CN104069886B - A kind of preparation method and applications of the catalyst for aqueous phase furfural hydrogenation Ketocyclopentane - Google Patents
A kind of preparation method and applications of the catalyst for aqueous phase furfural hydrogenation Ketocyclopentane Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of catalyst for aqueous phase furfural hydrogenation Ketocyclopentane, first with a step hydrothermal crystallizing fabricated in situ multi-stage porous Y type molecular sieve carrier, then prepare molecular sieve carried type catalyst by infusion process.The method that the invention also discloses this catalyst aqueous phase furfural hydrogenation Ketocyclopentane.The inventive method step is simple, and operating condition is easily controlled.Synthesized multi-stage porous Y molecular sieve relative crystallinity is high, not only contains micropore but also contain mesoporous, and has bigger specific surface area.The catalyst utilizing described system with molecular sieve for preparing standby possesses the multi-stage porous gap structure of prosperity so that the diffusion of reactant, mass transfer are accelerated, and catalyst surface is not easily formed carbon distribution, decreases the generation of side reaction simultaneously.The catalyst standby with conventional molecular sieve series is compared, it will be apparent that accelerate reaction rate, and improves the yield of target product, and catalytic effect is fine, has good industrial prospect.
Description
Technical field
The present invention relates to molecular sieve carried type catalyst technical field, be specifically related to a kind of for aqueous phase furfural hydrogenation ring penta
The preparation method and applications of the catalyst of ketone.
Background technology
Ketocyclopentane is a kind of important fine-chemical intermediate, it be prepare novel spice MDJ and
The raw material of the products such as white orchid ketone and antianxiety drugs buspirone.Owing to it has good solubility property to various resins,
It is used widely as solvent in electron trade.The synthetic method of Ketocyclopentane is a lot, and traditional Ketocyclopentane synthesis is for oneself
Diacid is cyclized under catalyst action, synthesizes Ketocyclopentane.The method uses acids reaction, and equipment is had corrosiveness,
In course of reaction, Ketocyclopentane is easily polymerized.In recent years, with C5Fraction is that the research of raw material production Ketocyclopentane causes people
Great interest.The direction of research focuses primarily upon cyclopentenes direct oxidation method and two kinds of techniques of indirect hydration method at present.
But catalytic oxidation of cyclopentene method is homogeneous reaction so that the separation of catalyst is relatively difficult, in technique or engineering also
There are some yet unresolved issues, development prospect is the most uncertain.
(Takehira K, Hayakawa T, Orita H, the et al.Mono-oxygenation of such as Takehira K
cyclopentene by molecular oxygen catalyzed by PdCl2-CuCl2inethanol[J].Journal of
Catalysis, 1989,53 (1): 15-21.) in research catalytic oxidation of cyclopentene method, with PdCl2—CuCl2For catalyst,
With ethanol as solution, the reaction conversion ratio of cyclopentenes can reach 98.2%, and Ketocyclopentane selectivity then only has 70.1%.
The selectivity obtaining Ketocyclopentane is the highest.Guo Shizhuo etc. (Guo Shizhuo, Xu Zehui, Huang Yaru, etc. cyclopentanol catalysis is de-
Hydrogen Ketocyclopentane [J]. fine chemistry industry, 2004,21 (5): 388-391.) use modified particles shape Raney ni-type
Metal alloy is as catalyst, and conversion per pass is typically more than 17%, and Ketocyclopentane selectivity reaches 100%.Although
Ketocyclopentane selectivity is the highest, but the conversion ratio of reactant is the lowest, does not meets industrial requirement.
(Omori Hideaki, KaseKeizo, the Shishikura Yoshio.Method for such as Omori Hideaki
Production of cyclopentanone [P] .J P:2002097166,2002-04-02.) use palladium is active component
Catalyst, prepare Ketocyclopentane by the dehydrogenation of gas phase catalytic reaction cyclopentanol, the selectivity of Ketocyclopentane can reach
96%.But its catalyst used is noble metal catalyst, and defect is expensive.
Therefore novel cheap catalyst must be searched out to prepare Ketocyclopentane.Molecular sieve have high heat stability,
High selectivity, easily recoverys, environmental friendliness, the advantage such as inexpensively, be often used as preparing catalyst.But due to tradition
The aperture of micro porous molecular sieve is less so that raw material Middle molecule diameter hardly enters molecular sieve pore passage more than this size macromole
In, it is unfavorable for that macromole participates in catalytic reaction.And multi-stage porous molecular sieve combines the advantage of various Porous materials, it is bigger
Specific surface area, flourishing multi-stage porous gap structure so that the diffusion of reactant, mass transfer are accelerated, and catalyst surface is not allowed
It is easily formed carbon distribution, decreases the generation of side reaction simultaneously.
Chinese patent CN101722022A uses alkali to process the USY molecular sieve that Y type molecular sieve obtains again through hydrothermal treatment consists
Do not only have the highest degree of crystallinity but also containing abundant secondary pore.This USY molecular sieve had when residual oil cracking is reacted
Higher heavy oil conversion performance and higher yield of light oil.Danny Verboekend et al. (Danny Verboekend,
GianvitoVilé,Javier Pérez-Ramírez.Hierarchical Y and USY Zeolites Designed by
Post-Synthetic [J] .Strategies Advanced Functional Materials, 2012,22:916 928.) first business is purchased
Y molecular sieve weak acid (the H bought4EDTA) process dealuminzation, more finally use weak acid with NaOH or TPAOH process desiliconization
Wash (Na2H2EDTA).Or Y molecular sieve is first carried out hydrothermal treatment consists and obtains USY, then with strong acid HCl or HNO3
Dealuminzation, then process desiliconization with NaOH or TPAOH.Two kinds of methods have respectively obtained multi-stage porous Y and USY molecular sieve.
It is used for this molecular sieve in the liquid phase alkylation reaction of toluene and benzyl alcohol showing good catalytic than common molecular sieve
Energy.But, the method that acid dealuminzation or alkali desiliconization belong to post processing, there is a lot of shortcomings: process is not easily controlled, hold very much
Being easily caused the avalanche of molecular sieve share price, demetallated speed is by the shadow of sodium content, sintering temperature and the steam partial pressure of zeolite
Ring.
Tao et al. (Yousheng Tao, Hirofumi Kanoh, Katsumi Kaneko.Uniform Mesopore-Donated
Zeolite Y Using Carbon Aerogel Templating[J].The Journal of Physical Chemistry B,2003,
107:10974-10976.) with there is homogeneous pore-size distribution mesoporous carbon aeroge as carrier, method is: with isopropyl aluminum
It is silicon source for aluminum source, Ludox and Tetramethylammonium hydroxide is template, be mixed and made into molecular sieve with sodium hydroxide and water
Synthesis liquid adds aeroge crystallization at 100 DEG C and is dried through washing for 216 hours, calcines 18 hours for 530 DEG C
To containing mesoporous NaY molecular sieve.In the method, carbon aerogels preparation process is comparatively laborious and preparation cost is high, and
And generated time is significantly larger than the generated time of conventional molecular sieve, carrier be not easy remove need long in oxygen atmosphere time
Between roasting.Therefore the synthetic method searching out step simple, easily controllable becomes needs.
Summary of the invention
For the problem existing for above-mentioned prior art and defect, present invention aim at providing one to add for aqueous phase furfural
The preparation method of the catalyst of hydrogen Ketocyclopentane, first prepares multi-stage porous Y type molecular sieve carrier, then prepares height by infusion process
Load capacity and highly active molecular sieve carried type catalyst.Preparation process is simple, easily controllable.Present invention also offers this
The method of catalyst aqueous phase furfural hydrogenation Ketocyclopentane.
The present invention is by the following technical solutions:
The preparation method of a kind of catalyst for aqueous phase furfural hydrogenation Ketocyclopentane, comprises the steps:
Step one, by Na2O:Al2O3: SiO2: H2O mol ratio is 10～16:1:10～16:180～370,
By sodium metaaluminate, sodium hydroxide, waterglass and deionized water mix homogeneously, stirring, aging after obtain Y type molecular sieve and lead
To agent；
Step 2, sodium metaaluminate is dissolved in deionized water, adds sodium hydroxide, then be slowly added dropwise waterglass, add afterwards
Entering mesoporous template and the Y type molecular sieve directed agents of step one preparation, mix homogeneously obtains aluminosilicate gels；Wherein,
Na in aluminosilicate gels2O:Al2O3: SiO2: H2The mol ratio of O is 3～6:1:8～12:180～370；Y
Al in type molecular sieve guiding agent2O3Quality is Al in aluminosilicate gels2O3The 5%～20% of quality；1ml aluminosilicate
Gel adds mesoporous template 0.01～0.05g；
Step 3, aluminosilicate gels step 2 prepared load crystallization in the water heating kettle sealed, and crystallization terminates rear solid
Product through sucking filtration, wash, be dried, then in Muffle furnace calcining remove mesoporous template, obtain multi-stage porous Y type molecular sieve；
Step 4, multi-stage porous Y type molecular sieve step 3 prepared obtain Hydrogen multi-stage porous Y type through ion exchange and divide
Son sieve, recycling equi-volume impregnating prepares molecular sieve carried type catalyst, i.e. described for aqueous phase furfural hydrogenation system
The catalyst of Ketocyclopentane.
Described in step one, the time of stirring is 0.5h, and the aging time is 24～72h.
One or several during mesoporous template is F127, APTES or sodium alginate described in step 2
Kind.
The temperature of crystallization described in step 3 is 90～120 DEG C, and the time is 15～40h.
The ion exchange liquid that ion exchange described in step 4 uses is 0.2～1mol/L NH4Cl solution；Described molecular sieve is born
The metal of supported catalyst load is the one or two kinds of in Cu, Ni, Co, Pt；The metal quality of load is molecule
The 10%～30% of sieve carrier quality.
A kind of method of aqueous phase furfural hydrogenation Ketocyclopentane, comprises the steps:
Step one, by the catalyst H of above-mentioned preparation2Put into after reduction in autoclave, add furfural, deionized water,
Mix homogeneously, seals still；Wherein, deionized water quality is 1.5～19 times of furfural quality, and catalyst quality is furfural matter
The 0.5%～10% of amount；
Step 2, use N2Air in displacement autoclave repeatedly, then uses H2N in displacement autoclave2Repeatedly, afterwards
It is filled with the H of 2～6MPa2, at 120～200 DEG C, react 6～12h.
Beneficial effects of the present invention:
The present invention utilizes a step hydrothermal crystallizing fabricated in situ multi-stage porous Y type molecular sieve, and step is simple, and operating condition is easily controlled
System.Synthesized multi-stage porous Y molecular sieve relative crystallinity is high, not only contains micropore but also containing mesoporous, combine both holes
The advantage of material, and there is bigger specific surface area.Recycle simple infusion process molecular sieve is made high capacity amount and
Highly active catalyst, flourishing multi-stage porous gap structure so that the diffusion of reactant, mass transfer are accelerated, and catalyst surface is not
Easily form carbon distribution, decrease the generation of side reaction simultaneously.The catalyst standby with conventional molecular sieve series is compared, it will be apparent that
Accelerating reaction rate, and improve the yield of target product, catalytic effect is fine, has good industrial prospect.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the multi-stage porous Y type molecular sieve of embodiment 4 preparation.
Fig. 2 is the stereoscan photograph of the multi-stage porous Y type molecular sieve of embodiment 4 preparation.
Fig. 3 is the nitrogen adsorption isotherm of the multi-stage porous Y type molecular sieve of embodiment 4 preparation.
Fig. 4 is the BJH graph of pore diameter distribution of the multi-stage porous Y type molecular sieve of embodiment 4 preparation.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing the present invention done and further explain.Following embodiment limits the most in any form
The present invention, the technical scheme that the mode of all employing equivalents or equivalent transformation is obtained, it is in the protection model of the present invention
Among enclosing.In an embodiment, furfural conversion ratio and Ketocyclopentane are optionally defined as:
Furfural content × 100% in furfural conversion ratio=(furfural content in furfural content-reactant liquor in raw material)/raw material
Ketocyclopentane selectivity=change into furfural × 100% that the furfural/hydrogenation of Ketocyclopentane consumes
The preparation method of a kind of catalyst for aqueous phase furfural hydrogenation Ketocyclopentane, comprises the steps:
Step one, by Na2O:Al2O3: SiO2: H2O mol ratio is 10～16:1:10～16:180～370,
By sodium metaaluminate, sodium hydroxide, waterglass and deionized water mix homogeneously, obtain after stirring 0.5h, aging 24～72h
Y type molecular sieve directed agents；In the calculating of mol ratio, Na2The quality of O refers to sodium hydroxide, sodium metaaluminate, waterglass
Na in three kinds of materials2The summation of O, Al2O3Quality refer to Al in sodium metaaluminate2O3Quality, SiO2Quality refer to
SiO in waterglass2Quality, H2The quality of O refers in waterglass and the H of deionized water2The summation of O；Wherein, partially
In sodium aluminate, the mole of Al is with Al2O3Meter, Na mole with Na2O counts；In sodium hydroxide the mole of Na with
Na2O counts, containing SiO in waterglass2、Na2O and H2O。
Step 2, sodium metaaluminate is dissolved in deionized water, adds sodium hydroxide, then be slowly added dropwise waterglass, add afterwards
Entering mesoporous template and the Y type molecular sieve directed agents of step one preparation, mix homogeneously obtains aluminosilicate gels；Wherein,
Na in aluminosilicate gels (including the Y type molecular sieve directed agents added)2O:Al2O3: SiO2: H2O mol ratio is
3～6:1:8～12:180～370, Al in Y type molecular sieve directed agents2O3Quality is that the aluminosilicate finally given coagulates
Al in glue2O3The 5%～20% of quality；1ml aluminosilicate gels adds mesoporous template 0.01～0.05g, mesoporous template
For one or more in F127, APTES or sodium alginate.
Step 3, aluminosilicate gels prepared by step 2 load seal water heating kettle at 90～120 DEG C crystallization
15～40h, crystallization terminate rear solid product through sucking filtration, wash, be dried, then in Muffle furnace calcining remove mesoporous template
Agent, obtains multi-stage porous Y type molecular sieve；
Step 4, multi-stage porous Y type molecular sieve step 3 prepared are through 0.2～1mol/L NH4Cl solion exchanges
Obtaining Hydrogen multi-stage porous Y type molecular sieve, recycling equi-volume impregnating prepares molecular sieve carried type catalyst, i.e. institute
State the catalyst for aqueous phase furfural hydrogenation Ketocyclopentane.Molecular sieve carried type catalyst load metal be Cu, Ni,
One or two kinds of in Co, Pt, metal promoter precursor is nitrate, hydrochlorate；The metal quality of load is molecular sieve
The 10%～30% of carrier quality.
A kind of method of aqueous phase furfural hydrogenation Ketocyclopentane, comprises the steps:
Step one, the catalyst of above-mentioned preparation is used H at 400 DEG C2Put in autoclave after reduction 4h, add
Furfural, deionized water, mix homogeneously, seals still；Wherein, deionized water quality is 1.5～19 times of furfural quality, urges
Agent quality is the 0.5%～10% of furfural quality；
Step 2, use N2Air in displacement autoclave 3 times, then use H2N in displacement autoclave23 times, fill afterwards
Enter the H of 2～6MPa2, at 120～200 DEG C, react 6～12h.
SiO in the waterglass that following example use2、Na2O and H2O content be respectively 26.5wt.%, 8.3wt.%,
65.2wt.%.
Embodiment 1:
(1) 0.68g sodium metaaluminate, 3.68g sodium hydroxide, 14.86g waterglass and 18mL deionized water are mixed
Close uniformly, the most aging 24h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 3.11g sodium metaaluminate is dissolved in 58mL deionized water, addition 1.94g sodium hydroxide, more slowly
Dropping 32.51g waterglass, adds 0.9g3-aminopropyltriethoxywerene werene and 9.31g step (1) system afterwards
Standby Y type molecular sieve directed agents, is stirred at room temperature 3h, obtains aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 15h at 90 DEG C.After crystallization terminates, Gu
Body product is through sucking filtration, washing and dried, then in Muffle furnace, 550 DEG C of calcining 5h remove mesoporous template, obtain
Multi-stage porous Y type molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 0.2mol/L4Ratio according to solid-to-liquid ratio 1:30
Example carries out ion exchange, repeated exchanged twice at 80 DEG C, and after having exchanged, washing sucking filtration is not until having in solution every time
Chloride ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Again
(the Ni mass of load is molecular sieve supported weight to prepare 30Ni/HY loaded catalyst with equi-volume impregnating
30%).
Take catalyst prepared by 0.5g said method to be placed in tube furnace, at 400 DEG C, use H20.15L is put into after reduction 4h
Autoclave in, add 5g furfural, 95g deionized water, mix homogeneously, seal still, use N2Air 3 in displacement still
Secondary, then use H2In displacement still, nitrogen 3 times, is filled with the H of 2MPa afterwards2, open stirring 600rpm, be heated to 120 DEG C
Reaction 6h.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, furfural conversion ratio 96%, ring
Pentanone selectivity 87%.
Embodiment 2:
(1) 0.89g sodium metaaluminate, 2.65g sodium hydroxide, 18.22g waterglass and 15mL deionized water are mixed
Close uniformly, aged at room temperature 36h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.46g sodium metaaluminate is dissolved in 34mL deionized water, addition 1.528g sodium hydroxide, more slowly
Dropping 18.99g waterglass, adds Y type molecule prepared by 1.6g sodium alginate and 7.35g step (1) afterwards
Sieve directed agents, is stirred at room temperature 3h, obtains aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 20h at 110 DEG C.After crystallization terminates,
Solid product is through sucking filtration, washing and dried, then 550 DEG C of calcining 5h remove mesoporous template in Muffle furnace,
To multi-stage porous Y molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 0.5mol/L4Ratio according to solid-to-liquid ratio 1:30
Example carries out ion exchange, repeated exchanged twice at 80 DEG C, and after having exchanged, washing sucking filtration is not until having in solution every time
Chloride ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Again
(the Ni mass of load is molecular sieve supported weight to prepare 25Ni-5Co/HY loaded catalyst with equi-volume impregnating
25%, Co mass is molecular sieve supported weight the 5% of load).
Take catalyst prepared by 0.1g said method to be placed in tube furnace, at 400 DEG C, use H20.15 is put into after reduction 4h
In the autoclave of L, add 10g furfural, 90g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 3MPa afterwards2, open stirring 600rpm, add
Heat reacts 9h to 140 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 92%, Ketocyclopentane selectivity 88%.
Embodiment 3:
(1) 1.08g sodium metaaluminate, 3.48g sodium hydroxide, 15.07g waterglass and 10mL deionized water are mixed
Close uniformly, the most aging 24h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.16g sodium metaaluminate is dissolved in 50mL deionized water, addition 2.56g sodium hydroxide, more slowly
Dropping 19.58g waterglass, the Y type molecular sieve that afterwards prepared by addition 1.1g F127 and 4.23g step (1) guides
Agent, is stirred at room temperature 3h, obtain aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 25h at 120 DEG C.After crystallization terminates,
Solid product is through sucking filtration, washing and dried, then 550 DEG C of calcining 5h remove mesoporous template in Muffle furnace,
To multi-stage porous Y type molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 0.8mol/L4Ratio according to solid-to-liquid ratio 1:30
Example carries out ion exchange, repeated exchanged twice at 80 DEG C, and after having exchanged, washing sucking filtration is not until having in solution every time
Chloride ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Again
(the Cu mass of load is molecular sieve supported weight to prepare 10Cu/HY loaded catalyst with equi-volume impregnating
10%).
Take catalyst prepared by 0.1g said method to be placed in tube furnace, at 400 DEG C, use H20.15 is put into after reduction 4h
In the autoclave of L, add 20g furfural, 80g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 4MPa afterwards2, open stirring 600rpm, add
Heat reacts 12h to 160 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 95%, Ketocyclopentane selectivity 89%.
Embodiment 4:
(1) 1.36g sodium metaaluminate, 4.52g sodium hydroxide, 24.07g waterglass and 30mL deionized water are mixed
Close uniformly, the most aging 24h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.79g sodium metaaluminate is dissolved in 35mL deionized water, addition 1.49g sodium hydroxide, more slowly
Dropping 20.84g waterglass, the Y type molecular sieve that afterwards prepared by addition 1.1g sodium alginate and 14.99g step (1)
Directed agents, is stirred at room temperature 3h, Y type molecular sieve
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 40h at 100 DEG C.After crystallization terminates,
Solid product is through sucking filtration, washing and dried, then 550 DEG C of calcining 5h remove mesoporous template in Muffle furnace,
To multi-stage porous Y type molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 1mol/L4Ratio according to solid-to-liquid ratio 1:30
Carrying out ion exchange, repeated exchanged twice at 80 DEG C, after having exchanged, washing sucking filtration is not until having chlorine in solution every time
Ion, 110 DEG C of dried overnight, then calcining 1h obtains Hydrogen multi-stage porous Y type molecular sieve at 550 DEG C.Use again
Volume impregnation method prepares 10Cu-10Co/HY loaded catalyst, and (the Cu mass of load is molecular sieve supported weight
10%, Co mass is molecular sieve supported weight the 10% of load).
Take catalyst prepared by 1.5g said method to be placed in tube furnace, at 400 DEG C, use H20.15 is put into after reduction 4h
In the autoclave of L, add 15g furfural, 85g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 3MPa afterwards2, open stirring 600rpm, add
Heat reacts 8h to 180 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 94%, Ketocyclopentane selectivity 89%.
Fig. 1 is the XRD figure of the multi-stage porous Y type molecular sieve of embodiment 4 preparation, it can be seen that synthesize
Molecular sieve be respectively provided with the architectural feature of typical Y type molecular sieve and there is good peak intensity.
Fig. 2 is the stereoscan photograph of the multi-stage porous Y type molecular sieve of embodiment 4 preparation, can be clearly from figure
Going out, synthesized sample has well-regulated crystal morphology, and single zeolite crystal is octahedral structure, plane of crystal relatively light
Sliding；Crystallization effect is fine.
Fig. 3 is the nitrogen adsorption isotherm of the multi-stage porous Y type molecular sieve of embodiment 4 preparation, from the figure, it can be seen that
The isothermal line of the sample synthesized is typical iv type isothermal line, and adsorption isotherm embodies micropore and Jie simultaneously
The feature of Porous materials: have the highest adsorbance under low nitrogen partial pressure, illustrate that there is micropore；0.4～1.0 point
With the presence of obvious hysteresis loop in nip, illustrate that it contains a number of mesoporous.
Fig. 4 is the BJH graph of pore diameter distribution of the multi-stage porous Y type molecular sieve of embodiment 4 preparation, it can be seen that
The mesoporous major part of molecular sieve is distributed in 2～40nm.
Result above proves, the Y type molecular sieve of synthesis is a kind of to have mesoporous and micropore canals multistage pore canal simultaneously and divide
Son sieve.
Embodiment 5:
(1) by 1.15g sodium metaaluminate, 4.01g sodium hydroxide, 25.36g waterglass and 28mL deionized water
Mix homogeneously, the most aging 72h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.48g sodium metaaluminate is dissolved in 46mL deionized water, addition 1.77g sodium hydroxide, more slowly
Dropping 20.59g waterglass, adds 3.5g3-aminopropyltriethoxywerene werene and 16.72g step (1) system afterwards
The Y type molecular sieve directed agents obtained, is stirred at room temperature 3h, obtain aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 30h at 120 DEG C.After crystallization terminates,
Solid product is through sucking filtration, washing and dried, then 550 DEG C of calcining 8h remove mesoporous template in Muffle furnace,
To multi-stage porous Y type molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 0.2mol/L4Ratio according to solid-to-liquid ratio 1:30
Example carries out ion exchange, repeated exchanged twice at 80 DEG C, and after having exchanged, washing sucking filtration is not until having in solution every time
Chloride ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Again
(the Co mass of load is molecular sieve supported weight to prepare 25Co/HY loaded catalyst with equi-volume impregnating
25%).
Take catalyst prepared by 1g said method to be placed in tube furnace, at 400 DEG C, use H20.15 is put into after reduction 4h
In the autoclave of L, add 40g furfural, 60g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 3MPa afterwards2, open stirring 600rpm, add
Heat reacts 12h to 200 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 97%, Ketocyclopentane selectivity 87%.
Embodiment 6:
(1) 1.68g sodium metaaluminate, 4.86g sodium hydroxide, 28.48g waterglass and 30mL deionization are mixed
Uniformly, the most aging 48h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.88g sodium metaaluminate is dissolved in 37mL deionized water, addition 1.16g sodium hydroxide, more slowly
Dropping 32.14g waterglass, adds 2.6g3-aminopropyltriethoxywerene werene and 6.51g step (1) system afterwards
The directed agents obtained, is stirred at room temperature 3h, obtains aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 35h at 110 DEG C.After crystallization terminates,
Solid product is through sucking filtration, washing and dried, then 550 DEG C of calcining 5h remove mesoporous template in Muffle furnace,
To multi-stage porous Y type molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 1mol/L4Ratio according to solid-to-liquid ratio 1:30
Carrying out ion exchange, repeated exchanged twice at 80 DEG C, after having exchanged, washing sucking filtration is not until having chlorine in solution every time
Ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Use again
Equi-volume impregnating prepares 15Pt/HY loaded catalyst (Pt mass is molecular sieve supported weight the 15% of load).
Take catalyst prepared by 0.15g said method to be placed in tube furnace, at 400 DEG C, use H2Put into after reduction 4h
In the autoclave of 0.15L, add 30g furfural, 70g deionized water, mix homogeneously, seal still, use N2Displacement still
Interior air 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 5MPa afterwards2, open stirring 600rpm,
It is heated to 160 DEG C of reaction 10h.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, furfural
Conversion ratio 97%, Ketocyclopentane selectivity 94%.
Embodiment 7:
(1) 1.96g sodium metaaluminate, 6.59g sodium hydroxide, 32.35g waterglass and 28mL deionized water are mixed
Close uniformly, the most aging 48h after stirring 0.5h, obtain Y type molecular sieve directed agents.
(2) 1.97g sodium metaaluminate is dissolved in 37mL deionized water, addition 3.12g sodium hydroxide, more slowly
Dropping 18.24g waterglass, the Y type molecular sieve that addition 2.4g F127 and 17.23g step (1) prepare afterwards is led
To agent, it is stirred at room temperature 3h, obtains aluminosilicate gels.
(3) aluminosilicate gels that obtains is loaded in water heating kettle crystallization 25h at 90 DEG C.After crystallization terminates, Gu
Body product is through sucking filtration, washing and dried, then in Muffle furnace, 550 DEG C of calcining 5h remove mesoporous template, obtain
Multi-stage porous Y molecular sieve.
(4) by the multi-stage porous Y type molecular sieve obtained and the NHCl of 1mol/L4Ratio according to solid-to-liquid ratio 1:30
Carrying out ion exchange, repeated exchanged twice at 80 DEG C, after having exchanged, washing sucking filtration is not until having chlorine in solution every time
Ion, 110 DEG C of dried overnight, then at 550 DEG C, calcine 1h, obtain Hydrogen multi-stage porous Y type molecular sieve.Use again
Equi-volume impregnating prepares 15Pt-10Co/HY loaded catalyst, and (the Pt mass of load is molecular sieve supported weight
10%, Co mass is molecular sieve supported weight the 10% of load)).
Take catalyst prepared by 1.0g said method to be placed in tube furnace, at 400 DEG C, use H20.15 is put into after reduction 4h
In the autoclave of L, add 20g furfural, 80g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 6MPa afterwards2, open stirring 600rpm, add
Heat reacts 10h to 200 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 98%, Ketocyclopentane selectivity 98%.
Embodiment 8:
The catalyst taking 2g embodiment 1 preparation is placed in tube furnace, uses H at 400 DEG C20.15 is put into after reduction 4h
In the autoclave of L, add 20g furfural, 80g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 5MPa afterwards2, open stirring 600rpm, add
Heat reacts 10h to 140 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 93%, Ketocyclopentane selectivity 88%.
Embodiment 9:
The catalyst taking 0.2g embodiment 1 preparation is placed in tube furnace, uses H at 400 DEG C20.15 is put into after reduction 4h
In the autoclave of L, add 40g furfural, 60g deionized water, mix homogeneously, seal still, with empty in N2 displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 4MPa afterwards2, open stirring 600rpm, add
Heat reacts 12h to 160 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 98%, Ketocyclopentane selectivity 90%.
Embodiment 10:
The catalyst taking 2g embodiment 1 preparation is placed in tube furnace, uses H at 400 DEG C20.15 is put into after reduction 4h
In the autoclave of L, add 30g furfural, 70g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 6MPa afterwards2, open stirring 600rpm, add
Heat reacts 6h to 120 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 94%, Ketocyclopentane selectivity 86%.
Embodiment 11:
The catalyst taking 1.5g embodiment 1 preparation is placed in tube furnace, uses H at 400 DEG C20.15 is put into after reduction 4h
In the autoclave of L, add 15g furfural, 85g deionized water, mix homogeneously, seal still, use N2Sky in displacement still
Gas 3 times, then use H2In displacement still, nitrogen 3 times, is filled with the H of 3MPa afterwards2, open stirring 600rpm, add
Heat reacts 10h to 200 DEG C.Gained feed liquid Filtration of catalyst, forms with gas chromatographic analysis product, and furfural turns
Rate 98%, Ketocyclopentane selectivity 92%.
Claims (5)
1. the preparation method for the catalyst of aqueous phase furfural hydrogenation Ketocyclopentane, it is characterised in that comprise the steps:
Step one, by Na2O:Al2O3: SiO2: H2O mol ratio is 10～16:1:10～16:180～370, by sodium metaaluminate, sodium hydroxide, waterglass and deionized water mix homogeneously, stirring, aging after obtain Y type molecular sieve directed agents；
Step 2, being dissolved in deionized water by sodium metaaluminate, add sodium hydroxide, then be slowly added dropwise waterglass, add mesoporous template and the Y type molecular sieve directed agents of step one preparation afterwards, mix homogeneously obtains aluminosilicate gels；Wherein, Na in aluminosilicate gels2O:Al2O3: SiO2: H2The mol ratio of O is 3～6:1:8～12:180～370；Al in Y type molecular sieve directed agents2O3Quality is Al in aluminosilicate gels2O3The 5% ~ 20% of quality；1ml aluminosilicate gels adds mesoporous template 0.01～0.05g；
Step 3, aluminosilicate gels prepared by step 2 load seal water heating kettle in crystallization, crystallization terminate rear solid product through sucking filtration, wash, be dried, then in Muffle furnace calcining remove mesoporous template, obtain multi-stage porous Y type molecular sieve；
Step 4, multi-stage porous Y type molecular sieve step 3 prepared obtain Hydrogen multi-stage porous Y type molecular sieve through ion exchange, and recycling equi-volume impregnating prepares molecular sieve carried type catalyst, the i.e. described catalyst for aqueous phase furfural hydrogenation Ketocyclopentane；The ion exchange liquid that the exchange of described ion uses is 0.2～1 mol/L NH4Cl solution；The metal of described molecular sieve carried type catalyst load is the one or two kinds of in Cu, Ni, Co, Pt；Metal quality is molecular sieve supported weight 10%～the 30% of load.
It is used for the preparation method of the catalyst of aqueous phase furfural hydrogenation Ketocyclopentane the most according to claim 1, it is characterised in that described in step one, the time of stirring is 0.5h, and the aging time is 24～72h.
It is used for the preparation method of the catalyst of aqueous phase furfural hydrogenation Ketocyclopentane the most according to claim 1, it is characterised in that one or more during mesoporous template is F127, APTES or sodium alginate described in step 2.
It is used for the preparation method of the catalyst of aqueous phase furfural hydrogenation Ketocyclopentane the most according to claim 1, it is characterised in that the temperature of crystallization described in step 3 is 90～120 DEG C, and the time is 15～40h.
5. the method for an aqueous phase furfural hydrogenation Ketocyclopentane, it is characterised in that comprise the steps:
Step one, catalyst H prepared by arbitrary for Claims 1 to 4 described method2Put into after reduction in autoclave, add furfural, deionized water, mix homogeneously, seal still；Wherein, deionized water quality is 1.5～19 times of furfural quality, and catalyst quality is the 0.5%～10% of furfural quality；
Step 2, use N2Air in displacement autoclave repeatedly, then uses H2N in displacement autoclave2Repeatedly, the H of 2～6MPa it is filled with afterwards2, at 120～200 DEG C, react 6～12h.
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| CN105330523A (en) * | 2015-10-22 | 2016-02-17 | 复旦大学 | Method for preparing cyclopentanone by taking biomass resource as raw material |
| CN108863738B (en) * | 2017-05-08 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing cyclopentanone |
| CN110339839A (en) * | 2018-04-03 | 2019-10-18 | 北京旭阳科技有限公司 | A kind of method preparing microspherical catalyst, by this method preparation microspherical catalyst and use the method for the catalyst preparation cyclopentanone |
| CN109134223B (en) * | 2018-09-21 | 2020-12-25 | 中国科学技术大学 | Method for preparing 3-hydroxymethylcyclopentanone from 5-hydroxymethylfurfural |
| CN109759126A (en) * | 2019-01-30 | 2019-05-17 | 东南大学 | A kind of preparation method and applications for glycerol aromatized catalyst |
| CN112642468B (en) * | 2020-12-04 | 2022-10-21 | 广东省科学院化工研究所 | Catalyst for catalyzing and oxidizing ethylene and preparation method thereof |
| CN114085136B (en) * | 2021-11-08 | 2023-07-07 | 南京工业大学 | Method for preparing cyclopentanone by catalyzing furfural |
| CN114749203B (en) * | 2022-04-21 | 2023-06-16 | 郑州大学 | Mesoporous molecular sieve HMS supported platinum nickel element catalyst |
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