CN104475147A - 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 PDF

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CN104475147A
CN104475147A CN201410706948.9A CN201410706948A CN104475147A CN 104475147 A CN104475147 A CN 104475147A CN 201410706948 A CN201410706948 A CN 201410706948A CN 104475147 A CN104475147 A CN 104475147A
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composite catalyst
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CN104475147B (en
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沈伟
潘文雅
黄亮
徐华龙
秦枫
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Fudan University
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Fudan University
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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

A kind of nano-ZSM-5 for preparing acrolein by dehydrating glycerin/γ-Al 2o 3composite catalyst and its preparation method and application
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of Catalysts and its preparation method and the application that are applied to preparing acrolein by dehydrating glycerin reaction.
Background technology
The high level trans-utilization technology of glycerine is the important component part of biodiesel technology; making full use of of by-product glycerin reduces biodiesel cost; promote one of biodiesel technology industrialization urgent need to solve the problem, have very important meaning for alleviating energy crisis.
It is one of selection of high level glycerine converting that dehydrating glycerin prepares acrolein technique, and this reaction key is to improve the stability of catalyst and the selective of product.In dehydrating glycerin process, there is the reactions such as cracking, condensation, oxidation simultaneously, easily produce large molecule aromatic compound and polymer etc., with the form covering catalyst avtive spot of carbon distribution or blocking catalyst duct, cause catalysqt deactivation.Due in dehydration and fill process, the existence of a large amount of water vapour, also has higher requirement to catalyst hydrothermal stability.In addition, the quantity of acidity of catalyst position, distribution, type also have great impact to reaction.
ZSM-5 zeolite catalyst is due to pore passage structure (the ten-ring straight hole road of its uniqueness, aperture is 0.54nm x 0.56nm, the sinusoidal duct 0.51nm x 0.54nm of ten-ring), suitable Acidity and high hydrothermal stability, usually as the catalyst of preparing acrolein by dehydrating glycerin.Selective very high to methacrylaldehyde of this catalyst, more stable to water vapour, have good initial activity, conversion ratio can reach 100%, and acrolein selectivity is close to 80%, but its deactivation rate is often very fast, and namely stoichiometric number hour activity has remarkable reduction.In order to improve the activity stability of ZSM-5 zeolite, CN103638965A discloses a kind of multi-stage porous ZSM-5 zeolite catalyst, and the activity stability of catalyst improves greatly, under optimal conditions catalyst stabilization 30 hours around.
γ-Al 2o 3the performance feature different from ZSM-5 in preparing acrolein by dehydrating glycerin reaction, conversion ratio is lower, is difficult to glycerine 100% is transformed, selective also lower, can only close to 60%, but its stability is much higher.As ZSM-5 and γ-Al 2o 3after making mixed catalyst, mixed catalyst performance is the average of two kinds of catalyst performances, therefore the simply composite performance that can not improve catalyst.
The invention provides a kind of by nano-ZSM-5 and nanometer γ-Al 2o 3the composite catalyst made, first adopts crystal seed revulsion to prepare the nano-ZSM-5 that crystal particle scale is 20 ~ 40nm, then under these nano-ZSM-5s exist, and preparation nanometer γ-Al 2o 3, obtain nano-composite catalyst.In this catalyst, nano-ZSM-5 is at nanometer γ-Al 2o 3in be uniformly distributed and between two kinds of nano particles, there is mutual synergy.Nano-ZSM-5 disclosed by the invention/γ-Al 2o 3composite catalyst shows extraordinary dehydrating glycerin activity, acrolein selectivity and activity stability in preparing acrolein by dehydrating glycerin reaction.
Summary of the invention
The object of the present invention is to provide a kind of nano-ZSM-5 for preparing acrolein by dehydrating glycerin/γ-Al with high dehydrating glycerin activity, high acrolein selectivity and high-activity stable 2o 3composite catalyst, and the preparation method of this catalyst and application.
The nano-ZSM-5 for preparing acrolein by dehydrating glycerin/γ-Al that the present invention proposes 2o 3composite catalyst, its preparation method concrete steps are as follows:
(1) nano-ZSM-5 that crystal particle scale is 20 ~ 40nm is first prepared:
(1) by Ludox, Al 2(SO 4) 3 .18H 2o, NaOH, KF and 4-propyl bromide (TPABr) are dissolved in deionized water makes solution; TPABr is organic formwork agent;
(2) the zeolite seed crystal solution of MFI type is added, stirred at ambient temperature 2 ~ 4 hours, hydrothermal crystallizing 1 ~ 24 hour at being then placed in 100 ~ 240 DEG C;
(3) by the sample separation after crystallization in step (2), massive laundering is washed to neutrality, and dries; Then in air atmosphere 520 ~ 580 DEG C keep 4 ~ 8 hours, roasting removing template;
(4) sample ions step (3) obtained exchanges ammonification type ZSM-5 zeolite;
(2) nano-ZSM-5/γ-Al is prepared 2o 3composite catalyst:
Under nano-ZSM-5 exists, prepare nanometer γ-Al by the precipitation method 2o 3, obtain nano-ZSM-5 and nanometer γ-Al 2o 3homogeneous phase mixing also has strong interactional composite catalyst;
(5) by Al (OH) 3use dense HNO 3dissolve, obtained aluminum nitrate solution, and then add molecular weight 800 ~ 6000 PEG, the obtained aluminum nitrate solution containing polyethylene glycol;
(6) nano-ZSM-5 of gained in step (4) is mixed with the aluminum nitrate solution of step (5) gained, stirred at ambient temperature 0.5 ~ 1 hour;
(7) in the mixed liquor of step (6) gained, precipitation alkali lye ammoniacal liquor-ammonium bicarbonate soln is dripped while stirring, until the pH of mixed liquor is stabilized in 8.0 ~ 8.1, stop dripping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 20 ~ 60 minutes, gained washing of precipitate is separated, n-butanol azeotropic distillation 0.5 ~ 1 hour dehydration, 100 ~ 150 DEG C of vacuum drying 2 ~ 4 hours, 500-600 DEG C of calcinations 2 ~ 4 hours, obtain nano-ZSM-5/γ-Al 2o 3composite catalyst.
In the present invention, described in step (1), Ludox is SiO 2colloidal sol; Raw material adds by following mol ratio: SiO 2/ al 2 o 3be 50 ~ 250, oH - / SiO 2be 0.05 ~ 0.8, KF/ SiO 2be 0.05 ~ 0.6, TPABr/SiO 2be 0.02 ~ 0.6, H 2o/SiO 2be 10 ~ 100, wherein TPABr is organic formwork agent, under agitation makes formation homogeneous mixture.
In the present invention, seed-solution used in step (2) is have the granule zeolite stoste of MFI structure, the aqueous solution or non-crystallized structure inducer completely; The consumption of crystal seed is total SiO 2and Al 2o 30.1 ~ 20wt% of amount, seed particles size is 10 ~ 200nm.
In the present invention, Al (OH) in step (5) 3amount be 5 ~ 10 times of the obtained ammonia type nano-ZSM-5 weight of step (4), the amount of PEG is Al (OH) 31 ~ 20wt% of amount.
In the present invention, the ammoniacal liquor described in step (7)-carbonic hydroammonium mixed solution, NH 3concentration be 2 ~ 4mol/L, NH 4hCO 3/ NH 3mol ratio is 1 ~ 3.
ZSM-5/ γ-Al of the present invention 2o 3composite catalyst is applied in preparing acrolein by dehydrating glycerin catalytic reaction, and material liquid is 1% ~ 80% glycerine water solution, and qualities of glycerin air speed is 0.2 ~ 8.0h -1, reaction temperature is 250 ~ 500 DEG C.The good catalytic performance of the performance of this catalyst in preparing acrolein by dehydrating glycerin catalytic reaction: catalyst activity high (air speed 2.4h -1under, glycerol conversion yield is greater than 99%), acrolein selectivity high (selective >80%), catalyst still life-span very long (air speed 2.4h under high-speed -1under, single pass life >300h).
The reason that catalyst of the present invention has excellent activity is:
1) nano-ZSM-5 has better appearance carbon ability than traditional ZSM-5, and activity all increases than traditional Z SM-5 with stability;
2) nanometer γ-Al 2o 3than traditional γ-Al 2o 3there is better glycerol conversion yield;
3) crystal particle scale be 20 ~ 40nm nano-ZSM-5 exist under fabricated in situ with nano-ZSM-5/γ-Al 2o 3in catalyst, nano-ZSM-5 and γ-Al 2o 3between have strong interaction, the cooperative effect of generation makes the activity of catalyst and stability all improve a lot, and the activity of catalyst compares nano-ZSM-5 and γ-Al with stability 2o 3all better.
Accompanying drawing explanation
Fig. 1 is nano-ZSM-5/γ-Al 2o 3the SEM figure of composite catalyst.
Fig. 2 is the TEM figure of nano-ZSM-5.
Detailed description of the invention
Below by example, the inventive method is illustrated, the restriction of embodiment not to content of the present invention.
embodiment 1
By molar ratio preparation Primogel: 1(SiO below 2): 0.004(Al 2o 3): 0.3(NaOH): 0.3(KF): 0.1(TPABr): 30(H 2o), Ludox, aluminum sulfate, NaOH are dissolved in deionized water respectively, under the condition constantly stirred, add the MFI crystal seed of 10 ~ 200nm size of potassium fluoride, 4-propyl bromide and 5wt%.Said mixture is at room temperature stirred aging 2 hours, then in tape loaded teflon-lined stainless steel static crystallization still, in 140 DEG C of reactions 12 hours.
After crystallization terminates, cooling, filters and spends deionized water 3 ~ 4 times, then at 80 ~ 120 DEG C, drying gained sample.Product, in Muffle furnace or tubular type kiln roasting removing template, to be generally in air atmosphere 550 DEG C of roastings 4 ~ 6 hours.By concentration be again 5wt% ammonium nitrate solution in 80 DEG C to roasting sample carry out continuous three secondary ions exchange (liquor capacity/product quality=10ml/g), each 4 hours, obtain the nano-ZSM-5 of ammonia type.
Separately get the Al (OH) of 10 times of weight of ammonia type nano-ZSM-5 3, use dense HNO 3dissolve obtained aluminum nitrate solution, and weight is Al (OH) 3the water-soluble solution mixing of the PEG800 of 15wt%, the obtained aluminum nitrate solution containing polyethylene glycol.Add obtained ammonia type nano-ZSM-5 in this solution, stirred at ambient temperature 1 hour.Then ammoniacal liquor-ammonium bicarbonate soln is dripped while stirring, NH 3concentration be 3mol/L, NH 4hCO 3/ NH 3mol ratio is 3, and the pH to mixed liquor is stabilized in 8.0 ~ 8.1, stops dripping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 30 minutes, gained washing of precipitate is separated, the dehydration in 1 hour of n-butanol azeotropic distillation, 130 DEG C of vacuum drying 3 hours, 550 DEG C of calcinations 3 hours, obtain nano-ZSM-5/γ-Al 2o 3composite catalyst.
embodiment 2
By molar ratio preparation Primogel: 1(SiO below 2): 0.01(Al 2o 3): 0.3(NaOH): 0.1(KF): 0.3(TPABr): 60(H 2o), Ludox, aluminum sulfate, NaOH are dissolved in deionized water respectively, under the condition constantly stirred, add the MFI crystal seed of 10 ~ 200nm size of potassium fluoride, 4-propyl bromide and 5wt%.Said mixture is at room temperature stirred aging 4 hours, then in tape loaded teflon-lined stainless steel static crystallization still, in 200 DEG C of reactions 8 hours.
After crystallization terminates, cooling, filters and spends deionized water 3 ~ 4 times, then at 80 ~ 120 DEG C, drying gained sample.Product, in Muffle furnace or tubular type kiln roasting removing template, to be generally in air atmosphere 550 DEG C of roastings 4 ~ 6 hours.By concentration be again 5wt% ammonium nitrate solution in 80 DEG C to roasting sample carry out continuous three secondary ions exchange (liquor capacity/product quality=10ml/g), each 4 hours, obtain the nano-ZSM-5 of ammonia type.
Separately get the Al (OH) of 5 times of weight of ammonia type nano-ZSM-5 3, use dense HNO 3dissolve obtained aluminum nitrate solution, and weight is Al (OH) 3the water-soluble solution mixing of the PEG6000 of 15wt%, the obtained aluminum nitrate solution containing polyethylene glycol.Add obtained ammonia type nano-ZSM-5 in this solution, stirred at ambient temperature 1 hour.Then ammoniacal liquor-ammonium bicarbonate soln is dripped while stirring, NH 3concentration be 2mol/L, NH 4hCO 3/ NH 3mol ratio is 2, and the pH to mixed liquor is stabilized in 8.0 ~ 8.1, stops dripping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 30 minutes, gained washing of precipitate is separated, the dehydration in 0.5 hour of n-butanol azeotropic distillation, 130 DEG C of vacuum drying 3 hours, 550 DEG C of calcinations 3 hours, obtain nano-ZSM-5/γ-Al 2o 3composite catalyst.
embodiment 3-4
Step in the present embodiment is identical with above-described embodiment 1.Unlike: in reactant mixture preparation process, the NaOH/ Si adopted 2o becomes 0.1,0.8 from 0.3.
embodiment 5-6
Step in the present embodiment is identical with above-described embodiment 1.Unlike: in reactant mixture preparation process, the SiO adopted 2/ Al 2o 3150,50 are become from 250.
embodiment 7-8
Step in the present embodiment is identical with above-described embodiment 2.Unlike: in reactant mixture preparation process, adopt that the amount of crystal seed becomes 1% from 5wt%, 15wt%.
embodiment 9-10
Step in the present embodiment is identical with above-described embodiment 2.Unlike: in reactant mixture preparation process, the PEG6000 amount adopted is by Al (OH) 3the 15wt% of amount becomes 5wt%, 20wt%.
embodiment 11
Case-based Reasoning 1-10, fixed-bed catalytic device carries out the catalytic reaction of preparing acrolein by dehydrating glycerin, and packed catalyst amount is 1.0g, and raw material is the glycerine water solution of 1 ~ 80wt%, and mass space velocity (relative to pure glycerin) is 0.2 ~ 8.0h -1, reaction temperature is 250 ~ 500 DEG C.Product is after auto injection, and adopt gas chromatographic analysis, detector is fid detector, and the reaction result of different catalysts lists in table 1.
The reactivity worth of table 1 different catalysts

Claims (7)

1. the nano-ZSM-5 for preparing acrolein by dehydrating glycerin/γ-Al 2o 3the preparation method of composite catalyst, is characterized in that concrete steps are as follows:
(1) by Ludox, Al 2(SO 4) 3 .18H 2o, NaOH, KF and 4-propyl bromide TPABr are dissolved in deionized water and make solution; TPABr is organic formwork agent;
(2) the zeolite seed crystal solution of MFI type is added, stirred at ambient temperature 2 ~ 4 hours, hydrothermal crystallizing 1 ~ 24 hour at being then placed in 100 ~ 240 DEG C;
(3) by the sample separation after crystallization in step (2), massive laundering is washed to neutrality, and dries; Then in air atmosphere 520 ~ 580 DEG C keep 4 ~ 8 hours, roasting removing template;
(4) sample ions step (3) obtained exchanges ammonification type ZSM-5 zeolite;
(5) by Al (OH) 3use dense HNO 3dissolve, obtained aluminum nitrate solution, and then add molecular weight 800 ~ 6000 PEG, the obtained aluminum nitrate solution containing polyethylene glycol;
(6) nano-ZSM-5 of gained in step (4) is mixed with the aluminum nitrate solution of step (5) gained, stirred at ambient temperature 0.5 ~ 1 hour;
(7) in the mixed liquor of step (6) gained, precipitation alkali lye ammoniacal liquor-ammonium bicarbonate soln is dripped while stirring, until the pH of mixed liquor is stabilized in 8.0 ~ 8.1, stop dripping ammoniacal liquor-ammonium bicarbonate soln, continue stirring 30 minutes, gained washing of precipitate is separated, n-butanol azeotropic distillation 0.5 ~ 1 hour dehydration, 130 DEG C of vacuum drying 2 ~ 4 hours, 500-600 DEG C of calcinations 2 ~ 4 hours, obtain nano-ZSM-5/γ-Al 2o 3composite catalyst.
2. preparation method as claimed in claim 1, is characterized in that described in step (1), Ludox is SiO 2colloidal sol; Raw material adds by following mol ratio: SiO 2/ Al 2o 3be 50 ~ 250, OH -/ SiO 2be 0.05 ~ 0.8, KF/ SiO 2be 0.05 ~ 0.6, TPABr/SiO 2be 0.02 ~ 0.6, H 2o/SiO 2be 10 ~ 100, wherein TPABr is organic formwork agent, under agitation makes formation homogeneous mixture.
3. preparation method as claimed in claim 1, is characterized in that seed-solution used in step (2) is have the granule zeolite stoste of MFI structure, the aqueous solution or non-crystallized structure inducer completely; The consumption of crystal seed is total SiO 2and Al 2o 30.1 ~ 20wt% of amount, seed particles size is 10 ~ 200nm.
4. preparation method as claimed in claim 1, is characterized in that Al (OH) in step (5) 3amount be 5 ~ 10 times of the obtained ammonia type nano-ZSM-5 weight of step (4), the amount of PEG is Al (OH) 31 ~ 20wt% of amount.
5. preparation method as claimed in claim 1, is characterized in that the ammoniacal liquor-carbonic hydroammonium mixed solution described in step (7), NH 3concentration be 2 ~ 4mol/L, NH 4hCO 3/ NH 3mol ratio is 1 ~ 3.
6. adopt nano-ZSM-5/γ-Al that the preparation method of one of claim 1 ~ 5 obtains 2o 3composite catalyst.
7. nano-ZSM-5/γ-Al as claimed in claim 6 2o 3the application of composite catalyst in preparing acrolein by dehydrating glycerin catalytic reaction, it is characterized in that material liquid is 1% ~ 80% glycerine water solution, qualities of glycerin air speed is 0.2 ~ 8.0h -1, reaction temperature is 250 ~ 500 DEG C.
CN201410706948.9A 2014-12-01 2014-12-01 Nano ZSM-5/gamma-Al2O3 composite catalyst for preparing acraldehyde by glycerol dehydration, and preparation method and application thereof Expired - Fee Related CN104475147B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105327711A (en) * 2015-08-24 2016-02-17 北京理工大学 ZSM-5-based solid acid catalyst 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

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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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105327711A (en) * 2015-08-24 2016-02-17 北京理工大学 ZSM-5-based solid acid catalyst and preparation method thereof
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

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