CN102773111B - Magnetic solid super acid nanotube catalytic agent and preparation method thereof - Google Patents

Magnetic solid super acid nanotube catalytic agent and preparation method thereof Download PDF

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CN102773111B
CN102773111B CN201210232686.8A CN201210232686A CN102773111B CN 102773111 B CN102773111 B CN 102773111B CN 201210232686 A CN201210232686 A CN 201210232686A CN 102773111 B CN102773111 B CN 102773111B
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tio
nanotube
magnetic solid
nano tube
solid superacid
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CN102773111A (en
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黄宇轩
张娜
房永征
王中驰
申晓璇
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Shanghai Institute of Technology
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Abstract

The invention discloses a magnetic solid super acid nanotube catalytic agent and a preparation method thereof. The magnetic solid super acid nanotube catalytic agent is formed by self-assembling of a magnetic matter Fe3O4 with superparamagnetism on a TiO2 nanotube carrier containing SO4<2->. The preparation method includes subjecting titanic acid nanotubes to dipping treatment by using sulfuric acid, roasting the titanic acid nanotubes to obtain TiO2 nanotube super acid, performing self-assembling of the Fe3O4 by using a one-pot method, separating precipitates by using a magnetic separation technology, and subjecting the precipitates to vacuum drying to obtain the magnetic solid super acid nanotube catalytic agent of a TiO2 nanotube, wherein the magnetic solid super acid nanotube catalytic agent contains the SO4<2-> and is provided with the superparamagnetism. According to the magnetic solid super acid nanotube catalytic agent, by means of magnetism, the separation and recycle of the catalytic agent and reactants are facilitated, and the catalytic agent has a high catalytic activity.

Description

A kind of magnetic solid superacid nano tube catalyst and preparation method thereof
Technical field
The present invention relates to a kind of magnetic solid superacid nano tube catalyst and preparation method thereof.
Background technology
Lewis acid catalyst (AlCl 3and BF 3) there is important application at many industrial reactions, as synthesizing ethyl benzene, isopropylbenzene, linear alkylbenzene (LAB) and aromatic ketone etc.Although this bronsted acid catalyst is active high, they have easy generation refuse, and catalyst is difficult to separation of products, and the critical defect such as corrosive equipment.
From eco-friendly angle, the use of solid acid catalyst can have been tried one's best minimumization and discharged poisonous byproduct.Meanwhile, because have acid/alkalescence and redox property simultaneously, metal oxide becomes the most widely used catalyst type in heterogeneous catalytic reaction.Find first TiO from Japanese scholars Teng Yu (Fujishima) in 1972 and this many (Honda) 2monocrystalline is made electrode at normal temperatures can light decomposition water, thereby has entered research TiO 2the epoch of photochemical catalyst, due to TiO 2have low compared with large specific area, good chemical stability, abrasion resistance, cost, the features such as human body nonhazardous to be widely used as to catalytic reaction catalyst base, environmental pollution treatment aspect application potential is huge.But, TiO 2greater band gap, its Detitanium-ore-type is 3.2eV, rutile-type is 3.0eV, can only be by higher ultraviolet ray excited of energy, therefore its solar energy utilization ratio is low.
In addition, nano-TiO 2while directly making catalyst, because particle is tiny, easily form stable colloid in liquid-phase catalysis reaction, easily inactivation, reclaims difficulty, is difficult to recycle, and causes current TiO 2application cost is higher cannot be used in industrialization.
Summary of the invention
The object of the invention is in order to utilize TiO 2tubular structure, photoelectron, mechanical property that nanotube is special, larger surface area, by adding the hope such as the synergy of co-catalyst to make its absorption band move to visible-range, improve it and utilize sunshine efficiency, simultaneously, improve to simplify and prepare at present magnetic solid super acidic catalyst, and the one proposing is passed through TiO 2self assembly Fe on nanotube 3o 4a kind of magnetic solid superacid nano tube catalyst forming and preparation method thereof.
Know-why of the present invention
A kind of magnetic solid superacid nano tube catalyst of the present invention, uses sulfuric acid impregnation process titanate radical nanopipe, makes TiO after roasting 2nanotube super acids, and utilize one kettle way self assembly Fe 3o 4, utilizing magnetic separation technique sediment separate out in water, sediment, through vacuum drying, just can obtain comprising SO 4 2-and there is the TiO of superparamagnetism 2the magnetic solid superacid nano tube catalyst of nanotube.
Technical scheme of the present invention
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4; SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4it is 0.053 ~ 0.424:1:0.067 ~ 0.152.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), hydro-thermal method is prepared titanate radical nanopipe;
Described hydro-thermal method is prepared titanate radical nanopipe and is about to 2 ~ 5g TiO 2the NaOH solution of powder and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 120 DEG C ~ 170 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), the sulfuric acid solution dipping 1h that is 0.1 ~ 1.0mol/L by the titanate radical nanopipe of gained in step (1) in concentration, after filtration, at 90 DEG C of vacuum drying 12h, in 400 ~ 650 DEG C of roasting 2 ~ 4h, obtain Anatase TiO 2nanotube is TiO 2nanotube super acids;
(3), in the ultrasonic wave of 40 ~ 100Hz, by the TiO of step (2) gained 2nanotube super acids is calculated in mass ratio, i.e. the TiO of 0.35 ~ 0.8g 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, again after the ultrasonic dispersion of 10 ~ 30min, transfer in the hydrothermal reaction kettle of 100mL, after 200 DEG C of reaction 8h, after cleaning 5 ~ 10 times with second alcohol and water successively, in 60 ~ 80 DEG C of vacuum drying 12 ~ 14h, obtain magnetic solid superacid nano tube catalyst.
The magnetic solid superacid nano tube catalyst of above-mentioned gained is at synthesizing ethyl benzene, isopropylbenzene, in the reactions such as linear alkylbenzene (LAB) and aromatic ketone and sewage treatment area be a kind of environmentally friendly efficient and have a catalyst of industrial applications prospect widely.
Beneficial effect of the present invention
A kind of magnetic solid superacid nano tube catalyst of the present invention, owing to having adopted one kettle way self assembly Fe 3o 4, adopt the disposable assembling of solvent-thermal method the Fe that reduces 3+technical scheme, and utilize Fe 2+with Fe 3+synthetic Fe 3o 4the particle again tradition compound with solid super-strong acid is prepared compared with magnetic solid super acidic catalyst scheme, a kind of magnetic solid superacid nano tube catalyst of the present invention, and its raw material sources are easy to get, and preparation technology is simple, the suitability for industrialized production of being more convenient for.
Meanwhile, due in its preparation process by titanate radical nanopipe with sulfuric acid dipping and when 400 ~ 650 DEG C of roastings, thereby make Anatase, and ensure SO in catalyst 4 2-content, thereby also improved the catalytic efficiency of magnetic solid superacid nano tube catalyst.
In addition, a kind of magnetic solid superacid nano tube catalyst of the present invention, due to TiO 2the introducing of nanotube negative electrical charge, can attract Fe 3+, the Fe being attracted 3+situ converting is the Fe with superparamagnetism 3o 4, available external magnetic field directly separates magnetic solid superacid nano tube catalyst from reaction system, thereby is convenient to the recycling of magnetic solid superacid nano tube catalyst, environmentally friendly.
Detailed description of the invention
Below by embodiment, the present invention is further set forth, but do not limit the present invention.
In various embodiments of the present invention, the model of capital equipment used and the information of manufacturer are as shown in table 1.
Model and the manufacturer of main equipment used in table 1, various embodiments of the present invention
Instrument title Model Manufacturer
Table model high speed centrifuge TG16-WS Hunan, Changsha instrument centrifuge instrument Co., Ltd
The multiplex vavuum pump of circulating water type SHZ-D(Ⅲ) Shanghai Yu Hua Instrument Ltd.
High-temperature electric resistance furnace SX2-12-12 Shanghai Zu Fa Industrial Co., Ltd.
Numerical control ultrasonic cleaner KQ-100DB type Kunshan Ultrasonic Instruments Co., Ltd.
In various embodiments of the present invention, the specification of primary raw material used and the information of manufacturer are as shown in table 2.
The specification of primary raw material used and manufacturer in table 2, various embodiments of the present invention
Reagent name Specification Manufacturer
P25 gas phase titanium dioxide Analyze pure, A.R. Guangzhou SunNa trade Co., Ltd
Sulfuric acid 95.0%~98.0%，A.R Taicang Zhi Tang Chemical Co., Ltd.
Ferric sesquichloride Analyze pure, A.R Chemical Reagent Co., Ltd., Sinopharm Group
Polyethylene glycol PEG 1000 Chemical pure, C.P Shanghai Ling Feng chemical reagent Co., Ltd
In embodiments of the invention, in water used, magnetic separation technique is shown in the people such as volume the 3rd phase Dong Huifang September the 27th in 2009 " application of water treatment magnetic separation technique and research ".
embodiment 1
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4for 0.265:1:0.808.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), by 5g TiO 2the NaOH solution of powder and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 150 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), the titanate radical nanopipe of step (1) gained is flooded to 1h in 0.5mol/L sulfuric acid, after filtration, at 90 DEG C of dry 12h, at 400 DEG C, roasting 2h, obtains TiO 2nanotube super acids;
(3), in the ultrasonic wave of 40Hz, by the TiO of gained in 0.66g step (2) 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, pass through again the ultrasonic dispersion of 30min, transfer in the hydrothermal reaction kettle of 100mL, after 200 DEG C of reaction 8h, after cleaning 5 times with second alcohol and water successively at 60 DEG C vacuum drying 14h, obtain magnetic solid superacid nano tube catalyst.
embodiment 2
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4for 0.424:1:0.152.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), by 2g TiO 2the NaOH solution of powder (P25 type) and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 170 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), the titanate radical nanopipe of step (1) gained is flooded to 1h in 0.1mol/L sulfuric acid, after filtration, at 90 DEG C of dry 12h, at 650 DEG C, roasting 2h, obtains TiO 2nanotube super acids;
(3), in the ultrasonic wave of 40Hz, by the TiO of gained in 0.35g step (2) 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, pass through again the ultrasonic dispersion of 30min, transfer in the hydrothermal reaction kettle of 100mL, after 200 DEG C of reaction 8h, after cleaning 8 times with second alcohol and water successively at 80 DEG C vacuum drying 14h, obtain magnetic solid superacid nano tube catalyst.
Get the magnetic solid superacid nano tube catalyst of the above-mentioned gained of 0.03g, under 8W UV-irradiation, after the methylene blue 1h that is 25mg/L for catalytic degradation 30mL concentration, the degradation rate that records methylene blue with UV-vis ultraviolet-uisible spectrophotometer reaches 80.4%.
Utilize magnetic separation technique in water that magnetic solid superacid nano tube catalyst is separated from above-mentioned reaction system, after drying, its rate of recovery can reach 95.5%.
embodiment 3
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4for 0.053:1:0.152.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), by 5g TiO 2the NaOH solution of powder and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 150 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), by 0.3mol/L sulfuric acid dipping 1h for the titanate radical nanopipe of step (1) gained, after filtration, at 90 DEG C of dry 12h, at 400 DEG C, roasting 2h, obtains TiO 2nanotube super acids;
(3), in the ultrasonic wave of 100Hz, by the TiO of gained in 0.35g step (2) 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, pass through again the ultrasonic dispersion of 30min, transfer in the hydrothermal reaction kettle of 100mL, after 200 DEG C of reaction 8h, after cleaning 9 times with second alcohol and water successively at 60 DEG C vacuum drying 14h, obtain magnetic solid superacid nano tube catalyst.
Get the magnetic solid superacid nano tube catalyst of the above-mentioned gained of 0.03g, after the methylene blue 1h that is 25mg/L for catalytic degradation 30mL concentration under 8W UV-irradiation, the degradation rate that records methylene blue with UV-vis ultraviolet-uisible spectrophotometer reaches 82.6%.
Utilize magnetic separation technique in water that magnetic solid superacid nano tube catalyst is separated from above-mentioned reaction system, after drying, its rate of recovery can reach 95.0%.
embodiment 4
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4for 0.424:1:0.067.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), by 5g TiO 2the NaOH solution of powder and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 120 DEG C after 20h hydro-thermal reaction, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), by 0.8mol/L sulfuric acid dipping 1h for the titanate radical nanopipe of step (1) gained, after filtration, at 90 DEG C of dry 12h, at 400 DEG C, roasting 4h, obtains TiO 2nanotube super acids;
(3), in the ultrasonic wave of 100Hz, by the TiO of gained in 0.8g step (2) 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, pass through again the ultrasonic dispersion of 30min, transfer in the hydrothermal reaction kettle of 100mL, after 200 DEG C of reaction 8h, after cleaning 7 times with second alcohol and water successively at 60 DEG C vacuum drying 12h, obtain magnetic solid superacid nano tube catalyst.
Get the magnetic solid superacid nano tube catalyst of the above-mentioned gained of 0.03g, after the methylene blue 1h that is 25mg/L for catalytic degradation 30mL concentration under 8W UV-irradiation, the degradation rate that records methylene blue with UV-vis ultraviolet-uisible spectrophotometer reaches 89.5%.
Utilize magnetic separation technique in water that magnetic solid superacid nano tube catalyst is separated from above-mentioned reaction system, after drying, its rate of recovery can reach 94.3%.
embodiment 5
A kind of magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, SO in described magnetic solid superacid nano tube catalyst 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4for 0.398:1:0.067.
The preparation method of above-mentioned a kind of magnetic solid superacid nano tube catalyst, specifically comprises the steps:
(1), by 5g TiO 2the NaOH solution of powder and 70mL 10mol/L in 100mL teflon-lined hydrothermal reaction kettle at 150 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), by the titanate radical nanopipe of step (1) gained with flooding 1h in 1.0mol/L sulfuric acid, after filtration, at 90 DEG C of dry 12h, at 650 DEG C, roasting 4h, obtains TiO 2nanotube super acids;
(3), in the ultrasonic wave of 100Hz, by the TiO of gained in 0.8g step (2) 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, pass through again the ultrasonic dispersion of 30min, transfer in 100mL hydrothermal reaction kettle, after 200 DEG C of reaction 8h, after cleaning 10 times with second alcohol and water successively at 80 DEG C vacuum drying 12h, obtain magnetic solid superacid nano tube catalyst.
Get the magnetic solid superacid nano tube catalyst of the above-mentioned gained of 0.03g, after the methylene blue 1h that catalytic degradation 30mL concentration is 25mg/L under 8W UV-irradiation, the degradation rate that records methylene blue with UV-vis ultraviolet-uisible spectrophotometer can reach 86.25%.
Utilize magnetic separation technique in water that magnetic solid superacid nano tube catalyst is separated from above-mentioned reaction system, after drying, its rate of recovery can reach 93.1%.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (2)

1. a preparation method for magnetic solid superacid nano tube catalyst, described magnetic solid superacid nano tube catalyst, is comprising SO 4 2-tiO 2on nano-tube support, in self assembly, there is the magnetisable material Fe of superparamagnetism 3o 4, it is characterized in that comprising the steps:
(1), hydro-thermal method prepares titanate radical nanopipe
By the P25 type TiO of 2 ~ 5g 2the NaOH aqueous solution of powder and 70 ml 10mol/L, in 100mL teflon-lined hydrothermal reaction kettle at 120 ~ 170 DEG C after hydro-thermal reaction 20h, is cooled to after room temperature with 0.1 mol/L HNO 3after solution rinses and is 7 to filtrate pH, then with deionized water rinsing to without NO 3 -, obtain titanate radical nanopipe;
(2), the sulfuric acid solution dipping 1h that is 0.1 ~ 1.0mol/L by the titanate radical nanopipe of step (1) gained in concentration, after filtration, at 90 DEG C of vacuum drying 12h, in 400 ~ 650 DEG C of roasting 2 ~ 4h, obtain Anatase TiO 2nanotube, i.e. TiO 2nanotube super acids;
(3), in the ultrasonic wave of 40 ~ 100Hz, by the TiO of step (2) gained 2nanotube super acids is calculated in molar ratio, i.e. the TiO of 0.35 ~ 0.8g 2nanotube super acids is distributed to and is dissolved with 0.54g FeCl 36H 2in the 70mL ethylene glycol solution of O, add again the polyethylene glycol that 3.6g sodium acetate and 1.0g molecular weight are 1000, again through the ultrasonic dispersion of 10 ~ 30min, transfer in the hydrothermal reaction kettle of 100ml, after 200 DEG C of reaction 8h, 60 ~ 80 DEG C of vacuum drying 12 ~ 14h after cleaning 5 ~ 10 times with second alcohol and water successively, obtain magnetic solid superacid nano tube catalyst.
2. preparation method as claimed in claim 1, is characterized in that SO in the magnetic solid superacid nano tube catalyst of gained 4 2-, TiO 2nanotube and Fe 3o 4calculate in molar ratio i.e. SO 4 2-: TiO 2nanotube: Fe 3o 4it is 0.053 ~ 0.424:1:0.067 ~ 0.152.
CN201210232686.8A 2012-07-06 2012-07-06 Magnetic solid super acid nanotube catalytic agent and preparation method thereof Expired - Fee Related CN102773111B (en)

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