CN103508476B - Mesoporous nanometer alumina, preparation method and application thereof - Google Patents
Mesoporous nanometer alumina, preparation method and application thereof Download PDFInfo
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- CN103508476B CN103508476B CN201210212154.8A CN201210212154A CN103508476B CN 103508476 B CN103508476 B CN 103508476B CN 201210212154 A CN201210212154 A CN 201210212154A CN 103508476 B CN103508476 B CN 103508476B
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Abstract
The present invention provides a mesoporous nanometer alumina preparation method, which comprises: preparing a gel system containing a template agent and an aluminum source, removing the solvent in the gel system, and calcining to obtain the mesoporous nanometer alumina, wherein the template agent is a block copolyether represented by a formula (1), R1 is amino-substituted hydrocarbyl, x, y and z independently and respectively are 1-100, and the aluminum source is an organic aluminum source. The present invention further provides mesoporous nanometer alumina prepared by using the preparation method and an application of the mesoporous nanometer alumina in propylene preparation through isopropanol dehydration. According to the present invention, the preparation method does not require adjustment on the pH value of the solution, and has characteristics of simpleness and environment burden reduction; the prepared mesoporous nanometer alumina has characteristics of large pore size and large specific surface area, and can achieve high isopropanol conversion rate and propylene selectivity in the propylene preparation reaction through isopropanol dehydration. The formula (1) is shown in the description.
Description
Technical field
The present invention relates to a kind of mesoporous nano-aluminum oxide and its preparation method and application.
Background technology
Aluminum oxide is the solid materials of a kind of porousness, high degree of dispersion, has good absorption property, surface acidity and thermostability, is a kind of important catalyzer or support of the catalyst, is widely used.In recent years, the preparations and applicatio research face of mesoporous nano-aluminum oxide is very wide.The preparation method of mesoporous nano-aluminum oxide, mainly contain template, activated aluminum powder hydrolysis method, exsiccated ammonium alum method, sol-gel method etc. at present, be wherein that the research of Template preparation alumina material is more with tensio-active agent, tensio-active agent is wherein divided into ionic surface active agent and nonionogenic tenside.Ionic surface active agent is divided into again cats product and anion surfactant.Cats product method mainly adds the cats products such as cetyl trimethylammonium bromide as template, is settled out aluminum oxide with aluminium source under acidity or alkaline action condition; Anion surfactant method mainly adds the anion surfactants such as sodium laurylsulfonate as template, is settled out aluminum oxide with aluminium source under acidity or alkaline action condition.The research of nonionogenic tenside method is more, and comprise TritonX series, polyoxyethylene glycol series, and polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is as tensio-active agent, general and aluminium source is precipitated out under acid action condition.The segmented copolymer related to mainly contains P123, F127, F84 etc.
Document (J Am Chem Soc, 2002,124,12294-12301) is reported, with aluminum nitrate or aluminum chloride for aluminium source, adopt P64, P65, P84, P123 etc. as template, the specific surface area scope of gained mesoporous nano-aluminum oxide is 249-367m
2/ g, mesoporous pore size is 4.0-9.6 nanometer, and wherein, take P65 as template, the specific surface area of aluminum oxide can reach 367m
2/ g, mesoporous pore size is 5.6 nanometers; Separately have document (Chem Mater, 2011,23,1147-1157) to report, employing P123 is template, has prepared a series of metal oxide mesoporous material, take wherein aluminum chloride as aluminium source, and can obtain specific surface area is 469m
2/ g, mesoporous pore size is the mesoporous nano-aluminum oxide of 6.6 nanometers.
CN101024503A discloses a kind of supergravity reactor and adopts the precipitator method to prepare the method for meso-porous alumina, and the specific surface area of the meso-porous alumina of preparation is 250-300m
2/ g, mesoporous pore size is 4-10 nanometer; CN101492170A discloses a kind of cationicsurfactants, and anion surfactant lauric acid etc., nonionogenic tenside P123, F127, prepare mesoporous nano-aluminum oxide in acid condition, and specific surface area is 300m
2/ below g, average mesopore aperture is below 6.7 nanometers; It is template with P123 that CN102219242A discloses a kind of, and mineral acid or mineral alkali are the method that meso-porous alumina prepared by precipitation agent, meso-porous alumina specific surface area 180-400m
2/ g, average mesopore aperture is 3.5-7.6 nanometer; CN101863499A discloses a kind of under organic acid promoter effect, with P123 or F27 for template prepares the method for macroporous-mesoporous alumina.
Although aforesaid method can obtain mesoporous alumina catalyst, generally all need to regulate acid-basicity after adding aluminium source, or directly select to prepare under acidic conditions, not only complex process, and the burden too increasing post-processed.
Summary of the invention
The object of the invention is the defect preparing mesoporous nano-aluminum oxide method complexity in order to overcome prior art, there is provided a kind of without the need to regulator solution acid-basicity, method is simple and alleviate the preparation method of the mesoporous nano-aluminum oxide of environmental pressure and the mesoporous nano-aluminum oxide prepared by the method and the application in isopropanol dehydration propylene thereof.
Under the instruction of aforementioned background art, most of investigator all thinks, in the process of synthesizing mesoporous nano aluminum oxide, all needs the acid-basicity of regulator solution.Within a very long time, the present inventor also holds above-mentioned viewpoint, the thinking and the present inventor breaks the normal procedure, find unexpectedly in research process, end group is adopted to be that the polypropylene glycol-polyethylene glycol-propylene glycol block copolyether of amino-substituted hydrocarbyl is as template and employing organoaluminum source, regulator solution acid-basicity is no longer needed in hydrolysis, the mesoporous nano-aluminum oxide of preparation has larger specific surface area and larger aperture, and the segmented copolymer that catalytic performance is better than commonly using is as P123 etc., and preparation method is simple.The present invention is completed based on above-mentioned discovery.
The invention provides a kind of preparation method of mesoporous nano-aluminum oxide, wherein, the method comprises: preparation contains the gelling system in template and aluminium source; Then remove the solvent in gelling system and roasting, obtain mesoporous nano-aluminum oxide; Wherein, described template is block co-polyether as the formula (1); Described aluminium source is organoaluminum source,
Formula (1)
Wherein, R
1for the alkyl that amino replaces, x, y and z are respectively 1-100 separately.
In addition, the present invention also provides the mesoporous nano-aluminum oxide obtained by above-mentioned preparation method.
In addition, present invention also offers the application of mesoporous nano-aluminum oxide in isopropanol dehydration propylene.
As can be seen from the method for the invention described above, method of the present invention is simple, and condition is easy to control.The present invention adopt end group be the polypropylene glycol-polyethylene glycol-propylene glycol block copolyether of amino-substituted hydrocarbyl as template to prepare mesoporous nano-aluminum oxide, in conjunction with organoaluminum source, avoid the acid-alkali accommodation directly selected in preparation under acidic conditions or sequential hydrolysis, thus overcome in prior art the defect needing to regulate pH, large and the mesoporous nano-aluminum oxide that mesopore size is also relatively large of specific surface area is obtained in relative ease mode, and during the catalyzer of mesoporous nano-aluminum oxide as isopropanol dehydration propylene, there is very high iso-propanol conversion rate and Propylene Selectivity.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the stereoscan photograph of the mesoporous nano-aluminum oxide that embodiment 1 obtains;
Fig. 2 is the stereoscan photograph of the mesoporous nano-aluminum oxide that embodiment 2 obtains;
Fig. 3 is the stereoscan photograph of the mesoporous nano-aluminum oxide that embodiment 3 obtains;
Fig. 4 is the stereoscan photograph of the aluminum oxide that comparative example 1 obtains;
Fig. 5 is the stereoscan photograph of the aluminum oxide that comparative example 2 obtains.
Embodiment
A preparation method for mesoporous nano-aluminum oxide, wherein, the method comprises: preparation contains the gelling system in template and aluminium source; Then remove the solvent in gelling system and roasting, obtain mesoporous nano-aluminum oxide; Wherein, described template is block co-polyether as the formula (1); Described aluminium source is organoaluminum source,
Formula (1)
Wherein, R
1for the alkyl that amino replaces; X, y and z are respectively 1-100 separately, and preferred y is 9-39, y:(x+z) be 2-7, when preferably y is 9 further, y:(x+z) be 2.5, y is when being 12.5, y:(x+z) be 2.08 or y when being 39, y:(x+z) be 6.5.
The preparation method of above-mentioned mesoporous nano-aluminum oxide is mainly through selecting block co-polyether to be as the formula (1) template and selecting organoaluminum source as aluminium source, do not need the acid-basicity of regulator solution, therefore other steps and condition can adopt step well known in the art and condition to carry out.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, in block co-polyether as the formula (1), R
1for the alkyl that amino replaces, R
1in amino be-NH
2,-NHR
2or-N (R
2)
2; R
2for carbonatoms is the alkyl of 1-4; R
1carbonatoms be 1-4, and, R
1carbonatoms when being 2-4, preferred R
1in amino be 1-replace or 2-replace.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, in order to realize object of the present invention further, preferred R
1for-CH
2nH
2,-CH
2nHCH
3,-CH
2n (CH
3)
2,-CH
2cH
2nH
2,-CH
2cH
2nH (C
2h
5) ,-CH
2cH
2n (C
2h
5)
2,-CH
2cHNH
2cH
3,-CH
2cH (NHCH
3) CH
3,-CH
2cHN (CH
3)
2cH
3or-CH
2cHNH
2cH
2cH
3, particularly preferably R
1for-CH
2cHNH
2cH
3.
The preferred template of the present invention is CH
3cHNH
2cH
2(C
3h
6o)
x(C
2h
4o)
y(C
3h
6o)
zcH
2cHNH
2cH
3(y=9, y:(x+z)=2.5), CH
3cHNH
2cH
2(C
3h
6o)
x(C
2h
4o)
y(C
3h
6o)
zcH
2cHNH
2cH
3(y=12.5, y:(x+z)=2.08) or CH
3cHNH
2cH
2(C
3h
6o)
x(C
2h
4o)
y(C
3h
6o)
zcH
2cHNH
2cH
3(y=39, y:(x+z)=6.5).
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, the present invention contains the step of the gelling system in template and aluminium source without particular requirement to preparation, under preferable case, this step comprises: template, at 30-60 DEG C, is dissolved in organic solvent by (1); (2) organoaluminum source being dissolved in step (1) gained solution, in order to make organoaluminum source fully to dissolve, after preferably adding organoaluminum source, stirring 10-60 minute, more preferably 15-50 minute; (3) in step (2) gained solution, drip suitable quantity of water and mix, forming gelling system, what mix to make the gelling system of formation is more even, preferably after dropping deionized water, continues to stir 2-20 hour, more preferably 4-16 hour.
Above-mentioned method for preparing catalyst according to the present invention can obtain mesoporous nano-aluminum oxide catalyzer, to the mol ratio of described template, organic solvent, organoaluminum source and water without particular requirement, can select in wider scope, under preferable case, the mol ratio of organoaluminum source, template, organic solvent and water is 1:0.05-0.7:5-120:3-15.In order to realize object of the present invention further, the mol ratio of preferred organoaluminum source, template, organic solvent and water is 1:0.1-0.5:10-100:3-8.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, the present invention to the kind in described organoaluminum source without particular requirement, but in order to better realize object of the present invention, preferred aluminium alcoholates salt, one or more in further particular methanol aluminium, aluminum ethylate, Tripropoxyaluminum, aluminum isopropylate and aluminium butoxide, more preferably aluminum isopropylate.
The present inventor finds, particularly aluminum isopropylate is dispersed better than inorganic aluminate in the solution to select organoaluminum source preferred aluminium alcoholates salt, because there is similar organic moiety to the organic solvent in this solution, template with the cosurfactant optionally added in organoaluminum source, the surface amino groups of possible template can act on organoaluminum source, thus affect some physicochemical property of final mesoporous nano-aluminum oxide, obtain aperture and the larger mesoporous nano-aluminum oxide of specific surface area; In addition, after using template and organoaluminum source, in hydrolysis, acid-alkali accommodation or acidic conditions is no longer needed.In order to make organoaluminum source fully be hydrolyzed, in system, dripping appropriate water, stir simultaneously, at a certain temperature, organoaluminum source is hydrolyzed, the milky gel system of final formation.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, the present invention without particular requirement, as long as template and cosurfactant can be made fully to dissolve in organic solvent, forms clear transparent solutions to the kind of described organic solvent.Under preferable case, described organic solvent is one or more in alcohol, nitrile and ketone.Further preferred described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and isopropylcarbinol, and described nitrile is acetonitrile, and described ketone is acetone.In order to further realize object of the present invention, preferred organic solvent is one or more in ethanol, Virahol and acetone, particularly preferably acetone.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, under preferable case, preparation contains in the process of the gelling system in template and aluminium source, also add and have cosurfactant, the addition sequence of the present invention to described cosurfactant does not specially require, and can carry out with reference to prior art.The kind of the present invention to described cosurfactant does not have particular requirement yet, can carry out with reference to prior art.In order to better realize object of the present invention, described cosurfactant and organic solvent are not identical, the saturated monohydroxy alcohol of described cosurfactant to be carbonatoms be 7-11, preferred isooctyl alcohol; In addition, the mol ratio in described cosurfactant and aluminium source, without particular requirement, can be selected in wider scope, and under preferable case, the mol ratio in described cosurfactant and aluminium source is 0.5-20:1, more preferably 1-10:1.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, the present invention to the condition of the solvent in described removal gelling system without particular requirement, under preferable case, the step of the solvent in described removal gelling system comprises: gelling system is carried out successively first time static solvent flashing and second time static solvent flashing; Described first time, the temperature of static solvent flashing was 30-80 DEG C, more preferably 30-60 DEG C, and the time is 2-20 hour, more preferably 5-15 hour; The temperature of the static solvent flashing of described second time is for being greater than 80 DEG C to being less than or equal to 95 DEG C, more preferably 85-95 DEG C, and the time is 6-18 hour, more preferably 8-14 hour.The static solvent flashing of second time is directly carried out further after static solvent flashing of preferred first time.The present invention by carrying out first time static solvent flashing and for the second time static solvent flashing successively to gelling system, can pore size distribution be obtained evenly mesoporous nano-aluminum oxide.
According to the preparation method of mesoporous nano-aluminum oxide of the present invention, wherein, the present invention to the condition of described roasting without particular requirement, under preferable case, the temperature of described roasting is 400-750 DEG C, more preferably 450-700 DEG C, time is 2-10 hour, more preferably 4-8 hour.
The present invention also provides the mesoporous nano-aluminum oxide obtained by above-mentioned preparation method.
Present invention also offers the application of mesoporous nano-aluminum oxide in isopropanol dehydration propylene.
The present invention is further described below in conjunction with embodiment.Scope of the present invention does not limit by these embodiments.
In following examples, the stereoscan photograph of sample is obtained by FEI Co. of U.S. XL-30 Flied emission environmental scanning electron microscope; BET characterizing method carries out on the full-automatic materialization adsorption instrument of MICROMERITICS company of U.S. ASAP2020-M+C.In catalyst performance evaluation, adopt the Agilent HP-6890 type chromatographic product composition being furnished with HP Plot-Q capillary column and fid detector.Being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant, the selectivity of product on this basis.
The transformation efficiency calculation formula of Virahol is as follows:
The optionally calculation formula of propylene to Virahol is as follows:
Wherein, X is transformation efficiency; S is selectivity; M is the quality of component; N is the molar weight of component; Wherein m
0and n
0represent the quality before component reaction and molar weight respectively.
In following examples, template purchased from American Aldrich company, other reagent are all from being purchased.
Embodiment 1
At 40 DEG C, by 3.20 grams of block co-polyether template (y=12.5, y:(x+z)=2.08, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-900) add stirring and dissolving in 13.20 grams of acetone, then add 3.00 grams of isooctyl alcohol and 1.90 grams of aluminum isopropylates and stir 50 minutes; Drip deionized water 0.60 gram wherein again, continue stirring 6 hours; Then, under 60 DEG C of conditions, static volatilization 5 hours, 85 DEG C of static volatilizations 14 hours; Last 500 DEG C of roastings 6 hours, obtain 0.41 gram of mesoporous nano-aluminum oxide.
Characterization result: mean pore size 14.18 nanometer; Specific surface area 341.1m
2/ g;
Stereoscan photograph is see Fig. 1.
Embodiment 2
At 30 DEG C, by 0.86 gram of block co-polyether template (y=12.5, y:(x+z)=2.08, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-900) add stirring and dissolving in 45.00 grams of acetone, then add 1.30 grams of isooctyl alcohol and 1.90 grams of aluminum isopropylates and stir 35 minutes; Drip deionized water 1.20 grams wherein again, continue stirring 4 hours; Then, under 45 DEG C of conditions, static volatilization 15 hours, 95 DEG C of static volatilizations 8 hours; Last 450 DEG C of roastings 8 hours, obtain 0.43 gram of mesoporous nano-aluminum oxide.
Characterization result: mean pore size 12.00 nanometer; Specific surface area 413.1m
2/ g;
Stereoscan photograph is see Fig. 2.
Embodiment 3
At 60 DEG C, by 4.00 grams of block co-polyether template (y=12.5, y:(x+z)=2.08, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-900) add stirring and dissolving in 13.00 grams of acetone, then add 5.81 grams of isooctyl alcohol and 1.62 gram of three aluminum ethylate and stir 15 minutes; Drip deionized water 0.90 gram wherein again, continue stirring 4 hours; Then, under 30 DEG C of conditions, static volatilization 10 hours, 90 DEG C of static volatilizations 12 hours; Last 700 DEG C of roastings 4 hours, obtain 0.43 gram of mesoporous nano-aluminum oxide.
Characterization result: mean pore size 11.85 nanometer; Specific surface area 369.7m
2/ g;
Stereoscan photograph is see Fig. 3.
Embodiment 4
At 40 DEG C, by 10.65 grams of block co-polyether template (y=12.5, y:(x+z)=2.08, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-900), 15.4 grams of isooctyl alcohol and 30.30 grams of aluminum isopropylates add in 64.30 grams of acetone, stir 30 minutes; Drip deionized water 23.9 grams wherein again, continue stirring 16 hours; Then, under 70 DEG C of conditions, static volatilization 4 hours, 80 DEG C of static volatilizations 16 hours; Last 400 DEG C of roastings 10 hours, obtain 7.51 grams of mesoporous nano-aluminum oxides.The stereoscan photograph of this sample is similar to Fig. 1.
Embodiment 5
Mesoporous nano-aluminum oxide is prepared according to the method for embodiment 1, unlike, template adopts 2.4 grams of block co-polyether template (y=9, y:(x+z)=2.5, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-600), 0.40 gram of mesoporous nano-aluminum oxide is finally obtained.The stereoscan photograph of this sample is similar to Fig. 1.
Embodiment 6
Mesoporous nano-aluminum oxide is prepared according to the method for embodiment 1, unlike, template adopts 7.55 grams of block co-polyether template (y=39, y:(x+z)=6.5, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-2003), 0.42 gram of mesoporous nano-aluminum oxide is finally obtained.The stereoscan photograph of this sample is similar to Fig. 1.
Embodiment 7
At 60 DEG C, by 3.30 grams of block co-polyether template (y=12.5, y:(x+z)=2.08, R as the formula (1)
1for-CH
2cHNH
2cH
3; Trade names:
eD-900) and 1.90 grams of aluminum isopropylates add in 14.00 grams of acetone, stir 15 minutes; Drip deionized water 0.70 gram wherein again, continue stirring 4 hours; Then, under 30 DEG C of conditions, static volatilization 10 hours, 90 DEG C of static volatilizations 12 hours; Last 600 DEG C of roastings 4 hours, obtain 0.40 gram of mesoporous nano-aluminum oxide.The stereoscan photograph of this sample is similar to Fig. 1.
Comparative example 1
Aluminum oxide is prepared according to the method for embodiment 1, unlike, template adopts 20.62 grams of P123(molecular-weight average about 5800).
Its stereoscan photograph is see Fig. 4.
Comparative example 2
With deionized water respectively configuration concentration be the sodium hydrogen carbonate solution of 0.1mol/L alum liquor and 0.2mol/L; Under agitation, 40 grams of 0.2mol/L sodium hydrogen carbonate solutions are slowly added drop-wise in 10 grams of 0.1mol/L alum liquors, are stirred to till not producing bubble; After filtration, washing, 110 DEG C of freeze-day with constant temperature 12 hours, then obtain aluminum oxide in 6 hours in 500 DEG C of constant temperature calcinings.
Its specific surface area is 13.9m
2/ g, its stereoscan photograph is see Fig. 5.
Application Example 1
Mesoporous nano-aluminum oxide embodiment 1 prepared obtains 10-20 object particle through compressing tablet, fragmentation, screening, and continuous flow fixed bed carries out the reaction evaluating of isopropanol dehydration propylene.
Reactor inside diameter is the stainless steel reaction pipe of 10 millimeters, and loaded catalyst is 2.00 grams, and reaction pressure is 0.1MPa, and temperature of reaction is 190 ~ 450 DEG C, Virahol feed weight air speed WHSV=1h
-1, nitrogen is as thinner, and the mol ratio of Virahol/(Virahol+nitrogen) is 0.3:1.Product adopts on-line chromatograph analysis, and data acquisition normalization method processes, and calculate iso-propanol conversion rate and Propylene Selectivity, result is as shown in table 1.
Table 1
| Temperature of reaction (DEG C) | Iso-propanol conversion rate (%) | Propylene Selectivity (%) |
| 250 | 99.4 | 99.5 |
| 270 | 99.5 | 99.8 |
| 290 | 99.7 | 99.8 |
| 350 | 100 | 99.0 |
| 400 | 100 | 97.4 |
| 440 | 100 | 96.3 |
Application Example 2
Mesoporous nano-aluminum oxide embodiment 2 prepared obtains 10-20 object particle through compressing tablet, fragmentation, screening, and continuous flow fixed bed carries out the reaction evaluating of isopropanol dehydration propylene.
The method in Application Example 1 is adopted to investigate the activity of mesoporous nano-aluminum oxide catalyzer, unlike, Virahol weight space velocity WHSV=0.5h
-1.
Experiment shows, as Virahol WHSV=0.5h
-1time, when the temperature of reaction of catalyzer is 240-350 DEG C, iso-propanol conversion rate is greater than 99%, and Propylene Selectivity is greater than 99%; When temperature of reaction continues to be elevated to 440 DEG C from 350 DEG C, Propylene Selectivity only drops to 96% from 99%.
Application Example 3
Mesoporous nano-aluminum oxide embodiment 3 prepared obtains 10-20 object particle through compressing tablet, fragmentation, screening, and continuous flow fixed bed carries out the reaction evaluating of isopropanol dehydration propylene.
The method in Application Example 1 is adopted to investigate the activity of mesoporous nano-aluminum oxide catalyzer, unlike, Virahol weight space velocity WHSV=2h
-1.
Experiment shows, as Virahol WHSV=2h
-1time, when the temperature of reaction of catalyzer is 250-350 DEG C, iso-propanol conversion rate is greater than 99%, and Propylene Selectivity is greater than 99%; When temperature of reaction continues to be elevated to 440 DEG C from 350 DEG C, Propylene Selectivity only drops to 96% from 99%.
Application Example 4
Mesoporous nano-aluminum oxide embodiment 4 prepared obtains 10-20 object particle through compressing tablet, fragmentation, screening, and continuous flow fixed bed carries out the reaction evaluating of isopropanol dehydration propylene.
The method in Application Example 1 is adopted to investigate the activity of mesoporous nano-aluminum oxide catalyzer, unlike, Virahol weight space velocity WHSV=2h
-1.
Experiment shows, as Virahol WHSV=2h
-1time, when the temperature of reaction of catalyzer is 260-350 DEG C, iso-propanol conversion rate is greater than 99%, and Propylene Selectivity is greater than 99%; When temperature of reaction continues to be elevated to 440 DEG C from 350 DEG C, Propylene Selectivity only drops to 96% from 99%.
Comparison study example 1
Aluminum oxide comparative example 1 prepared obtains 10-20 object particle through compressing tablet, fragmentation, screening, and continuous flow fixed bed carries out the reaction evaluating of isopropanol dehydration propylene.
The method in Application Example 1 is adopted to investigate the activity of aluminium oxide catalyst.
Experiment shows, as Virahol WHSV=1h
-1time, when the temperature of reaction of catalyzer is 270-320 DEG C, iso-propanol conversion rate is greater than 99%, but Propylene Selectivity is 97 ~ 99%; Temperature of reaction continues to be elevated to 440 DEG C from 320 DEG C, and Propylene Selectivity drops to 93% from 98%.
Visible according to the data of embodiment 1-3, the preparation method of mesoporous nano-aluminum oxide provided by the invention can prepare mean pore size (11-15 nanometer) and specific surface area (330-450m
2/ g) larger mesoporous nano-aluminum oxide.And clearly can find out that the sample obtained by embodiment 1-3 has more regular vermiform by Fig. 1-3, and size is more even.Embodiment 4 has the feature similar to embodiment 1 sample.According to embodiment 5-7, by adopting the polypropylene glycol of different amino-substituted hydrocarbyl-polyethylene glycol-propylene glycol block copolyether and not adding cosurfactant isooctyl alcohol, the object that the present invention prepares the mesoporous nano-aluminum oxide that mean pore size is comparatively large and specific surface area is larger can be realized equally.
Can find out that the sample shape homogeneity of comparative example 1 is poor according to Fig. 4 and Fig. 3 contrast, arrangement is comparatively chaotic.Contrasted by Fig. 5 and Fig. 2 and can find out that comparative example 2 sample is reunited serious, lack of homogeneity.Illustrated by Fig. 1-5, the shape of the mesoporous nano-aluminum oxide that the mesoporous nano-aluminum oxide obtained according to preparation method provided by the invention prepares than the preparation method of comparative example 1 and 2, size homogeneity are better.
Can find out according to Application Example 1-4, the mesoporous nano-aluminum oxide adopting the present invention to obtain has very high catalytic activity in the reaction of isopropanol dehydration propylene, when temperature of reaction is 260-350 DEG C, iso-propanol conversion rate and Propylene Selectivity are all greater than 99%, its catalytic performance is obviously better than not regulating solution ph according to comparative example 1, adopt the catalytic performance of aluminum oxide in the reaction of isopropanol dehydration propylene prepared by P123 template and organoaluminum source, the range of reaction temperature be mainly manifested in when iso-propanol conversion rate and Propylene Selectivity are all greater than 99% is relatively wide, and Propylene Selectivity is relatively high.
This shows, the present invention is by adopting end group to be that the polypropylene glycol-polyethylene glycol-propylene glycol block copolyether of amino-substituted hydrocarbyl is as template, in conjunction with organoaluminum source, avoid the acid-alkali accommodation directly selected in preparation under acidic conditions or sequential hydrolysis, thus overcome in prior art the defect needing to regulate pH, and the activity of mesoporous nano-aluminum oxide in the reaction of isopropanol dehydration propylene obtained is also higher.Overcome in the preparation process of existing mesoporous nano-aluminum oxide, the problem that the fussy degree of technique and the activity of obtained mesoporous nano-aluminum oxide cannot be taken into account simultaneously.
Claims (21)
1. a preparation method for mesoporous nano-aluminum oxide, is characterized in that, the method comprises: preparation contains the gelling system in template and aluminium source; Then remove the solvent in gelling system and roasting, obtain mesoporous nano-aluminum oxide; Wherein, described template is for such as formula the block co-polyether shown in (1); Described aluminium source is organoaluminum source,
Wherein, R
1for the alkyl that amino replaces, x, y and z are respectively 1-100 separately.
2. preparation method according to claim 1, wherein, R
1in amino be-NH
2,-NHR
2or-N (R
2)
2; R
2for carbonatoms is the alkyl of 1-4;
Wherein, R
1carbonatoms be 1-4.
3. preparation method according to claim 2, wherein, R
1carbonatoms be 2-4, R
1in amino be 1-replace or 2-replace.
4. the preparation method according to Claims 2 or 3, wherein, described R
1for-CH
2nH
2,-CH
2nHCH
3,-CH
2n (CH
3)
2,-CH
2cH
2nH
2,-CH
2cH
2nH (C
2h
5) ,-CH
2cH
2n (C
2h
5)
2,-CH
2cHNH
2cH
3,-CH
2cH (NHCH
3) CH
3,-CH
2cHN (CH
3)
2cH
3or-CH
2cHNH
2cH
2cH
3.
5. preparation method according to claim 4, wherein, described R
1for-CH
2cHNH
2cH
3.
6. preparation method according to claim 1, wherein, the step that preparation contains the gelling system in template and aluminium source comprises:
(1) at 30-60 DEG C, template is dissolved in organic solvent;
(2) organoaluminum source is dissolved in step (1) gained solution;
(3) in step (2) gained solution, drip suitable quantity of water and mix, forming gelling system.
7. preparation method according to claim 6, wherein, the mol ratio of organoaluminum source, template, organic solvent and water is 1:0.05-0.7:5-120:3-15.
8. preparation method according to claim 7, wherein, the mol ratio of organoaluminum source, template, organic solvent and water is 1:0.1-0.5:10-100:3-8.
9. according to the preparation method in claim 1,6-8 described in any one, wherein, described organoaluminum source is aluminium alcoholates salt.
10. preparation method according to claim 9, wherein, described organoaluminum source is one or more in aluminum methylate, aluminum ethylate, Tripropoxyaluminum and aluminium butoxide.
11. preparation methods according to claim 10, wherein, described organoaluminum source is aluminum isopropylate.
12. according to the preparation method in claim 6-8 described in any one, and wherein, described organic solvent is one or more in alcohol, nitrile and ketone.
13. preparation methods according to claim 12, wherein, described alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and isopropylcarbinol, and described nitrile is acetonitrile, and described ketone is acetone.
14. preparation methods according to claim 6, wherein, in the process of the gelling system of preparation containing template and aluminium source, also add and have cosurfactant, the saturated monohydroxy alcohol of described cosurfactant to be carbonatoms be 7-11; The mol ratio in described cosurfactant and aluminium source is 0.5-20:1.
15. preparation methods according to claim 14, wherein, described saturated monohydroxy alcohol is isooctyl alcohol; The mol ratio in described cosurfactant and aluminium source is 1-10:1.
16. preparation methods according to claim 1, wherein, the step of the solvent in described removal gelling system comprises: gelling system is carried out successively first time static solvent flashing and second time static solvent flashing; Described first time, the temperature of static solvent flashing was 30-80 DEG C, and the time is 2-20 hour; The temperature of the static solvent flashing of described second time is for being greater than 80 DEG C to being less than or equal to 95 DEG C, and the time is 6-18 hour.
17. preparation methods according to claim 16, wherein, described first time the temperature of static solvent flashing be 30-60 DEG C, the time is 5-15 hour; The temperature of the static solvent flashing of described second time is 85-95 DEG C, and the time is 8-14 hour.
18. preparation methods according to claim 1, wherein, the temperature of described roasting is 400-750 DEG C, and the time is 2-10 hour.
19. preparation methods according to claim 18, wherein, the temperature of described roasting is 450-700 DEG C, and the time is 4-8 hour.
The mesoporous nano-aluminum oxide that preparation method in 20. claim 1-19 described in any one obtains.
21. application of mesoporous nano-aluminum oxide according to claim 20 in isopropanol dehydration propylene.
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| CN104692426A (en) * | 2015-02-05 | 2015-06-10 | 中国矿业大学 | Synthesis method of high-hydrothermal-stability mesoporous gamma-Al2O3 |
| CN104944455A (en) * | 2015-06-24 | 2015-09-30 | 南京理工大学 | Sol-gel method for preparing aluminum oxide |
| CN104961146B (en) * | 2015-06-26 | 2017-04-12 | 吉林大学 | Nanometer sheet aluminum hydroxide gel and preparation method thereof |
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| CN106984303B (en) * | 2017-04-28 | 2019-09-10 | 武汉理工大学 | A kind of foramen magnum-mesoporous γ-Al in grade hole supporting noble metal2O3Catalyst and preparation method thereof |
| WO2019053956A1 (en) * | 2017-09-12 | 2019-03-21 | 花王株式会社 | Method for producing olefin |
| CN109675577A (en) * | 2019-03-04 | 2019-04-26 | 福州大学 | A kind of nickel-base catalyst and preparation method thereof for carbon dioxide methanation |
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