CN104475121A - Preparation method and application of hydrodesulfurization catalyst by taking TiO2 nanotube as carrier - Google Patents

Preparation method and application of hydrodesulfurization catalyst by taking TiO2 nanotube as carrier Download PDF

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CN104475121A
CN104475121A CN201410757771.5A CN201410757771A CN104475121A CN 104475121 A CN104475121 A CN 104475121A CN 201410757771 A CN201410757771 A CN 201410757771A CN 104475121 A CN104475121 A CN 104475121A
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catalyst
tio
nanotube
carrier
preparation
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赵德智
宫哲
王德慧
宋关龙
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Liaoning Shihua University
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Liaoning Shihua University
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Abstract

The invention relates to a preparation method for a hydrogenation desulfurization catalyst by taking TiO2 nanotube as a carrier. The preparation method comprises the following steps: (1) preparing TiO2 nanotube with different topography parameters as the carrier of the hydrodesulfurization catalyst; (2) modifying the TiO2 nanotube by boric acid; and (3) loading a metal active center. Compared with the existing catalyst in the existing industrial production, the hydrodesulfurization catalyst prepared by the method disclosed by the invention has equivalent catalytic activity, and relatively wide applicability for special oil materials due to artificially controllable pore size and specific surface area. Meanwhile, micro pores and/or meso pores in the existing catalyst carrier preparation process are greatly reduced, the possibility that the diffusion rate of macromolecular substrates is increased by introducing the macromolecular substrates into a dust through diffusion is increased, the poisoning possibility of the catalyst is reduced, and the service life of the catalyst is prolonged.

Description

A kind of with TiO 2nanotube is preparation method and the application of the Hydrobon catalyst of carrier
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of with TiO 2nanotube is preparation method and the application of the Hydrobon catalyst of carrier.
Background technology
In recent years, PM2.5 haze air pollution episode is subject to country and the showing great attention to of government, and again pushes the quality problems of petrochemical industry product oil to public opinion top of the waves.In order to reach state IV and the sulfur content requirement by the state V standard implemented, poor ignition quality fuel has to pass through deep hydrodesulfurizationof process could be up to standard.The difficult point of deep hydrogenation process is catalyst green coke and poisoning and catalytic activity that is that cause declines, so development of new deep desulfurization catalyst just seems particularly urgent.
Summary of the invention
The object of this invention is to provide a kind of with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, solves prior art catalyst green coke and the poisoning and catalytic activity that causes declines problem in hydrodesulfurization.
For achieving the above object, the technical solution used in the present invention comprises the steps:
1. the TiO of different-shape parameter is prepared 2nanotube is as the carrier of catalytic hydrogenation catalyst;
2. adopt boric acid to TiO 2nanotube carries out modification;
3. carried metal activated centre.
Step is middle preparation TiO 1. 2nano-tube support adopts electrochemistry anodic oxidation, sol-gel process or hydro-thermal method.
The 1. described electrochemistry anodic oxidation of step is: adopting high-purity 99.8% titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin; With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 0.8%-2.6% of F, provides stable voltage to carry out anodic oxidation with 15-35V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nano-tube array; After reaction terminates, by powdered through ultrasonic vibration for producing nanotubes array, then after 400-450 DEG C of annealing 2-3h, changing Anatase into by amorphous state must stablize TiO 2nano-tube support.
The boron modification method employing dry method or wet-process modified that step is 2. described.
Step is 2. described is wet-process modifiedly: by TiO 2it is in the boric acid aqueous solution of 5%-25% that nanotube joins mass concentration, stirring and refluxing 1-4h at 90-120 DEG C, cooling, filtration, dry 4h at 110 DEG C.
Step 3. carrying method is: with phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, by the phosphoric acid of the weighing scale of component containing 4-10g/100mL in maceration extract, the MoO of 20-100g/100mL 3, the WO of the NiO of 4-15g/100mL, 15-100g/100mL 3, by the TiO of boron modification 2nanotube is with after above-mentioned solution impregnation 2-6h, and dry 3-5h at 80-120 DEG C, obtains final catalyst after roasting 4-6h at 400-600 DEG C.
Described dipping comprised volume impregnation, incipient impregnation, spray dipping.
Preferred volume impregnation excessively in described dipping method.
The physical parameter of described final goal catalyst is: most probable pore size is 40-150nm, and pore volume is 0.6-0.8mLg -1, unit volume specific area is 150-380m 2cm -3; Catalyst is containing 11-14wt%MoO 3, containing 0.1-10wt%NiO, containing 2-19wt%WO 3, containing 0.05-0.1wt% phosphorus, containing 1-15wt% boron.
The preferred physical parameter of described final goal catalyst is: most probable pore size is 65-95nm, and pore volume is 0.85-0.9mLg -1, unit volume specific area is 180-260m 2cm -3; Catalyst is containing 4-11wt%MoO 3, containing 0.6-4wt%NiO, containing 4-16wt%WO 3, containing 0.06-0.08wt% phosphorus, containing 3-12wt% boron.
Advantageous effect of the present invention is as follows:
Catalyst of the present invention adopts the TiO with human controllable aperture, bigger serface, the advantage such as high, the surperficial lewis acidity of heat endurance is strong, polymolecularity, preparation condition are ripe 2nano-tube support, has prepared the nanotube pattern Hydrobon catalyst of Large Diameter Pipeline and specific area by boron and the metal means such as P Modification and load Mo-Ni-W.Hydrobon catalyst prepared by the method has the catalytic activity suitable with existing catalyst in current industrial production, and the pore size of human controllable and specific area have wider applicability for special oils.Greatly reduce micropore in existing catalyst support preparation process and/or mesoporous simultaneously, increase macromolecule substrate increases its diffusion rate probability by diffusing into inside, duct, and reduce catalyst poisoning probability, add catalyst life.
Detailed description of the invention
Further illustrate effect of the present invention below in conjunction with embodiment, but be not limited to following examples.
Embodiment one
Adopting high-purity 99.8% titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin.With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 2% of F, provides stable voltage to carry out anodic oxidation with 15V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nanotube.After reaction terminates, producing nanotubes is powdered through ultrasonic vibration, then after 400 DEG C of annealing 2h, stable TiO 2nano-tube support.
By TiO 2it is in the boric acid aqueous solution of 25% that nanotube joins mass concentration, stirring and refluxing 2h at 100 DEG C, cooling, filtration, dry 4h at 110 DEG C.
With phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, presses the phosphoric acid of weighing scale containing 6g/100mL of oxide, the MoO of 40g/100mL in maceration extract 3, the WO of the NiO of 8g/100mL, 40g/100mL 3, by the TiO of boron modification 2after nanotube crosses volume impregnation 4h with above-mentioned solution, dry 3h at 100 DEG C, obtains final catalyst C-B-MO-Ni-1 after roasting 4h at 450 DEG C.This catalyst exterior appearance: most probable pore size is 66.3nm, pore volume is 0.72mLg -1, unit volume specific area is 146m 2cm -3.Catalyst is containing 11.6%MoO 3, containing 3.1%NiO, containing 17.3%WO 3, containing 0.06% phosphorus, containing 6.2% boron.
Embodiment two
Adopting high-purity (99.8%) titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin.With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 2% of F, provides stable voltage to carry out anodic oxidation with 25V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nanotube.After reaction terminates, by powdered through ultrasonic vibration for producing nanotubes array, then after 400 DEG C of annealing 2h, stable TiO 2nano-tube support.
By TiO 2it is in the boric acid aqueous solution of 25% that nanotube joins mass concentration, stirring and refluxing 2h at 100 DEG C, cooling, filtration, dry 4h at 110 DEG C.
With phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, presses the phosphoric acid of weighing scale containing 6g/100mL of oxide, the MoO of 40g/100mL in maceration extract 3, the WO of the NiO of 8g/100mL, 40g/100mL 3, by the TiO of boron modification 2after nanotube crosses volume impregnation 4h with above-mentioned solution, dry 3h at 100 DEG C, obtains final catalyst C-B-MO-Ni-2 after roasting 4h at 450 DEG C.This catalyst exterior appearance: most probable pore size is 92.4nm, pore volume is 0.85mLg -1, unit volume specific area is 232.2m 2cm -3.Catalyst is containing 12.1%MoO 3, containing 3.3%NiO, containing 18.2%WO 3, containing 0.06% phosphorus, containing 6.6% boron.
Embodiment three
Adopting high-purity (99.8%) titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin.With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 2% of F, provides stable voltage to carry out anodic oxidation with 35V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nanotube.After reaction terminates, producing nanotubes is powdered through ultrasonic vibration, then after 400 DEG C of annealing 2h, stable TiO 2nano-tube support.
By TiO 2it is in the boric acid aqueous solution of 25% that nanotube joins mass concentration, stirring and refluxing 2h at 100 DEG C, cooling, filtration, dry 4h at 110 DEG C.
With phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, presses the phosphoric acid of weighing scale containing 6g/100mL of oxide, the MoO of 40g/100mL in maceration extract 3, the WO of the NiO of 8g/100mL, 40g/100mL 3, by the TiO of boron modification 2after nanotube crosses volume impregnation 4h with above-mentioned solution, dry 3h at 100 DEG C, obtains final catalyst C-B-MO-Ni-3 after roasting 4h at 450 DEG C.This catalyst exterior appearance: most probable pore size is 120.1nm, pore volume is 0.90mLg -1, unit volume specific area is 265.2m 2cm -3.Catalyst is containing 12.5%MoO 3, containing 3.35%NiO, containing 19.3%WO 3, containing 0.07% phosphorus, containing 7.9% boron.
Embodiment four
Adopting high-purity 99.8% titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin; With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 0.8% of F, provides stable voltage to carry out anodic oxidation with 15V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nano-tube array; After reaction terminates, by powdered through ultrasonic vibration for producing nanotubes array, then after 450 DEG C of annealing 3h, changing Anatase into by amorphous state must stablize TiO 2nano-tube support.
By TiO 2it is in the boric acid aqueous solution of 5% that nanotube joins mass concentration, stirring and refluxing 4h at 90 DEG C, cooling, filtration, dry 4h at 110 DEG C.
With phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, by the phosphoric acid of the weighing scale of component containing 4g/100mL in maceration extract, the MoO of 20g/100mL 3, the WO of the NiO of 4g/100mL, 15g/100mL 3, by the TiO of boron modification 2nanotube is with after above-mentioned solution incipient impregnation 2h, and dry 5h at 80 DEG C, obtains final catalyst after roasting 6h at 400 DEG C.
The physical parameter of described final goal catalyst is: most probable pore size is 40nm, and pore volume is 0.6mLg -1, unit volume specific area is 150m 2cm -3; Catalyst is containing 11wt%MoO 3, containing 0.1wt%NiO, containing 2wt%WO 3, containing 0.05wt% phosphorus, containing 1wt% boron.
Embodiment five
Adopting high-purity 99.8% titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin; With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 2.6% of F, provides stable voltage to carry out anodic oxidation with 35V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nano-tube array; After reaction terminates, by powdered through ultrasonic vibration for producing nanotubes array, then after 450 DEG C of annealing 2h, changing Anatase into by amorphous state must stablize TiO 2nano-tube support.
By TiO 2it is in the boric acid aqueous solution of 15% that nanotube joins mass concentration, stirring and refluxing 1h at 120 DEG C, cooling, filtration, dry 4h at 110 DEG C.
With phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, by the phosphoric acid of the weighing scale of component containing 10g/100mL in maceration extract, the MoO of 100g/100mL 3, the WO of the NiO of 15g/100mL, 100g/100mL 3, by the TiO of boron modification 2nanotube is with after above-mentioned solution spraying dipping 6h, and dry 3h at 120 DEG C, obtains final catalyst after roasting 4h at 600 DEG C.
The physical parameter of described final goal catalyst is: most probable pore size is 150nm, and pore volume is 0.8mLg -1, unit volume specific area is 380m 2cm -3; Catalyst is containing 14wt%MoO 3, containing 10wt%NiO, containing 19wt%WO 3, containing 0.1wt% phosphorus, containing 15wt% boron.
Embodiment six
TiO 2nano-tube support adopts sol-gel process, and other step is with embodiment 1, and the preferred physical parameter of described final goal catalyst is: most probable pore size is 65nm, and pore volume is 0.85mLg -1, unit volume specific area is 180m 2cm -3; Catalyst is containing 4wt%MoO 3, containing 0.6wt%NiO, containing 4wt%WO 3, containing 0.06wt% phosphorus, containing 3wt% boron.
Embodiment seven
TiO 2nano-tube support adopts hydro-thermal method, and other step is with embodiment 1, and the preferred physical parameter of described final goal catalyst is: most probable pore size is 95nm, and pore volume is 0.9mLg -1, unit volume specific area is 260m 2cm -3; Catalyst is containing 11wt%MoO 3, containing 4wt%NiO, containing 16wt%WO 3, containing 0.08wt% phosphorus, containing 12wt% boron.
Catalyst application of the present invention is in the hydrodesulfurization of various fraction oil.
The reference agent adopted in the catalyst prepare above-mentioned example and current industrial production carries out activity rating, more above-mentioned each catalyst activity.Target TiO is loaded in 5mL fixed bed lab scale reactor 2nano-tube support catalyst, investigates the desulfurization degree of its hydrogenation catalyst isolated island delayed coking diesel oil.The physical property of raw material diesel oil is as follows: density (25 DEG C) 867kgm -3, sulfur mass fraction 14000 μ g/g, aniline point 60.4 DEG C, containing nitrogen content 3850 μ g/g, Cetane number 40.5.Process conditions: reaction temperature 360 DEG C, pressure 7MPa, hydrogen to oil volume ratio 600:1, volume space velocity 1.5h -1.Desulfurization degree as shown in Table 1.
As can be seen from table one, provided by the invention with TiO 2nanotube is that the catalytic activity that in the Hydrobon catalyst of carrier and current industrial production, existing catalyst is suitable is suitable.
Provided by the invention with TiO 2nanotube is that the Hydrobon catalyst of carrier operates after 500h in reaction unit, and catalytic efficiency, without substantially not changing, illustrates that catalyst of the present invention has longer catalytic life.
Table one

Claims (10)

1. one kind with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that comprising the steps:
1. the TiO of different-shape parameter is prepared 2nanotube is as the carrier of catalytic hydrogenation catalyst;
2. adopt boric acid to TiO 2nanotube carries out modification;
3. carried metal activated centre.
2. one according to claim 1 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that preparing TiO during described step 1. 2nano-tube support adopts electrochemistry anodic oxidation, sol-gel process or hydro-thermal method.
3. one according to claim 2 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that described electrochemistry anodic oxidation is: adopting high-purity 99.8% titanium plate, after cleaning and drying, as anode, is negative electrode with size copper coin; With NH 4the ethylene glycol solution of F is electrolyte, NH 4the mass fraction 0.8%-2.6% of F, provides stable voltage to carry out anodic oxidation with 15-35 V constant voltage source under room temperature and prepares TiO in the both sides of titanium sheet 2nano-tube array; After reaction terminates, by powdered through ultrasonic vibration for producing nanotubes array, then after 400-450 DEG C of annealing 2-3h, changing Anatase into by amorphous state must stablize TiO 2nano-tube support.
4. one according to claim 1 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that described step 2. boron modification method employing dry method or wet-process modified.
5. one according to claim 4 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that described being wet-process modifiedly: by TiO 2it is in the boric acid aqueous solution of 5%-25% that nanotube joins mass concentration, stirring and refluxing 1-4 h at 90-120 DEG C, cooling, filtration, dry 4 h at 110 DEG C.
6. one according to claim 1 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that step 3. carrying method be: with phosphoric acid, MoO 3, NiO and WO 3configuration dipping solution, by the phosphoric acid of the weighing scale of component containing 4-10g/100mL in maceration extract, the MoO of 20-100g/100mL 3, the WO of the NiO of 4-15g/100mL, 15-100g/100mL 3, by the TiO of boron modification 2nanotube is with after above-mentioned solution impregnation 2-6h, and dry 3-5h at 80-120 DEG C, obtains final catalyst after roasting 4-6h at 400-600 DEG C.
7. one according to claim 6 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that described dipping comprised volume impregnation, incipient impregnation, spray dipping; Preferred volume impregnation excessively in described dipping method.
8. one according to claim 6 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that the physical parameter of described final goal catalyst is: most probable pore size is 40-150 nm, and pore volume is 0.6-0.8 mLg -1, unit volume specific area is 150-380 m 2cm -3; Catalyst is containing 11-14wt%MoO 3, containing 0.1-10 wt %NiO, containing 2-19 wt %WO 3, containing 0.05-0.1 wt % phosphorus, containing 1-15 wt % boron.
9. one according to claim 8 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that the preferred physical parameter of described final goal catalyst is: most probable pore size is 65-95 nm, and pore volume is 0.85-0.9 mLg -1, unit volume specific area is 180-260 m 2cm -3; Catalyst is containing 4-11 wt %MoO 3, containing 0.6-4 wt %NiO, containing 4-16 wt %WO 3, containing 0.06-0.08 wt % phosphorus, containing 3-12 wt % boron.
10. one according to claim 1 is with TiO 2nanotube is the preparation method of the Hydrobon catalyst of carrier, it is characterized in that gained catalyst application is in the hydrodesulfurization of various fraction oil.
CN201410757771.5A 2014-12-10 2014-12-10 Preparation method and application of hydrodesulfurization catalyst by taking TiO2 nanotube as carrier Pending CN104475121A (en)

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CN110102301A (en) * 2019-05-20 2019-08-09 上海海事大学 A kind of load preparation method of the nano-metal-oxide based on anodizing
CN112138642A (en) * 2020-09-27 2020-12-29 福州大学 Preparation method and application of cracking catalyst

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Publication number Priority date Publication date Assignee Title
CN110102301A (en) * 2019-05-20 2019-08-09 上海海事大学 A kind of load preparation method of the nano-metal-oxide based on anodizing
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