CN104475147B - Nano ZSM-5/gamma-Al2O3 composite catalyst for preparing acraldehyde by glycerol dehydration, and preparation method and application thereof - Google Patents
Nano ZSM-5/gamma-Al2O3 composite catalyst for preparing acraldehyde by glycerol dehydration, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical industry catalysts, and particularly relates to a nano ZSM-5/gamma-Al2O3 composite catalyst for preparing acraldehyde by glycerol dehydration, and a preparation method and application thereof. In the presence of nano ZSM-5, nano gamma-Al2O3 is prepared by a precipitation process, and the nano ZSM-5 and nano gamma-Al2O3 are uniformly mixed to obtain the composite catalyst with strong interaction. The nano ZSM-5/gamma-Al2O3 composite catalyst solves the problems of poor ZSM-5 stability and low gamma-Al2O3 selectivity in the acraldehyde catalytic reaction by glycerol dehydration. The prepared catalyst has excellent catalytic activity, selectivity and stability in the glycerol dehydration reaction.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts is and in particular to a kind of be applied to what preparing acrolein by dehydrating glycerin reacted
Catalyst and preparation method and application.
Background technology
The high level conversion of glycerine is using the important component part that technology is biodiesel technology, the abundant profit of by-product glycerin
With being to reduce biodiesel cost, promote one of biodiesel technology industrialization urgent need to solve the problem, endanger for alleviating the energy
Machine has very important meaning.
Dehydrating glycerin preparation acrolein technique is one of selection of high level conversion glycerine, and this reaction it is critical only that raising catalysis
The stability of agent and the selectivity of product.During dehydrating glycerin, there is the reaction such as cracking, condensation, oxidation simultaneously, easily produce
Macromolecular aromatic compound and polymer etc., covering catalyst avtive spot or blocking catalyst hole in the form of carbon distribution
Road, leads to catalyst to inactivate.Because, in dehydration and fill process, the presence of a large amount of water vapours, to catalyst hydrothermal stability
There is the requirement that comparison is high.In addition, the quantity of acidity of catalyst position, distribution, type also have great impact to reaction.
Due to its unique pore passage structure, (ten-ring straight hole road, aperture is 0.54nm x to zsm-5 zeolite catalyst
0.56nm, ten-ring sine duct 0.51nm x 0.54nm), suitable Acidity and high hydrothermal stability, often as
The catalyst of preparing acrolein by dehydrating glycerin.This catalyst is very high to the selectivity of methacrylaldehyde, more stable to water vapour, has very well
Initial activity, up to 100%, acrolein selectivity is close to 80%, but its deactivation rate is often quickly, and stoichiometric number is little for conversion ratio
When activity significantly reduce.In order to improve the activity stability of zsm-5 zeolite, cn103638965a discloses a kind of multi-stage porous
Zsm-5 zeolite catalyst, the activity stability of catalyst greatly improves, and the catalyst stabilization time is close to 30 under optimal conditions
Hour.
γ-al2o3Show the features different from zsm-5 in preparing acrolein by dehydrating glycerin reaction, conversion ratio is relatively low, be difficult to
Glycerine 100% is made to convert, selectively relatively low, can only be close to 60%, but its stability is much higher.As zsm-5 and γ-al2o3System
After becoming mixed catalyst, mixed catalyst performance is the average of two kinds of catalyst performances, therefore simply compounds and can not carry
The performance of high catalyst.
The invention provides one kind is by nanometer zsm-5 and nanometer γ-al2o3The composite catalyst made, initially with crystal seed
Revulsion prepares nanometer zsm-5 that crystal particle scale is 20～40nm, then in the presence of these nanometer of zsm-5, preparation nanometer γ-
al2o3, obtain nano-composite catalyst.In this catalyst, nanometer zsm-5 is in nanometer γ-al2o3In be uniformly distributed and two kinds
There is between nano-particle mutual synergy.Nanometer zsm-5/ γ-al disclosed by the invention2o3Composite catalyst is in dehydrating glycerin
Extraordinary dehydrating glycerin activity, acrolein selectivity and activity stability is shown in acrolein reaction.
Content of the invention
Have that high dehydrating glycerin is active, high acrolein selectivity and high activity are steady it is an object of the invention to provide a kind of
Qualitatively it is used for the nanometer zsm-5/ γ-al of preparing acrolein by dehydrating glycerin2o3Composite catalyst, and the preparation side of this catalyst
Method and application.
Nanometer zsm-5/ γ-al for preparing acrolein by dehydrating glycerin proposed by the present invention2o3Composite catalyst, its preparation
Method specifically comprises the following steps that
(1) prepare nanometer zsm-5 that crystal particle scale is 20～40nm first:
(1) by Ludox, al2(so4)3 .18h2O, naoh, kf and 4-propyl bromide (tpabr) are dissolved in deionized water
Make solution；Tpabr is organic formwork agent；
(2) add the zeolite seed crystal solution of mfi type, stir 2～4 hours under room temperature, be subsequently placed in water at 100～240 DEG C
Thermal crystallisation 1～24 hour；
(3) sample after crystallization in step (2) is separated, massive laundering is washed to neutrality, and dries；Then in air atmosphere
Lower 520～580 DEG C keep 4～8 hours, and roasting removes template；
(4) sample ions that step (3) obtains are exchanged ammonification type zsm-5 zeolite；
(2) prepare nanometer zsm-5/ γ-al2o3Composite catalyst:
In the presence of nanometer zsm-5, prepare nanometer γ-al by the precipitation method2o3, obtain nanometer zsm-5 and nanometer γ-
al2o3Uniformly mix the composite catalyst being associated with strong interaction；
(5) by al (oh)3Use dense hno3Dissolving, prepared aluminum nitrate solution, then add molecular weight 800～6000 peg,
Aluminum nitrate solution containing polyethylene glycol is obtained；
(6) nanometer zsm-5 of gained in step (4) is mixed with the aluminum nitrate solution of step (5) gained, stir under room temperature
0.5～1 hour；
(7) in the mixed liquor of step (6) gained, dropping precipitates alkali lye ammoniacal liquor-ammonium bicarbonate soln while stirring, until
The ph of mixed liquor stable 8.0～8.1, stop dropping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 20～60 minutes, by gained
Washing of precipitate separates, n-butanol azeotropic distillation dehydration in 0.5～1 hour, and 100～150 DEG C are vacuum dried 2～4 hours, 500- 600
DEG C calcination 2～4 hours, obtains a nanometer zsm-5/ γ-al2o3Composite catalyst.
In the present invention, Ludox described in step (1) is sio2Colloidal sol；Raw material is pressed following mol ratio and is added: sio2/
al2o3For 50～250, oh-/sio2For 0.05～0.8, kf/ sio2For 0.05～0.6, tpabr/sio2For 0.02～0.6,
h2o/sio2For 10～100, wherein tpabr is organic formwork agent, makes formation homogeneous mixture under agitation.
In the present invention, in step (2), seed-solution used is to have little particle zeolite stoste, the aqueous solution of mfi structure
Or non-crystallized completely structure inducer；The consumption of crystal seed is total sio2And al2o30.1～20wt% of amount, seed particles size
For 10～200nm.
In the present invention, al (oh) in step (5)3Amount be step (4) be obtained ammonia type nanometer zsm-5 weight 5～10
Times, the amount of peg is al (oh)31～20wt% of amount.
In the present invention, ammoniacal liquor-ammonium hydrogen carbonate mixed solution described in step (7), nh3Concentration be 2～4mol/l,
nh4hco3/nh3Mol ratio is 1～3.
Zsm-5/ γ-the al of the present invention2o3Composite catalyst is applied in preparing acrolein by dehydrating glycerin catalytic reaction, raw material
Liquid is 1%～80% glycerine water solution, and qualities of glycerin air speed is 0.2～8.0h-1, reaction temperature be 250～500 DEG C.This catalyst
It is demonstrated by good catalytic performance in preparing acrolein by dehydrating glycerin catalytic reaction: catalyst activity height (air speed 2.4h-1Under,
Glycerol conversion yield is more than 99%), acrolein selectivity high (selectively > 80%), catalyst under high-speed still the life-span very long
(air speed 2.4h-1Under, single pass life > 300h).
The reason catalyst of the present invention has excellent activity is:
1) nanometer zsm-5 has more preferable appearance carbon ability than traditional zsm-5, and activity is with stability all than traditional zsm-5
Increase；
2) nanometer γ-al2o3Than traditional γ-al2o3There is more preferable glycerol conversion yield；
3) crystal particle scale be 20～40nm nanometer zsm-5 in the presence of fabricated in situ with nanometer zsm-5/ γ-al2o3
In catalyst, nanometer zsm-5 and γ-al2o3Between have a strong interaction, the cooperative effect of generation make catalyst activity and
Stability all improves a lot, and the activity of catalyst compares a nanometer zsm-5 and γ-al with stability2o3All more preferable.
Brief description
Fig. 1 is nanometer zsm-5/ γ-al2o3The sem figure of composite catalyst.
Fig. 2 is the tem figure of nanometer zsm-5.
Specific embodiment
Below by example, the inventive method is illustrated, the embodiment not restriction to present invention.
Embodiment 1
Prepare Primogel: 1(sio by following molar ratio2): 0.004(al2o3): 0.3(naoh): 0.3
(kf): 0.1(tpabr): 30(h2O), Ludox, aluminum sulfate, NaOH are dissolved in deionized water respectively, continuous
The mfi crystal seed of 10 ~ 200nm size of potassium fluoride, 4-propyl bromide and 5wt% is added under conditions of stirring.Will be above-mentioned mixed
Compound is stirred at room temperature aging 2 hours, is then charged into carrying in teflon-lined stainless steel static crystallization kettle, in 140
DEG C reaction 12 hours.
After crystallization terminates, cooling, filter and be washed with deionized 3 ~ 4 times, at 80 ~ 120 DEG C, then dry gained sample
Product.Product removes template in Muffle furnace or tubular type kiln roasting, 550 DEG C of roastings 4 ~ 6 hours generally in air atmosphere.Use again
Concentration is that the ammonium nitrate solution of 5wt% carries out continuous three secondary ions exchange (liquor capacities/product in 80 DEG C to roasting sample
Amount of substance=10ml/g), 4 hours every time, obtain nanometer zsm-5 of ammonia type.
Separately take the al (oh) of 10 times of weight of ammonia type nanometer zsm-53, use dense hno3Dissolving is obtained aluminum nitrate solution, and weight
For al (oh)315wt% peg800 be dissolved in water solution mixing, be obtained containing polyethylene glycol aluminum nitrate solution.In this solution
Ammonia type nanometer zsm-5 that middle addition is obtained, stirs 1 hour under room temperature.Then drip ammoniacal liquor-ammonium bicarbonate soln while stirring,
nh3Concentration be 3mol/l, nh4hco3/nh3Mol ratio is 3, to mixed liquor ph stable 8.0～8.1, stop dropping ammonia
Water-ammonium bicarbonate soln, continues stirring 30 minutes, and gained washing of precipitate is separated, n-butanol azeotropic distillation dehydration in 1 hour, and 130
DEG C vacuum drying 3 hours, 550 DEG C of calcinations 3 hours, obtain a nanometer zsm-5/ γ-al2o3Composite catalyst.
Embodiment 2
Prepare Primogel: 1(sio by following molar ratio2): 0.01(al2o3): 0.3(naoh): 0.1
(kf): 0.3(tpabr): 60(h2O), Ludox, aluminum sulfate, NaOH are dissolved in deionized water respectively, continuous
The mfi crystal seed of 10 ~ 200nm size of potassium fluoride, 4-propyl bromide and 5wt% is added under conditions of stirring.Will be above-mentioned mixed
Compound is stirred at room temperature aging 4 hours, is then charged into carrying in teflon-lined stainless steel static crystallization kettle, in 200
DEG C reaction 8 hours.
After crystallization terminates, cooling, filter and be washed with deionized 3 ~ 4 times, at 80 ~ 120 DEG C, then dry gained sample
Product.Product removes template in Muffle furnace or tubular type kiln roasting, 550 DEG C of roastings 4 ~ 6 hours generally in air atmosphere.Use again
Concentration is that the ammonium nitrate solution of 5wt% carries out continuous three secondary ions exchange (liquor capacities/product in 80 DEG C to roasting sample
Amount of substance=10ml/g), 4 hours every time, obtain nanometer zsm-5 of ammonia type.
Separately take the al (oh) of 5 times of weight of ammonia type nanometer zsm-53, use dense hno3Dissolving is obtained aluminum nitrate solution, and weight
For al (oh)315wt% peg6000 be dissolved in water solution mixing, be obtained containing polyethylene glycol aluminum nitrate solution.In this solution
Ammonia type nanometer zsm-5 that middle addition is obtained, stirs 1 hour under room temperature.Then drip ammoniacal liquor-ammonium bicarbonate soln while stirring,
nh3Concentration be 2mol/l, nh4hco3/nh3Mol ratio is 2, to mixed liquor ph stable 8.0～8.1, stop dropping ammonia
Water-ammonium bicarbonate soln, continues stirring 30 minutes, and gained washing of precipitate is separated, n-butanol azeotropic distillation dehydration in 0.5 hour,
130 DEG C are vacuum dried 3 hours, and 550 DEG C of calcinations 3 hours obtain a nanometer zsm-5/ γ-al2o3Composite catalyst.
Embodiment 3-4
Step in the present embodiment is identical with above-described embodiment 1.Except for the difference that: in reactant mixture preparation process
In, the naoh/ si that adopted2O is changed into 0.1,0.8 from 0.3.
Embodiment 5-6
Step in the present embodiment is identical with above-described embodiment 1.Except for the difference that: in reactant mixture preparation process
In, the sio that adopted2/al2o3It is changed into 150,50 from 250.
Embodiment 7-8
Step in the present embodiment is identical with above-described embodiment 2.Except for the difference that: in reactant mixture preparation process
In, 1%, 15wt% is changed into from 5wt% using the amount of crystal seed.
Embodiment 9-10
Step in the present embodiment is identical with above-described embodiment 2.Except for the difference that: in reactant mixture preparation process
In, the peg6000 being adopted measures by al (oh)3The 15wt% of amount is changed into 5wt%, 20wt%.
Embodiment 11
Case-based Reasoning 1-10, carries out the catalytic reaction of preparing acrolein by dehydrating glycerin, catalyst on fixed-bed catalytic device
Loading is 1.0g, and raw material is the glycerine water solution of 1～80wt%, and mass space velocity (with respect to pure glycerin) is 0.2～8.0h-1, instead
Temperature is answered to be 250～500 DEG C.After auto injection, using gas chromatographic analysis, detector is fid detector to product, and difference is urged
The reaction result of agent is listed in table 1.
The reactivity worth of table 1 different catalysts
Claims (7)
1. a kind of nanometer zsm-5/ γ-al for preparing acrolein by dehydrating glycerin2o3The preparation method of composite catalyst, its feature
It is to specifically comprise the following steps that
(1) by Ludox, al2(so4)3 .18h2O, naoh, kf and 4-propyl bromide tpabr be dissolved in deionized water make molten
Liquid；Tpabr is organic formwork agent；
(2) add the zeolite seed crystal solution of mfi type, stir 2～4 hours under room temperature, be subsequently placed in hydro-thermal at 100～240 DEG C brilliant
Change 1～24 hour；
(3) sample after crystallization in step (2) is separated, massive laundering is washed to neutrality, and dries；Then in air atmosphere
520～580 DEG C keep 4～8 hours, and roasting removes template；
(4) sample ions that step (3) obtains are exchanged ammonification type zsm-5 zeolite；
(5) by al (oh)3Use dense hno3Dissolving, prepared aluminum nitrate solution, then add molecular weight 800～6000 peg, be obtained
Aluminum nitrate solution containing polyethylene glycol；
(6) nanometer zsm-5 of gained in step (4) is mixed with the aluminum nitrate solution of step (5) gained, under room temperature, stir 0.5
～1 hour；
(7) in the mixed liquor of step (6) gained, dropping precipitates alkali lye ammoniacal liquor-ammonium bicarbonate soln while stirring, until mixing
The ph of liquid stable 8.0～8.1, stop dropping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 30 minutes, by gained washing of precipitate
Separate, n-butanol azeotropic distillation dehydration in 0.5～1 hour, 130 DEG C are vacuum dried 2～4 hours, and 600 DEG C of calcinations 2～4 of 500- are little
When, obtain a nanometer zsm-5/ γ-al2o3Composite catalyst.
2. preparation method as claimed in claim 1 is it is characterised in that Ludox described in step (1) is sio2Colloidal sol；Raw material
Add by following mol ratio: sio2/al2o3For 50～250, oh-/sio2For 0.05～0.8, kf/ sio2For 0.05～
0.6, tpabr/sio2For 0.02～0.6, h2o/sio2For 10～100, wherein tpabr is organic formwork agent, makes shape under agitation
Uniformly mixture.
3. preparation method as claimed in claim 1 is it is characterised in that seed-solution used in step (2) is to have mfi knot
The little particle zeolite stoste of structure, the aqueous solution or non-crystallized completely structure inducer；The consumption of crystal seed is total sio2And al2o3Amount
0.1～20wt%, seed particles size be 10～200nm.
4. preparation method as claimed in claim 1 is it is characterised in that al (oh) in step (5)3Amount be step (4) be obtained
5～10 times of ammonia type nanometer zsm-5 weight, the amount of peg is al (oh)31～20wt% of amount.
5. preparation method as claimed in claim 1 is it is characterised in that the ammoniacal liquor-ammonium hydrogen carbonate mixing described in step (7) is molten
Liquid, nh3Concentration be 2～4mol/l, nh4hco3/nh3Mol ratio is 1～3.
6. adopt the nanometer zsm-5/ γ-al that the preparation method of one of claim 1 ~ 5 obtains2o3Composite catalyst.
7. as claimed in claim 6 nanometer of zsm-5/ γ-al2o3Composite catalyst is in preparing acrolein by dehydrating glycerin catalytic reaction
In application it is characterised in that material liquid be 1%～80% wt% glycerine water solution, qualities of glycerin air speed be 0.2～8.0h-1, instead
Temperature is answered to be 250～500 DEG C.
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| CN105327711B (en) * | 2015-08-24 | 2018-04-13 | 北京理工大学 | A kind of solid acid catalyst based on ZSM 5 and preparation method thereof |
| CN109534378A (en) * | 2018-11-27 | 2019-03-29 | 东华大学 | A kind of preparation method of anti-hard aggregation nano alumina particles |
| CN109999894A (en) * | 2019-04-24 | 2019-07-12 | 中建西部建设贵州有限公司 | A kind of ardealite extracts aluminum for the method for composite catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052993A2 (en) * | 2006-11-01 | 2008-05-08 | Bioecon International Holding N.V. | Process for production of acrolein and other oxygenated compounds from glycerol in a transported bed reactor |
| CN101538195A (en) * | 2009-04-23 | 2009-09-23 | 上海华谊丙烯酸有限公司 | Acrylaldehyde preparation method by glycerin dehydration under inert gas dilution |
| CN101580461A (en) * | 2009-06-22 | 2009-11-18 | 上海华谊丙烯酸有限公司 | Method for preparing acrolein by dehydrating glycerin with catalyst macropore alumina |
| CN103638965A (en) * | 2013-12-27 | 2014-03-19 | 复旦大学 | Hierarchical porous ZSM-5 zeolite catalyst for preparing acrolein through glycerin dehydration as well as preparation method and application of hierarchical porous ZSM-5 zeolite catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052993A2 (en) * | 2006-11-01 | 2008-05-08 | Bioecon International Holding N.V. | Process for production of acrolein and other oxygenated compounds from glycerol in a transported bed reactor |
| CN101538195A (en) * | 2009-04-23 | 2009-09-23 | 上海华谊丙烯酸有限公司 | Acrylaldehyde preparation method by glycerin dehydration under inert gas dilution |
| CN101580461A (en) * | 2009-06-22 | 2009-11-18 | 上海华谊丙烯酸有限公司 | Method for preparing acrolein by dehydrating glycerin with catalyst macropore alumina |
| CN103638965A (en) * | 2013-12-27 | 2014-03-19 | 复旦大学 | Hierarchical porous ZSM-5 zeolite catalyst for preparing acrolein through glycerin dehydration as well as preparation method and application of hierarchical porous ZSM-5 zeolite catalyst |
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