CN102614926A - Method for preparing loaded solid super acidic catalyst directly by microwave method - Google Patents
Method for preparing loaded solid super acidic catalyst directly by microwave method Download PDFInfo
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- CN102614926A CN102614926A CN2012100615365A CN201210061536A CN102614926A CN 102614926 A CN102614926 A CN 102614926A CN 2012100615365 A CN2012100615365 A CN 2012100615365A CN 201210061536 A CN201210061536 A CN 201210061536A CN 102614926 A CN102614926 A CN 102614926A
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Abstract
The invention relates to a method for preparing a loaded solid super acidic catalyst directly by a microwave method, and belongs to a method for preparing a super acidic catalyst. The method comprises the following steps of: (1) mixing and stirring NaHCO3 and a carbon nano tube in a weight ratio of 1:500 fully, and roasting in a microwave reactor to obtain a Na-loaded catalyst carrier; (2) heating the Na-loaded catalyst carrier by microwave radiation, adding a mixed solution of antimony pentachloride (SbCl5) and trimethylsilyl trifluoromethanesulfonate (F3CSO3Si(CH3)3) dropwise, stirring and immersing to obtain a suspension mixed solution; (3) filtering the suspension mixed solution to obtain a solid precursor and a mixed solution; (4) putting the solid precursor into the microwave reactor, heating by the microwave radiation, and roasting to obtain a solid super acidic catalyst prototype; and (5) performing operation for 1 to 5 times by taking the solid super acidic catalyst prototype as a raw material according to the steps (2), (3) and (4) to obtain the solid-loaded super acidic catalyst. The method has the advantages that: the loaded solid super acidic catalyst prepared by the microwave method is high in catalytic hydrocracking activity and selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of super acidic catalyst, particularly a kind of microwave method directly prepares the method for supported solid superacid acid catalyst.
Background technology
Acid catalyzed reaction relates to petroleum refining process such as hydrocarbon cracking, reformation, isomery; Also relate to petrochemical industry and fine chemistry industry plurality of cells courses of reaction such as olefin hydration, olefinic polymerization, alkylating aromatic hydrocarbon, aromatic hydrocarbons acylated, alcoholic acid esterification, we can say that acid catalyst is the basis of a series of essential industrys.
At present, solid super acid catalyst mainly comprises following several types, is respectively the unit process that has utilized isomerization reaction, alkylated reaction, esterification, acylation reaction, oligomeric anti-, substitution reaction, acetal and ketal, directly prepares super acidic catalyst.
(1) with SbF
5, TaF
5, BF
3, SbF
3Monobasics such as-HF or multi-component liquid acid load on the carriers such as suitable porous oxide, graphite, ion exchange resin;
(2) with the mixed solid super-strong acid that gets of two or more inorganic salts, like AlCl
3-CuCl, AlCl
3-Ti
2(SO
4)
3
(3) resin is made perfluor macromolecular material Nafion-H with the fluorine modification;
(4) with the molecular sieve modified strong acid type molecular sieve that makes, like peracidity modenite HM;
(5) compound with elements such as phosphorous, tungsten, germanium makes heteropoly acid through different chemical or physical process;
(6) solid super-strong acid that two or more metal oxide roasting is made is like W0
3/ TiO
2-ZrO
2
(7) sulfate radical is carried on the metal oxide surface roasting and makes solid super-strong acid, like SO
4 2-/ MxOy;
(8) load acid and the collaborative super acidic catalyst of metal composite are as at SO
4 2-/ ZrO
2Improve the component (like Pt) in catalyst activity and life-span or the like in the catalyst in interpolation.
Above-mentioned super acidic catalyst preparation is complicated, the time is long, and the active principle of catalyst is easy to run off, poor heat stability, does not particularly have significant aromatic ring bridged bond catalytic hydrogenation, and catalytic efficiency is low.
Summary of the invention
The objective of the invention is to provide a kind of microwave method directly to prepare the method for supported solid superacid acid catalyst; Solve that the preparation of present super acidic catalyst is complicated, the time is long; The active principle of catalyst is easy to run off, poor heat stability; Particularly there is not significant aromatic ring bridged bond catalytic hydrogenation, the problem that catalytic efficiency is low.
The objective of the invention is to realize like this: the preparation method is:
(1) with weight ratio is the NaHCO of 1:500
3Fully mix stirring, NaHCO with CNT
3Weight concentration be 1 ‰ to 1%; And mixed material is positioned in the microwave reactor of 300W to 320W power, the temperature that in nitrogen stream, keeps carry out microwave radiation heating is at 200 ° of C to 220 ° of C, and static roasting obtains load Na catalyst carrier after 10 minutes to 20 minutes;
(2) place the above-mentioned load Na catalyst carrier for preparing of 10g to 500g in the flask in microwave reactor; Under 100W to 120W power microwave irradiation; The temperature of carry out microwave radiation heating is at 30 ° of C to 50 ° of C in nitrogen gas atmosphere, dropwise add gross weight in the flask and be 100g to 1000g, volume ratio and be 1:1 to 1:5 Antimony pentachloride (
SbCl 5 ) and the TFMS trimethylsilyl group (
F 3 CSO 3 Si (CH 3 ) 3 ) mixed solution, system fully stirs, floods and keeps obtaining after 10 minutes to 20 minutes flooding
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution;
(3) under the hydrogen stream protection, filter above-mentioned load by bottle,suction with organic film
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of super acidic catalyst solid precursor obtains dipping
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor and remaining
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution; The residue that obtains
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The hybrid infusion agent that mixed solution can be used as in the step (2) recycles;
(4) above-mentioned acquisition 10g to 100g is flooded
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 400W to 500W power; The temperature that in hydrogen stream, keeps carry out microwave radiation heating is at 350 ° of C to 400 ° of C, and static roasting obtains the solid super acid catalyst blank after 60 minutes to 120 minutes;
(5) be raw material with the solid super acid catalyst blank that repeatedly obtains in the step (4); According to step (2), (3) and (4) step repeatable operation 1-5 time; Accomplished whole preparation processes of solid super acid catalyst, also airtight, subsequent use with taking out solid super acid catalyst under hydrogen shield.
Beneficial effect, owing to adopted such scheme, through TPD-NH
3Temperature programmed desorption figure has confirmed prepared novel load in the above-mentioned several kinds of schemes
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The surface acid intensity of/CNT solid super acid catalyst
HoAll less than-10.80, the solid acid catalyst of preparation belongs to the solid super acid catalyst category.Experimental result shows that such catalyst is good to catalytic hydrogenation lytic activity height and the selectivity that contains fragrant ring change bridged bond sample, in the experimentation to equipment do not have burn into can be repeatedly used and regenerate, best at the catalytic effect of 150 ℃ of-350 ℃ of serviceability temperature scopes.Adopt that the novel carriers solid super acid catalyst of full heating using microwave preparation has that suitable specific area, active principle crystallization velocity are fast, uniform crystal particles, sharpness of border and more even tiny and fine and close even aperture distribution and regular; High degree of dispersion is on the surfaces externally and internally of carrier; Effectively stop the reunion effect between the catalyst particle of load crystal, adopted microwave method to prepare the time that solid acid catalyst has effectively shortened the preparation catalyst, improved the crystal type of catalyst surface; The good thermal stability of catalyst; Technical process is simple, and efficient is high, has reached the object of the invention.
Advantage: the catalytic hydrogenation lytic activity height that the novel load SbCl5 that utilizes microwave method preparation and F3CSO3Si (CH3) 3/CNT solid super acid catalyst can impel fragrant ring change bridged bond sample and have selectivity preferably, especially for coal and coal model compound bridged bond catalytic hydrogenation cracking reaction.
It is short that the inventive method prepares the super acidic catalyst time, the Heat stability is good of catalyst, and the active principle of catalyst is stable, particularly is applicable to aromatic ring bridged bond catalytic hydrogenation, and the hydro-conversion efficient and the selectivity of this catalyst significantly improve.
The specific embodiment
Embodiment 1: the performance indications of the preparation method of supported solid superacid acid catalyst, operating condition and catalyst and catalytic effect:
1, Preparation of catalysts:
(1) be that 1g, weight concentration are 1% NaHCO with weight
3With weight is that the CNT of 500g fully mixes stirring, and mixed material is positioned in the microwave reactor of 300W power, in nitrogen stream, keeps the temperature of carry out microwave radiation heating to obtain load Na catalyst carrier after 10 minutes 220 ° of static roastings of C.
(2) place the above-mentioned load Na catalyst carrier for preparing of 100g in the flask in microwave reactor; In 100W power microwave irradiation; The temperature of carry out microwave radiation heating is under 50 ° of C conditions in nitrogen stream, and dropwise the adding gross weight is that 200g, volume ratio are 1:2's in the flask
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution, system fully stir, flood and keep obtaining after 20 minutes flooding
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under the hydrogen stream protection, filter above-mentioned load by bottle,suction with organic film
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of super acidic catalyst solid precursor obtains dipping
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor and remaining
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution.The residue that obtains
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The impregnating agent that mixed solution can be used as in the step (2) recycles.
(4) with the dipping of above-mentioned acquisition
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The 10g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, and the temperature that in hydrogen stream, keeps carry out microwave radiation heating is at 400 ° of C, and static roasting obtains the solid super acid catalyst blank after 60 minutes.
(5) be raw material with the solid super acid catalyst blank that 10 times obtain in the step (4); According to step (2), (3) and (4) step repeatable operation 3-5 time; Accomplished whole preparation processes of solid super acid catalyst, also airtight, subsequent use with taking out solid super acid catalyst under hydrogen shield.
2, the performance indications of catalyst and catalytic effect:
The mass content of effective element is respectively in the supported solid superacid acid catalyst: 1.6% O, 4.5% F, 0.1% Si, 0.1% S, 0.6% Cl, 0.9% Sb, specific area is 487.6 m
2/ g, total pore volume is 0.38 cm
3/ g, average pore size 55.95, the catalyst super acids
HO acidity is-11.20.In reactor, add raw material dinaphthyl methane 1g, the absolute magnitude of catalyst is 0.4 g, and initial pressure is 5MPa, keeps reaction temperature 300
oStir 3h under the C in the scope, the conversion ratio of dinaphthyl methane is 98%.Main effectively product comprises naphthalene and methyl naphthalene, and the selectivity of both one way is 100%.Catalyst through with conventional method thermal decomposition acquisition compares, and the super acidic catalyst of this method preparation has higher bridged bond catalytic hydrogenation lytic effect.
Embodiment 2: the performance indications of the preparation method of supported solid superacid acid catalyst, operating condition and catalyst and catalytic effect:
1, Preparation of catalysts:
(1) be that 1g, weight concentration are 8 ‰ NaHCO with weight
3With weight is that the CNT of 500g fully mixes stirring, and mixed material is positioned in the microwave reactor of 300W power, in nitrogen stream, keeps the temperature of carry out microwave radiation heating to obtain load Na catalyst carrier after 20 minutes 200 ° of static roastings of C.
(2) place the above-mentioned load Na catalyst carrier for preparing of 200g in the flask in microwave reactor; In 100W power microwave irradiation; The temperature of carry out microwave radiation heating is under 30 ° of C conditions in nitrogen stream, and dropwise the adding gross weight is that 500g, volume ratio are 1:4's in the flask
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution, system fully stir, flood and keep obtaining after 15 minutes flooding
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under the hydrogen stream protection, filter above-mentioned load by bottle,suction with organic film
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of super acidic catalyst solid precursor obtains dipping
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor and remaining
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution.The residue that obtains
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The impregnating agent that mixed solution can be used as in the step (2) recycles.
(4) with the dipping of above-mentioned acquisition
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The 50g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, and the temperature that in hydrogen stream, keeps carry out microwave radiation heating is at 350 ° of C, and static roasting obtains the solid super acid catalyst blank after 100 minutes.
(5) be raw material with the solid super acid catalyst blank that 2 times obtain in the step (4); According to step (2), (3) and (4) step repeatable operation 3-5 time; Accomplished whole preparation processes of solid super acid catalyst, also airtight, subsequent use with taking out solid super acid catalyst under hydrogen shield.
2, the performance indications of catalyst and catalytic effect:
The mass content of effective element is respectively in the supported solid superacid acid catalyst: 2.0% O, 4.2% F, 0.2% Si, 0.1% S, 0.3% Cl, 0.6% Sb, specific area is 492.0m
2/ g, total pore volume is 0.39 cm
3/ g, average pore size 3.12 nm, the catalyst super acids
HO acidity is-10.89.In reactor, add raw material dinaphthyl methane 1g, the absolute magnitude of catalyst is 0.6g, and initial pressure is 5MPa, keeps reaction temperature 290
oStir 3h under the C in the scope, the conversion ratio of dinaphthyl methane is 97%.Main effectively product comprises naphthalene and methyl naphthalene, and the selectivity of both one way is 100%.Catalyst through with conventional method thermal decomposition acquisition compares, and the super acidic catalyst of this method preparation has higher bridged bond catalytic hydrogenation lytic effect.
Embodiment 3: the performance indications of the preparation method of supported solid superacid acid catalyst, operating condition and catalyst and catalytic effect:
1, Preparation of catalysts:
(1) be that 1g, weight concentration are 4 ‰ NaHCO with weight
3With weight is that the CNT of 500g fully mixes stirring, and mixed material is positioned in the microwave reactor of 300W power, in nitrogen stream, keeps the temperature of carry out microwave radiation heating to obtain load Na catalyst carrier after 20 minutes 200 ° of static roastings of C.
(2) place the above-mentioned load Na catalyst carrier for preparing of 150g in the flask in microwave reactor; In 120W power microwave irradiation; The temperature of carry out microwave radiation heating is under 40 ° of C conditions in nitrogen stream, and dropwise the adding gross weight is that 600g, volume ratio are 1:1's in the flask
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution, system fully stir, flood and keep obtaining after 20 minutes flooding
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under the hydrogen stream protection, filter above-mentioned load by bottle,suction with organic film
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of super acidic catalyst solid precursor obtains dipping
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor and remaining
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution.The residue that obtains
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The impregnating agent that mixed solution can be used as in the step (2) recycles.
(4) with the dipping of above-mentioned acquisition
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The 100g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, and the temperature that in hydrogen stream, keeps carry out microwave radiation heating is at 400 ° of C, and static roasting obtains the solid super acid catalyst blank after 120 minutes.
(5) be raw material with the solid super acid catalyst blank that 1 time obtains in the step (4); According to step (2), (3) and (4) step repeatable operation 3-5 time; Accomplished whole preparation processes of solid super acid catalyst, also airtight, subsequent use with taking out solid super acid catalyst under hydrogen shield.
2, the performance indications of catalyst and catalytic effect:
The mass content of effective element is respectively in the solid super acid catalyst: 1.7% O, 4.0% F, 0.2% Si, 0.1% S, 0.5% Cl, 1.1% Sb; Specific area is 477.6 m2/g; Total pore volume is 0.43 cm3/g, average pore size 54.00, the catalyst super acids
HO acidity is-11.4.In reactor, add raw material Lingwu ub-bituminous coal 1g, the absolute magnitude of catalyst is 0.5 g, and initial pressure is 5MPa, keeps reaction temperature 280
oStir 4h under the C in the scope, the efficient of Lingwu ub-bituminous coal catalytic hydrogenation is about 45%, and main effectively product comprises naphthalene and methyl naphthalene, phenyl ring class monobasic ring product, naphthalene nucleus class binary ring product and other three-membered ring products such as part anthracene and phenanthrene.Catalyst through with conventional method thermal decomposition acquisition compares, and the super acidic catalyst of this method preparation has higher bridged bond catalytic hydrogenation lytic effect.
Claims (1)
1. a microwave method directly prepares the method for supported solid superacid acid catalyst, and it is characterized in that: the preparation method is:
(1) with weight ratio is the NaHCO of 1:500
3Fully mix stirring, NaHCO with CNT
3Weight concentration be 1 ‰ to 1%; And mixed material is positioned in the microwave reactor of 300W to 320W power, the temperature that in nitrogen stream, keeps carry out microwave radiation heating is at 200 ° of C to 220 ° of C, and static roasting obtains load Na catalyst carrier after 10 minutes to 20 minutes;
(2) place the above-mentioned load Na catalyst carrier for preparing of 10g to 500g in the flask in microwave reactor; Under 100W to 120W power microwave irradiation; The temperature of carry out microwave radiation heating is at 30 ° of C to 50 ° of C in nitrogen gas atmosphere, dropwise add gross weight in the flask and be 100g to 1000g, volume ratio and be 1:1 to 1:5 Antimony pentachloride (
SbCl 5 ) and the TFMS trimethylsilyl group (
F 3 CSO 3 Si (CH 3 ) 3 ) mixed solution, system fully stirs, floods and keeps obtaining after 10 minutes to 20 minutes flooding
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution;
(3) under the hydrogen stream protection, filter above-mentioned load by bottle,suction with organic film
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The suspension mixed liquor of super acidic catalyst solid precursor obtains dipping
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor and remaining
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 Mixed solution; The residue that obtains
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The hybrid infusion agent that mixed solution can be used as in the step (2) recycles;
(4) above-mentioned acquisition 10g to 100g is flooded
SbCl 5 With
F 3 CSO 3 Si (CH 3 ) 3 The solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 400W to 500W power; The temperature that in hydrogen stream, keeps carry out microwave radiation heating is at 350 ° of C to 400 ° of C, and static roasting obtains the solid super acid catalyst blank after 60 minutes to 120 minutes;
(5) be raw material with the solid super acid catalyst blank that repeatedly obtains in the step (4); According to step (2), (3) and (4) step repeatable operation 1-5 time; Accomplished whole preparation processes of solid super acid catalyst, also airtight, subsequent use with taking out solid super acid catalyst under hydrogen shield.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258858A (en) * | 2014-08-12 | 2015-01-07 | 中国矿业大学 | Preparation method of magnetic core supported solid super basic catalyst |
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| WO2008032459A1 (en) * | 2006-09-13 | 2008-03-20 | Japan Science And Technology Agency | Acid catalyst having organic group bound thereto |
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| CN101327437A (en) * | 2008-07-22 | 2008-12-24 | 西安交通大学 | Microwave-absorption type solid acid catalyst and use thereof in preparing biodiesel |
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2012
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| CN1246385A (en) * | 1998-08-27 | 2000-03-08 | 中国石油化工集团公司 | Carried catalyst of compound heteropoly acid and preparing process thereof |
| JP2007161682A (en) * | 2005-12-16 | 2007-06-28 | Toyo Ink Mfg Co Ltd | Method for producing solid acid and solid acid |
| WO2008032459A1 (en) * | 2006-09-13 | 2008-03-20 | Japan Science And Technology Agency | Acid catalyst having organic group bound thereto |
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| CN104258858A (en) * | 2014-08-12 | 2015-01-07 | 中国矿业大学 | Preparation method of magnetic core supported solid super basic catalyst |
| CN104258858B (en) * | 2014-08-12 | 2016-03-09 | 中国矿业大学 | The preparation method of gap load type solid super basic catalyst |
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