocatalytic layer and the protective layer is as follows: 700-1000:0.3-2:100-500.
Preferably, the photocatalyst in the photocatalytic layer comprises g-C 3 N 4 And rGO.
Further, the g-C 3 N 4 And the mass ratio of rGO is 92-96:4-8.
Further, the high polymer with the light guiding effect is modified polyethylene terephthalate.
Preferably, the refractive index of the protective layer is 1.52-1.57.
Preferably, the nanofibers of the TPU nanofiber membrane have a diameter of 500-800nm.
Preferably, the protective layer comprises macropores and pinholes, the diameter of the macropores is 90-110nm, and the diameter of the pinholes is 15-25nm.
Preferably, the equivalent diameter of the light guide fiber is 0.8-1.5mm.
The invention also provides the photocatalytic CO 2 The preparation method of the light guide fiber for preparing the methanol comprises the following steps:
s1: performing hot-press molding on the high polymer with the light guide effect to obtain the light guide layer;
the pressure of the hot compression molding is 5-10MPa, and the temperature is 260-280 ℃;
s2: calcining the slurry and coating the calcined slurry on the light guide layer to obtain a prefabricated member;
the slurry is prepared by mixing a photocatalyst and NaHCO 3 Adding polyethylene glycol aqueous solutionIs obtained by mixing;
s3: carrying out hot stretching on the prefabricated part to obtain fibrous filaments;
s4: blowing, spraying and spinning the outer surface of the fibrous filament to obtain the photocatalytic CO 2 Preparing light guide fibers of methanol; the solute of the spinning solution for blowing and spraying spinning is TPU, the solvent is DMF, and the concentration of the TPU is 8-12wt%.
Preferably, in the step S3, the temperature of the hot stretching temperature ranges from 80 to 90 ℃, from 260 to 280 ℃ and from 90 to 100 ℃;
preferably, in the step S4, the drafting wind pressure of the blowing spinning is 0.08-0.4MPa, the extrusion speed is 2-5mL/h, and the receiving distance is 15-25cm.
The invention also provides a flexible PU (polyurethane) pipe, which comprises the photocatalytic CO 2 Preparing light guide fibers of methanol;
the bending angle of the flexible PU pipe is 0-60 degrees;
100-200 photocatalytic CO are arranged in the flexible PU pipe 2 Preparing light guide fibers of methanol;
the upper surface of the flexible PU pipe is provided with a gas inlet;
the lower surface of the flexible PU pipe is provided with a gas outlet; a light source is arranged on one side of the flexible PU pipe.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The cross section of the whole light guide fiber is designed to be cross-shaped, so that on one hand, the structure can enable light rays to be transmitted inside the light guide layer and simultaneously more conveniently reflect the light rays from the light guide layer to start a photocatalytic reaction, and on the other hand, compared with the conventional circular cross section, the structure has larger surface area and can load more photocatalytic layers.
(2) The TPU nanofiber membrane is prepared by blowing and spinning to serve as the protective layer, a certain gap exists between TPU nanofibers on one hand, and a plurality of macropores and pores which are self-contained and are caused by solvent volatilization are distributed on the TPU nanofibers on the other hand, and the two structures ensure that the protective layer cannot resist CO 2 The passage of gas has an influence and can simultaneously enableThe light is reflected and refracted to the photocatalytic layer for multiple times in the protective layer to perform multiple reactions.
(3) The TPU nanofiber prepared by blowing and spinning is used as the protective layer, so that the high polymer light guide layer with the flexible structure inside can be protected, the influence of shaking on the conduction of internal light and the progress of photocatalytic reaction caused by the interference of air flow generated by the introduced air is prevented, and the refractive index of the external protective layer is larger than that of the internal light guide layer, so that the total reflection condition is not satisfied, the light can be conducted forwards inside the light guide layer, and the light can be refracted out of the light guide layer to cause the photocatalytic reaction.
(4) The invention is designed to coat the photocatalysis layer outside the preformed member of the light guide layer to jointly carry out hot stretching, and can utilize the viscosity of the high polymer of the light guide layer at high temperature to act as hot melt adhesive to bond the photocatalysis layer, so that the photocatalysis layer is ensured not to fall off, the use of conventional adhesives is reduced, and the pollution is reduced.
(5) The invention designs a one-step on-line forming optical fiber, a blowing spinning device is arranged at an outlet of hot stretching, residual high temperature after hot stretching is utilized to dry and volatilize residual solvent in the blown spinning nanofiber, so that subsequent drying is reduced, energy is saved, and the TPU protective layer obtained by blowing has a certain bonding effect.
(6) The invention uses the high polymer modified PET as the light guide layer of the light guide fiber, the modified PET can well refract light to the outside to initiate reaction, and the high polymer is applied to the photocatalytic reactor, and the flexibility and toughness of the high polymer are utilized, so that the production and transportation and the replacement of the light guide fiber in the reactor are facilitated. In addition, the PU pipe used for building the closed environment is a flexible PU pipe, can be well matched with the flexible optical fiber, and is bent for a certain angle, so that the application range of the whole system is enlarged.
Drawings
FIG. 1 is a schematic side view of the overall process of the present invention;
FIG. 2 shows a method for photocatalytic CO according to the present invention 2 Schematic cross-sectional view of a light guide fiber reduced to methanol;
FIG. 3 is a schematic diagram of the transmission path of light in the cross section of the optical fiber according to the present invention;
FIG. 4 is an enlarged view of the inside of the protective layer according to the present invention;
FIG. 5 is a schematic illustration of the placement of the guide fiber of the present invention in a flexible PU tube.
Reference numerals illustrate: 1-light guide fiber, 2-hot stretching heater, 3-blowing spinning injector, 4-air compressor, 5-suction fan, 6-wind-up roll, 7-flexible PU pipe, 8-gas inlet, 9-gas outlet, 101-light guide layer, 102-photocatalytic layer, 103-protective layer, 104-light source, 105-macropore, 106-aperture.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
TPU is purchased from Jingjiang city crystal and trade company and is named PPC-TPU.
PET is available from Guangzhou City general plastics Co., ltd under the trademark TH0769.
g-C 3 N 4 Purchased from Jiangsu Xianfeng nanomaterials technology Co., ltd and designated XFI10.
rGO is purchased from Sichuan-Gem technology development Co., ltd, and is named CRG2210.
Example 1
This example provides a method for photocatalytic CO 2 The preparation method of the light guide fiber comprises the following steps:
referring to FIGS. 1-5, a granular modified PET is formed into a cross-shaped prefabricated member, namely a light guide layer 101, by a specific cross-shaped die through a flat vulcanizing machine at a certain temperature and pressure, and the prefabricated member is powdered g-C 3 N 4 NaHCO is added with rGO composite material 3 Adding polyethylene glycol aqueous solution into the solution after ultrasonic dispersion, and stirring to form uniformThe glass plate is coated with the homogenate in a scraping mode, the calcinated and shaped photocatalysis layer 102 is taken down to cover the outside of the light guide layer 101 which is not subjected to hot stretching, then the light guide layer 101 and the photocatalysis layer 102 are subjected to hot stretching together through a hot stretching heater 2, a right blowing spinning device is arranged at an outlet of the hot stretching, spinning solution extruded by a blowing spinning injector 3 is driven to be sprayed to the outside of the light guide layer 101 and the photocatalysis layer 102 which are subjected to hot stretching under the air flow generated by an air compressor 4 to obtain a protective layer 103, macropores 105 and small holes 106 are formed in nano fibers of the protective layer, a suction fan 5 is arranged at the other side of the blowing spinning injector 3 relative to the hot stretching heater 2, the volatilized solvent in the blowing spinning solution is recovered, the environment is prevented from being polluted, and finally formed light guide fibers 1 are collected on a winding roller 6. Finally, the light guide fiber 1 is arranged in the flexible PU pipe 7, the light emitted by the light source 104 is injected into one end surface of the flexible PU pipe 7, and the gas inlet 8 is arranged at the upper part of the injection end of the light source 104 and is used for CO 2 A gas outlet 9 is arranged at the lower part of the other end of the reaction kettle for discharging methanol obtained by photocatalysis.
In this case, the g-C 3 N 4 With rGO composite material, the weight portion is 92 portions of g-C 3 N 4 With 8 parts rGO.
In this example, the modified PET has a total light transmittance of 90% and a refractive index of 1.50.
In this example, the preform forming pressure was 5MPa, the temperature was 280 ℃, and the temperatures in the three hot stretching zones were 80 ℃,260 ℃ and 90 ℃, respectively.
In this example, the blowing and spinning process parameters are that the concentration of the spinning solution is 12%, the draft wind pressure is 0.2MPa, the extrusion speed is 5mL/h, and the receiving distance is 25cm.
In this example, the diameter of the TPU nanofiber ranges from 500 nm to 800nm, two types of holes, namely a large hole 105 and a small hole 106 exist in the TPU nanofiber, the diameter of the large hole 105 ranges from 90 nm to 110nm, the diameter of the small hole 106 ranges from 15 nm to 25nm, and the refractive index of the protective layer is 1.55.
In this example, the equivalent thickness of the light guide layer is 0.9mm; the equivalent thickness of the photocatalytic layer is 1 mu m; the equivalent thickness of the protective layer is 400 mu m.
In this example, the number of the optical fibers 1 inside the flexible PU tube 7 is 160, and the bending angle of the flexible PU tube 7 is 30 °.
The equivalent diameter of the finally obtained light guide fiber 1 was 1.3mm.
Example 2
Substantially the same as in example 1, the only difference is that:
in this case, the g-C 3 N 4 With rGO composite material, the weight part is 95 parts g-C 3 N 4 With 5 parts rGO.
In this example, the modified PET has a total light transmittance of 88% and a refractive index of 1.45.
In this example, the preform pressure was 10MPa, the temperature was 260℃and the temperatures in the three hot stretching zones were 90℃and 280℃and 100℃respectively.
In this example, the blowing and spinning process parameters were 8% dope concentration, 0.4MPa draft wind pressure, 3mL/h extrusion speed, and 15cm receiving distance.
In this example, the diameter of the nanofiber is 500-800nm, the diameter of the macropores is 90-110nm, the diameter of the micropores is 15-25nm, and the refractive index of the protective layer is 1.52.
In this example, the equivalent thickness of the light guide layer is 0.9mm; the equivalent thickness of the photocatalytic layer is 2 mu m; the equivalent thickness of the protective layer is 100 mu m.
The final equivalent diameter of the obtained optical fiber is 1.0mm.
Example 3
Substantially the same as in example 1, the only difference is that:
in this case, the g-C 3 N 4 With rGO composite material, the weight part is calculated by 96 g-C 3 N 4 And 4 parts of rGO.
In this example, the modified PET has a total light transmittance of 89% and a refractive index of 1.47.
In this example, the preform pressure was 8MPa, the temperature was 270℃and the temperatures in the three hot stretching zones were 85℃and 270℃and 95℃respectively.
The final equivalent diameter of the obtained optical fiber is 1.0mm.
Comparative example 1
Substantially the same as in example 1, the only difference is that:
in this example, the light guiding layer prefabricated member is prepared by a mold with a circular cross section, the cross section of the coated photocatalytic layer is also circular, and the cross section of the final light guiding fiber is a circular cross section.
In this example, the thickness of the light guide layer is 0.9mm; the thickness of the photocatalytic layer is 1 mu m; the thickness of the protective layer is 400 μm.
In this example, the final optical fiber diameter was 1.3mm.
Comparative example 2
Substantially the same as in example 1, the only difference is that:
in this example, the optical fiber has only a light guiding layer and a photocatalytic layer, and no TPU nanofiber protective layer prepared by blow-jet spinning is provided.
In this example, there are no blow spinning injectors, air compressors and suction fans.
In this example, the equivalent thickness of the light guide layer is 0.9mm; the equivalent thickness of the photocatalytic layer is 1 mu m; there is no protective layer.
In this example, the final optical fiber equivalent diameter was 0.9mm.
Comparative example 3
Substantially the same as in example 1, the only difference is that:
in this example, the protective layer is obtained by melt-coating the TPU on the outside of the light guiding layer and the photocatalytic layer, not by blow spinning.
In this case the TPU is a particulate TPU and the protective layer is obtained by melt extrusion coating.
In this example, the raw materials were dried at 100℃for 2 hours and then melt-extruded at 200℃by means of a screw extruder.
In this example, the equivalent thickness of the light guide layer is 0.9mm; the equivalent thickness of the photocatalytic layer is 1 mu m; the equivalent thickness of the protective layer is 100 mu m.
In this example, the final optical fiber equivalent diameter was 1.0mm.
Comparative example 4
Substantially the same as in example 1, the only difference is that:
in this example, the light guiding layer is made of quartz.
In this example, a circular cross-section preform was prepared using a conventional OVD process for a quartz preform, followed by a hot stretch temperature of 2100 ℃.
In this example, the photocatalytic layer is g-C in the form of powder 3 N 4 NaHCO is added with rGO composite material 3 Adding polyethylene glycol aqueous solution into the solution after ultrasonic dispersion, stirring, immersing the thermally stretched light guide fiber into the slurry to load the photocatalytic layer after uniform slurry is formed, and calcining at 600 ℃ to obtain the light guide layer and the photocatalytic layer.
In this example, the blow-jet spinning is performed outside the light guiding layer and the photocatalytic layer of the fiber after the calcination has been completed to obtain a protective layer.
In this example, the thickness of the light guide layer is 0.9mm; the thickness of the photocatalytic layer is 1 mu m; the thickness of the protective layer is 400 μm.
In this example, the diameter of the finally obtained light guide fiber was 1.3mm.
Comparative example 5
Substantially the same as in example 1, the only difference is that:
in this example, the light guiding layer material is PMMA, and the refractive index thereof is 1.52.
In this example, the light guide layer is also prepared by a prefabricated member-hot stretching method, the cross section is cross-shaped, the light guide layer is coated with the photocatalytic layer to jointly carry out hot stretching, and then a protective layer is blown on line.
In this example, the preform forming pressure was 5MPa, the temperature was 230℃and the hot stretch three temperature zone temperature was 80℃and 210℃and 90 ℃.
In this example, the equivalent thickness of the light guide layer is 0.9mm; the equivalent thickness of the photocatalytic layer is 1 mu m; the equivalent thickness of the protective layer is 400 mu m.
In this example, the diameter of the finally obtained light guide fiber was 1.3mm.
Performance testing
The relevant properties of examples 1-2 and comparative examples 1-5 are shown in the following table, wherein the diameter or equivalent diameter of the light guiding fiber is the diameter of a circular cross section and the equivalent diameter of a non-circular cross section; the refractive brightness is the light brightness of the light guiding layer after the total incident light enters the light guiding layer inside the light guiding fiber; the refractive light ratio is the percentage of refractive light brightness to total incident light brightness; the methanol production rate is the production rate of the reaction product methanol.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. Photocatalytic CO 2 The light guide fiber for preparing methanol is characterized by having a skin-core structure and comprising a light guide layer, a photocatalysis layer covered on the light guide layer and a protective layer covered on the photocatalysis layer;
the light guide layer is cross-shaped and comprises a high polymer with a light guide effect; the total light transmittance of the high polymer is 88% -90%, and the refractive index is 1.45-1.50;
the protective layer comprises TPU nanofibers;
the equivalent thickness ratio of the light guide layer, the photocatalytic layer and the protective layer is as follows: 700-1000:0.3-2:100-500.
2. Photocatalytic CO as set forth in claim 1 2 A light guide fiber for preparing methanol, characterized in that the photocatalyst in the photocatalytic layer comprises g-C 3 N 4 And rGO.
3. Photocatalytic CO as set forth in claim 2 2 The light guide fiber for preparing methanol is characterized in that the g-C 3 N 4 And the mass ratio of rGO is 92-96:4-8.
4. Photocatalytic CO as set forth in claim 1 2 The light guide fiber for preparing methanol is characterized in that the high polymer with light guide effect is modified polyethylene terephthalate.
5. Photocatalytic CO as set forth in claim 1 2 The light guide fiber for preparing methanol is characterized in that the refractive index of the protective layer is 1.52-1.57.
6. Photocatalytic CO as set forth in claim 1 2 The light guide fiber for preparing methanol is characterized in that the protective layer comprises a large hole and a small hole, the diameter of the large hole is 90-110nm, and the diameter of the small hole is 15-25nm.
7. Photocatalytic CO as set forth in claim 1 2 The light guide fiber for preparing methanol is characterized in that the equivalent diameter is 0.8-1.5mm.
8. Photocatalytic CO according to any of the claims 1-7 2 The preparation method of the light guide fiber for preparing the methanol is characterized by comprising the following steps:
s1: performing hot-press molding on the high polymer with the light guide effect to obtain the light guide layer;
s2: calcining the slurry and coating the calcined slurry on the light guide layer to obtain a prefabricated member;
the slurry is prepared by mixing a photocatalyst and NaHCO 3 Adding the solution into polyethylene glycol aqueous solution, and mixing to obtain the final product;
s3: carrying out hot stretching on the prefabricated part to obtain fibrous filaments;
s4: blowing, spraying and spinning the outer surface of the fibrous filament to obtain the photocatalytic CO 2 Guide for preparing methanolAn optical fiber.
9. A flexible PU tube comprising the light guide fiber of any one of claims 1-7.
10. The flexible PU tube of claim 9, having a bend angle of 0-60 °.
CN202210801392.6A 2022-07-08 2022-07-08 Photocatalytic CO 2 Optical fiber for preparing methanol and preparation method thereof Active CN115595689B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN205570308U (en) * 2016-03-14 2016-09-14 中国神华能源股份有限公司 Photocatalysis reactor for optic fibre formula
CN105983410A (en) * 2015-02-16 2016-10-05 北京纳米能源与系统研究所 Heterogeneous compound photocatalyst and preparation method thereof
CN106824243A (en) * 2017-01-25 2017-06-13 东南大学 Z-type BiVO4‑Au/g‑C3N4The preparation of catalysis material and its photo catalytic reduction CO2Application
US10047027B1 (en) * 2017-11-08 2018-08-14 King Fahd University Of Petroleum And Minerals Method of forming methanol via photocatalytic reduction of carbon dioxide
CN109957850A (en) * 2019-04-16 2019-07-02 江苏碳谷二维世界科技有限公司 A kind of preparation method of graphene modified photocatalytic polyester fiber
KR102231426B1 (en) * 2019-11-11 2021-03-23 중앙대학교 산학협력단 Core-shell structure photocatalyst fiber complex, and preparation method of thereof
CN113769787A (en) * 2021-08-24 2021-12-10 同济大学 Photocatalytic material based on plastic optical fiber and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105983410A (en) * 2015-02-16 2016-10-05 北京纳米能源与系统研究所 Heterogeneous compound photocatalyst and preparation method thereof
CN205570308U (en) * 2016-03-14 2016-09-14 中国神华能源股份有限公司 Photocatalysis reactor for optic fibre formula
CN106824243A (en) * 2017-01-25 2017-06-13 东南大学 Z-type BiVO4‑Au/g‑C3N4The preparation of catalysis material and its photo catalytic reduction CO2Application
US10047027B1 (en) * 2017-11-08 2018-08-14 King Fahd University Of Petroleum And Minerals Method of forming methanol via photocatalytic reduction of carbon dioxide
CN109957850A (en) * 2019-04-16 2019-07-02 江苏碳谷二维世界科技有限公司 A kind of preparation method of graphene modified photocatalytic polyester fiber
KR102231426B1 (en) * 2019-11-11 2021-03-23 중앙대학교 산학협력단 Core-shell structure photocatalyst fiber complex, and preparation method of thereof
CN113769787A (en) * 2021-08-24 2021-12-10 同济大学 Photocatalytic material based on plastic optical fiber and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TiO_2-CuO/g-C_3N_4复合纳米材料合成及光催化还原CO_2制CH_3OH研究;何恩;谭正德;赵雅丽;区泽堂;;湖南工程学院学报(自然科学版)(03);全文 *

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