CN107115860A - A kind of nano-fiber catalyst and preparation method thereof - Google Patents

A kind of nano-fiber catalyst and preparation method thereof Download PDF

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Publication number
CN107115860A
CN107115860A CN201710504505.5A CN201710504505A CN107115860A CN 107115860 A CN107115860 A CN 107115860A CN 201710504505 A CN201710504505 A CN 201710504505A CN 107115860 A CN107115860 A CN 107115860A
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catalyst
nano
preparation
fiber
yttrium
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CN107115860B (en
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王卫超
张同
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Tianjin Chaoxin Environmental Protection Technology Co ltd
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Nankai University
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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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The present invention relates to some group of the lanthanides and yttrium, bismuth composite nano fiber catalyst and preparation method thereof.Using Hydrothermal Synthesiss or the synthesis of the method for co-precipitation more than conventional commercial catalysts, floury structure is can be only formed, and easily reunite；Part industrial catalyst is successfully spun into nanometer fibrous by the present invention using the method for electrostatic spinning, and simple and easy to do, and the diameter of fiber is maintained between 60 800nm, length range is or even longer between 0.3 30 μm；While experimental implementation is simplified, in NO Catalysis experiments, composite nano fiber catalyst presents higher catalytic performance compared with the sample that conventional method is synthesized.

Description

A kind of nano-fiber catalyst and preparation method thereof
Technical field
The present invention relates to a kind of nano-fiber catalyst and preparation method thereof.
Background technology
Catalyst has been widely used in all types of industries production process and environmental treatment, such as petroleum cracking, hydrogenation, catalysis The fields such as oxidation, desulphurization and denitration.Catalyst mainly includes activated carbon, molecular sieve, noble metal and metal oxide catalyst etc.. Infusion process is used usual catalyst more, being co-precipitated, ion exchange, and the method synthesis, these synthesis mode systems such as Hydrothermal Synthesiss The catalyst made generally exists with powder, in addition it is also necessary to further by granulation, can just make after the method machine-shaping such as press strip With.In granulation, the molding process such as press strip, catalyst inevitably loses part specific surface area and catalytic performance. And due to being molded more than 1,000 times generally up to powder size itself of the size of rear catalyst, reactant and reaction product exist Spread and be inevitably affected in catalyst after shaping.Particularly some reaction rates are depended on the diffusion speed of molecule For the catalytic reaction of degree, improve the specific surface area of catalyst and eliminate design of the influence of diffusion process to catalyst as far as possible Shaping is particularly significant.
In order to accelerate reactant molecule from be in fluid communication be attached to gas, the stagnant gas film (or liquid film) in solid boundary layer reaches Grain outer surface, or product molecule enter the external diffusion process of fluid phase from particle exterior surface by quiescent layer, a kind of effective Method be by the powder coating of catalyst ceramics or Metal Substrate cellular or corrugated plate shape carrier on.But this method is not But the manufacturing cost of catalyst is added, and the pay(useful) load amount of catalyst is limited in unit volume in catalytic converter.It is right Ceramic base carrier also needs to consider that its is shatter-proof, and solvent resistance.
The content of the invention
External diffusion speed for catalyst in solution shaping of catalyst technique is relatively low, and cellular or corrugated plate shape carrier is negative The catalyst manufacturing process of load is complicated, costly, and in unit volume catalyst pay(useful) load amount it is limited the problem of, I By the method for electrostatic spinning, be successfully prepared nanometer fibrous oxide catalyst, show good catalytic performance.
[AB2O5Type oxide]
AB2O5For the oxide of mullite type, mullite refers generally to aluminosilicate oxide, and we grind in this patent What is studied carefully is the mullite of manganese base, compared with other transition metals, and Mn oxide species and corresponding manganese element valence state are more, Between oxidation state each at low temperature can mutual inversion of phases, therefore with good low temperature active, B is manganese element, and A is rare earth member Element.
The present invention devises a kind of nano-fiber catalyst, it is characterised in that the catalyst is AMn2O5Type oxide is urged Agent, wherein A represent lanthanide series (La, Ce, Pr, Sm, Eu, Gd, Tb, Lu, Nd etc.) or yttrium (Y), bismuth (Bi) element；It is described to receive The diameter range of rice fiber is between 60~800nm, and length range is between 0.3~30 μm.
This nanofiber AMn2O5Type oxide catalyst, it is characterised in that the preparation method of the catalyst include with Lower step：
1.1 are uniformly dispersed lanthanide series salt or yttrium, bismuth (III) salt, manganese (II) salt and adhesive in a solvent, stir quiet Put and obtain mixed solution 1.1；
1.2 using mixed solution 1.1 as electrostatic spinning solution, nanofiber is spun at room temperature, then by nanofiber Drying, is cooled to room temperature.
1.3 nanofibers carry out high-temperature calcination, finally obtain the corresponding lanthanide series/yttrium salt/bismuth salt and manganese of fiber morphology The composite catalyst of salt.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that each group in described electrostatic spinning solution The percentage by weight divided is as follows：Lanthanide series salt or yttrium salt/bismuth salt 2%~4%；Manganese salt 2%~5%；Adhesive 4%~ 10%；Polar solvent 80%~95%.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described lanthanide series salt be samaric nitrate, Lutecium nitrate, ytterbium nitrate, lanthanum nitrate, cerous nitrate, praseodymium nitrate, europium nitrate are one or more of, preferably samaric nitrate.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described yttrium salt is by yttrium carbonate, nitric acid One or more in yttrium, yttrium chloride, preferably yttrium nitrate.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described bismuth salt is by bismuth nitrate, bismuth chloride In one or more, preferred bismuth nitrate.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described manganese salt is by manganese chloride, permanganic acid One or more in potassium, manganese acetate, preferably manganese acetate.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described polar solvent by water, ethanol, The mixed solution of one or more in dimethylformamide, tetrahydrofuran, ethylene glycol, polyvinyl alcohol, preferred alcohol and water.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that in described alcohol water mixed solvent alcohol and The ratio of water is one kind in 2: 1,3: 2,1: 1,2: 3,1: 2, preferably 1: 1.
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described adhesive is polyvinyl pyrrole Alkanone (PVP), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polycaprolactone (PCL) etc. In one or more, preferred polyvinylpyrrolidone (PVP).
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described organic solvent is by dimethyl methyl Acid amides (DMF), tetrahydrofuran (THF), isopropanol are one or more, preferably dimethylformamide (DMF).
Described nanofiber AMn2O5Type oxide catalyst, it is characterised in that described specific heating rate is usually 3 DEG C/below min, preferably 2 DEG C/below min, more optimize 1 DEG C/below min.For calcining heat, preferably 600 DEG C~900 DEG C, More preferably 700 DEG C~800 DEG C.
The present invention provides nano-fiber catalyst and preparation method thereof, prepares spinning solution using solution-gel method first, then Fiber is prepared by electrostatic spinning, high-temperature calcination is eventually passed and prepares nano-fiber catalyst, the simple synthetic method is easy, And the nano-fiber catalyst of synthesis is high to the catalytic conversion efficiency of oxynitrides, have in field of Environment Protection before wide application Scape.
Brief description of the drawings
Fig. 1 is the nanofiber electron scanning micrograph of embodiment 1
Fig. 2 is the nanofiber electron scanning micrograph of embodiment 2
Fig. 3 is the fine catalyst YMn of comparative example 12O5Electron scanning micrograph
Fig. 4 is the fine catalyst SmMn of comparative example 22O5Electron scanning micrograph
Fig. 5 is nano-fiber catalyst YMn2O5With fine catalyst YMn2O5Figure is compared to NO catalytic effects
Fig. 6 is nano-fiber catalyst SmMn2O5With fine catalyst SmMn2O5Figure is compared to NO catalytic effects
Embodiment
Below will by instantiation, the present invention is further illustrated, but the present invention the scope of application do not limited by it System.
[NO catalytics]
The catalytic activity test of catalyst is carried out in fixed bed reactors, and specific process of the test is as follows：
1) take 100mg catalyst to be placed in characteristic present's instrument and carry out catalytic reaction；
2) carry out before Catalysis experiments, all samples are required for being pre-processed, and treatment conditions are as follows：It is passed through 30cc/ Min pure nitrogen gas, 355 DEG C are raised to 10 DEG C/min heating rate from room temperature, and then Temperature fall is to 50 DEG C.So contribute to Eliminate the adsorbate such as O of catalyst surface2, H2O etc..
3) in Catalysis experiments, gas overall flow rate is maintained at 200cc/min, wherein NO/N2The flow velocity of mixing is 15cc/ Min, 20%O2/N2Gaseous mixture flow velocity is maintained at 60cc/min, also 125cc/min pure N2Balance Air, in order to react fully The reacting gas oxygen being passed through is excessive.
4) Catalysis experiments of catalyst are carried out after pretreatment terminates：First it is passed through NO/N2And 20%O2/N2Gaseous mixture, 50 DEG C adsorption reaction 30 minutes.Then 100 DEG C are raised to 10 DEG C/min heating rate and are incubated 30 minutes.Then with same liter Warm speed is raised to assigned temperature respectively, and is incubated 30 minutes in each temperature spot.The purpose for the arrangement is that in order that reaction is in spy Determine to reach balance during temperature spot.The NO concentration Cs of each temperature section are detected, then with NO initial concentration C0Subtract C, acquired results With initial concentration C0The ratio between be catalytic conversion.
[NO concentration testers]
The NO concentration testers used in this patent are the AMI-300 of ALTAMIRA companies production.
[embodiment 1]
By Y (NO3)3·6H2O(1.8754mmol)、Mn(CH3COO)2·4H2O (3.75mmol), polyvinylpyrrolidone (PVP, K=90,1g) is dissolved in ethanol (9mL) and deionized water (10mL), is continuously stirred at room temperature 10h and is obtained mixed solution A；
Mixed solution A is put into syringe pump, the distance of syringe needle to receiver board is set as 15cm, voltage Tiao Jiedao 15KV, injects speed and is set as 0.05mm/min, air humidity adjusts to 15%, spins colloidal sol under room temperature (22.7 DEG C), Then by spun nanofiber, high temperature is dried in an oven, is cooled to after room temperature, by the resulting Nanowire containing yttrium and manganese Dimension is put into the calcining of Muffle furnace high temperature；Heating rate setting is as follows：450 DEG C of insulations are raised to from room temperature with 25 DEG C/h heating rate 2h, then 600 DEG C of insulation 2h are raised to same heating rate, to 800 DEG C of insulation 4h, finally it is naturally cooling to room temperature.It can obtain To nano-fiber catalyst YMn2O5, a diameter of 100~250nm of fiber, length is 18 μm.
Nano-fiber catalyst YMn2O5Catalytic performance be shown in Table 1.
[embodiment 2]
Sm (NO will be used as3)3·6H2O(1.8754mmol)、Mn(CH3COO)2·4H2O (3.75mmol), polyvinyl pyrrole Alkanone (PVP, K=90,1g) is dissolved in ethanol (9mL) and deionized water (10mL), is continuously stirred at room temperature 10h and is mixed Solution B；
Mixed solution B is put into syringe pump, the distance of syringe needle to receiver board is set as 15cm, voltage Tiao Jiedao 15KV, injects speed and is set as 0.05mm/min, air humidity adjusts to 15%, spins colloidal sol under room temperature (22.7 DEG C), Then by spun nanofiber, high temperature is dried in an oven, is cooled to after room temperature, resulting nanofiber is put into Muffle Stove high temperature is calcined；Heating rate setting is as follows：450 DEG C of insulation 2h are raised to from room temperature with 25 DEG C/h heating rate, then with same The heating rate of sample is raised to 600 DEG C of insulation 2h, to 800 DEG C of insulation 4h, is finally naturally cooling to room temperature.It can obtain nanofiber Catalyst SmMn2O5, a diameter of 200~300nm of fiber, length is up to 30 μm.
Nano-fiber catalyst SmMn2O5Catalytic performance be shown in Table 1.
[comparative example 1]
By Y (NO3)3·6H2O (2.5mmol) is dissolved in 25mL deionized water, and stirring obtains solution C；Then will KMnO4(1.5mmol)、Mn(CH3COO)2·4H2O (3.5mmol) is well mixed, and is poured slowly into solution C, add water to 40~ 50mL, stirs to obtain solution D.NaOH solution is added dropwise dropwise into solution D, continues stirring and obtains solution E.By obtained solution E dress Enter in reactor, 12h is incubated at 200 DEG C, be cooled to room temperature taking-up；Suction filtration, reclaims sample.Washing 2 times, is washed 2 times with nitric acid, Then wash again 1 time.Dried at 80 DEG C, you can obtain powdered YMn2O5Catalyst.
Powder YMn2O5The catalytic performance of catalyst is shown in Table 1.
[comparative example 2]
SmMn is prepared using hydrothermal synthesis method2O5Catalyst.
Sm (NO will be used as3)3·6H2O (2.5mmol) is dissolved in 25mL deionized water, and stirring obtains solution F.Then By KMnO4(1.5mmol)、Mn(CH3COO)2·4H2O (3.5mmol) is well mixed, and is poured slowly into solution F, add water to 40~ 50mL, stirs to obtain solution G.NaOH solution is added dropwise dropwise into solution G, continues stirring and obtains Solution H.By obtained Solution H dress Enter in reactor, 12h is incubated at 200 DEG C, be cooled to room temperature taking-up；Suction filtration, reclaims sample.Washing 2 times, is washed 2 times with nitric acid, Then wash again 1 time.Dried at 80 DEG C, you can obtain powdered SmMn2O5Catalyst.
Powder SmMn2O5The catalytic performance of catalyst is shown in Table 1.
Table 1：
It was found from embodiment and the result of comparative example, nano-fiber catalyst YMn2O5Catalytic activity be significantly higher than powder YMn2O5Catalyst, nano-fiber catalyst SmMn2O5Catalytic effect be significantly higher than powder SmMn2O5Catalyst, illustrates nanometer Fiber catalyst has higher catalytic activity.

Claims (6)

1. a kind of nano-fiber catalyst, it is characterised in that the catalyst is AMn2O5Type oxide catalyst, wherein A are represented Lanthanide series (La, Ce, Pr, Sm, Eu, Gd, Tb, Lu etc.) or yttrium (Y)；The diameter range of the nanofiber 60~ Between 800nm, length range is between 0.3~30 μm.
2. a kind of preparation method of nano-fiber catalyst, it is characterised in that：
1) first will the compounds precursors containing lanthanide series as claimed in claim 1 or yttrium and manganese element (Mn) with And adhesive is mixed, spinning solution is prepared；
2) by method of the foregoing spinning solution by spinning, the nanofiber containing lanthanide series or yttrium and manganese element is prepared；
3) nanofiber obtained by spinning is calcined, and finally obtains the catalyst with nanofiber pattern.
3. the preparation method of nano-fiber catalyst as claimed in claim 2, it is characterised in that the weight of each component in spinning solution Measure percentage as follows：Lanthanide series salt or yttrium salt 2%~4%；Manganese salt 2%~5%；Adhesive 4%~10%；Solvent 80%~ 95%.
4. the preparation method of nano-fiber catalyst as claimed in claim 2, it is characterised in that adhesive is poly- in spinning solution One or more in vinylpyrrolidone, polyacrylonitrile, polyvinyl alcohol, polymethyl methacrylate, polycaprolactone etc., preferably Polyvinylpyrrolidone.
5. the preparation method of nano-fiber catalyst as claimed in claim 2, it is characterised in that the heating speed in calcination process Rate is usually 3 DEG C/below min, preferably 2 DEG C/below min, more optimizes 1 DEG C/below min.
6. the preparation method of nano-fiber catalyst as claimed in claim 2, it is characterised in that calcining heat, preferably 600 Less than 900 DEG C more than DEG C, more preferably less than more than 700 DEG C 800 DEG C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107790121A (en) * 2017-11-01 2018-03-13 上海纳米技术及应用国家工程研究中心有限公司 The preparation method of manganese oxide/ceria catalyst of hollow nano fiber structure and product and application
CN109671956A (en) * 2019-02-15 2019-04-23 钟祥博谦信息科技有限公司 Electrode preparation method and system based on mullite fiber catalysis material
CN111501136A (en) * 2019-01-30 2020-08-07 宁波方太厨具有限公司 Preparation method of ozone catalytic nanofiber

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CN102517692A (en) * 2011-12-02 2012-06-27 清华大学 PAN (Polyacrylonitrile)-based porous carbon nanofiber for removing NOx from air, and preparation method and application thereof
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CN102517692A (en) * 2011-12-02 2012-06-27 清华大学 PAN (Polyacrylonitrile)-based porous carbon nanofiber for removing NOx from air, and preparation method and application thereof
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107790121A (en) * 2017-11-01 2018-03-13 上海纳米技术及应用国家工程研究中心有限公司 The preparation method of manganese oxide/ceria catalyst of hollow nano fiber structure and product and application
CN111501136A (en) * 2019-01-30 2020-08-07 宁波方太厨具有限公司 Preparation method of ozone catalytic nanofiber
CN109671956A (en) * 2019-02-15 2019-04-23 钟祥博谦信息科技有限公司 Electrode preparation method and system based on mullite fiber catalysis material

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