CN102614926B - A kind of microwave method directly prepares the method for supported solid superacid acid catalyst - Google Patents
A kind of microwave method directly prepares the method for supported solid superacid acid catalyst Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 64
- 239000003930 superacid Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 230000002378 acidificating effect Effects 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 230000005855 radiation Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims abstract description 4
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 230000003068 static effect Effects 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 11
- 230000002101 lytic effect Effects 0.000 abstract description 6
- 238000006424 Flood reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- ZMESHQOXZMOOQQ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZMESHQOXZMOOQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 229910004529 TaF 5 Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
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Abstract
Microwave method directly prepares a method for supported solid superacid acid catalyst, belongs to the preparation method of super acidic catalyst.(1) be the NaHCO of 1:500 by weight ratio
3mix and blend abundant with CNT, and be placed in microwave reactor roasting, obtain load Na catalyst carrier; (2) load Na catalyst carrier is placed on carry out microwave radiation heating, dropwise adds Antimony pentachloride (<b>SbCl
5and Trimethylsilyl trifluoromethanesulfonate (<b>F </b>)
3cSO
3si (CH
3)
3</b>) mixed solution, stirs, floods, obtain suspension mixed liquor; (3) filter suspension mixed liquor, obtain solid precursor and mixed solution; (4) solid precursor is positioned in microwave reactor, carry out microwave radiation heating, roasting, obtains solid super acid catalyst blank; (5) with solid super acid catalyst blank for raw material, according to step (2), (3) and (4) operation 1-5 time, complete.Advantage: the catalytic hydrogenation lytic activity of the supported solid superacid acid catalyst utilizing microwave method to prepare is high and have selective preferably.
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 the petroleum refining process such as hydrocarbon cracking, reformation, isomery; also relate to petrochemical industry and the fine chemistry industry plurality of cells courses of reaction such as olefin hydration, olefinic polymerization, alkylating aromatic hydrocarbon, aromatic hydrocarbons acyl group, alcoholic acid esterification, can say that acid catalyst is the basis of a series of essential industry.
At present, solid super acid catalyst mainly comprises following a few class, is the unit process that make use of isomerization reaction, alkylated reaction, esterification, acylation reaction, oligomeric anti-, substitution reaction, acetal and ketal respectively, directly prepares super acidic catalyst.
(1) by SbF
5, TaF
5, BF
3, SbF
3the unitary such as-HF or multi-component liquid acid load are on the carriers such as suitable porous oxide, graphite, ion exchange resin;
(2) by solid super-strong acid obtained for the mixing of two or more inorganic salts, as AlCl
3-CuCl, AlCl
3-Ti
2(SO
4)
3;
(3) resin fluorine richness is obtained perfluoro-polymer material Nafion-H;
(4) by molecular sieve modified obtained strong acid type molecular sieve, as peracidity modenite HM;
(5) compound of the element such as phosphorous, tungsten, germanium is obtained heteropoly acid through different chemical or physical process;
(6) by the solid super-strong acid that two or more metal oxide roasting is obtained, as W0
3/ TiO
2-zrO
2;
(7) sulfate radical is carried on metal oxide surface roasting and obtains solid super-strong acid, as SO
4 2-/ MxOy;
(8) load acid works in coordination with super acidic catalyst with metal composite, as at SO
4 2-/ ZrO
2in interpolation component (as Pt) improving catalyst activity and life-span etc. in catalyst.
Above-mentioned super acidic catalyst preparation is complicated, the time is long, and the active principle of catalyst is easy to loss, poor heat stability, and particularly without significant aromatic ring bridged bond catalytic hydrogenation, catalytic efficiency is low.
Summary of the invention
The object 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 loss, poor heat stability, particularly without significant aromatic ring bridged bond catalytic hydrogenation, the problem that catalytic efficiency is low.
The object of the present invention is achieved like this: preparation method is:
(1) be the NaHCO of 1:500 by weight ratio
3mix and blend abundant with CNT, NaHCO
3weight concentration be 1 ‰ to 1%; And mixed material is positioned in the microwave reactor of 300W to 320W power, in nitrogen stream, keep the temperature of carry out microwave radiation heating at 200 DEG C to 220 DEG C, static roasting obtains load Na catalyst carrier after 10 minutes to 20 minutes;
(2) the above-mentioned load Na catalyst carrier prepared of 10g to 500g is placed in the flask in microwave reactor, under 100W to 120W power microwave irradiates, in nitrogen gas atmosphere, the temperature of carry out microwave radiation heating is at 30 DEG C to 50 DEG C, in flask, dropwise add the Antimony pentachloride (SbCl that gross weight is 100g to 1000g, volume ratio is 1:1 to 1:5
5) and Trimethylsilyl trifluoromethanesulfonate (F
3cSO
3si (CH
3)
3) mixed solution, system fully stirs, flood and keep after 10 minutes to 20 minutes obtain (load) SbCl
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution;
(3) under hydrogen stream protection, above-mentioned load SbCl is filtered by the bottle,suction with organic film
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of super acidic catalyst solid precursor, obtains dipping SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor and remaining SbCl
5and F
3cSO
3si (CH
3)
3mixed solution; The residue SbCl obtained
5and F
3cSO
3si (CH
3)
3the hybrid infusion agent that mixed solution can be used as in step (2) recycles;
(4) above-mentioned acquisition 10g to 100g is flooded SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 400W to 500W power, keep the temperature of carry out microwave radiation heating at 350 DEG C to 400 DEG C in the hydrogen gas stream, static roasting obtains solid super acid catalyst blank after 60 minutes to 120 minutes;
(5) with the solid super acid catalyst blank repeatedly obtained in step (4) for raw material; repeatedly operate 1-5 time according to step (2), (3) and (4) step; complete whole preparation process of solid super acid catalyst, under hydrogen shield, take out solid super acid catalyst and airtight, for subsequent use.
Beneficial effect, owing to have employed such scheme, passes through TPD-NH
3temperature programmed desorption figure determines novel load SbCl prepared in above-mentioned several scheme
5and F
3cSO
3si (CH
3)
3the surface acid strength Ho of/CNT solid super acid catalyst is all less than-10.80, and the solid acid catalyst of preparation belongs to solid super acid catalyst category.Experimental result shows that such catalyst is high and selective good to the catalytic hydrogenation lytic activity containing fragrant ring change bridged bond sample, corrosion-free to equipment in experimentation, can repeatedly use and regenerate, best at the catalytic effect of 150 DEG C-350 DEG C serviceability temperature scopes.The carrier solids super acidic catalyst adopting full heating using microwave to prepare has suitable specific area, active principle crystallization velocity is fast, crystal grain is even, sharpness of border and more even tiny and fine and close even aperture distribution and regular, be highly dispersed on the surfaces externally and internally of carrier, agglomerating effect between the catalyst particle effectively preventing load crystal, microwave method is adopted to prepare the time that solid acid catalyst effectively shortens Kaolinite Preparation of Catalyst, improve the crystal type of catalyst surface, the good thermal stability of catalyst, technical process is simple, efficiency is high, reach object of the present invention.
Advantage: load SbCl5 and F3CSO3Si (CH3) the 3/ CNT solid super acid catalyst utilizing microwave method to prepare can impel the catalytic hydrogenation lytic activity of fragrant ring change bridged bond sample high and have selective 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 stablized, and is particularly applicable to aromatic ring bridged bond catalytic hydrogenation, the hydro-conversion efficiency of this catalyst and selectively to significantly improve.
Detailed description of the invention
Embodiment 1: the performance indications of the preparation method of supported solid superacid acid catalyst, operating condition and catalyst and catalytic effect:
1, the preparation of catalyst:
(1) be 1g by weight, weight concentration is the NaHCO of 1%
3with the abundant mix and blend of CNT that weight is 500g, 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 DEG C of static roastings.
(2) the above-mentioned load Na catalyst carrier prepared of 100g is placed in the flask in microwave reactor, in 100W power microwave irradiates, in nitrogen stream, the temperature of carry out microwave radiation heating is under 50 DEG C of conditions, in flask, dropwise add that gross weight is 200g, volume ratio is the SbCl of 1:2
5and F
3cSO
3si (CH
3)
3mixed solution, system fully stirs, flood and keep after 20 minutes obtain (load) SbCl
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under hydrogen stream protection, above-mentioned load SbCl is filtered by the bottle,suction with organic film
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of super acidic catalyst solid precursor, obtains dipping SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor and remaining SbCl
5and F
3cSO
3si (CH
3)
3mixed solution.The residue SbCl obtained
5and F
3cSO
3si (CH
3)
3the impregnating agent that mixed solution can be used as in step (2) recycles.
(4) by the dipping SbCl of above-mentioned acquisition
5and F
3cSO
3si (CH
3)
3the 10g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, keeps the temperature of carry out microwave radiation heating at 400 DEG C in the hydrogen gas stream, and static roasting obtained solid super acid catalyst blank after 60 minutes.
(5) with in step (4) 10 times obtain solid super acid catalyst blank for raw material; repeatedly operate 3-5 time according to step (2), (3) and (4) step; complete whole preparation process of solid super acid catalyst, under hydrogen shield, take out solid super acid catalyst and airtight, for subsequent use.
2, the performance indications of catalyst and catalytic effect:
In supported solid superacid acid catalyst, the mass content of effective element is respectively: 1.6%O, 4.5%F, 0.1%Si, 0.1%S, 0.6%Cl, 0.9%Sb, and specific area is 487.6m
2/ g, total pore volume is 0.38cm
3/ g, average pore size 55.95, the Ho acidity of catalyst super acids is-11.20.Add raw material dinaphthyl methane 1g in the reactor, the absolute magnitude of catalyst is 0.4g, and initial pressure is 5MPa, keeps reaction temperature 300
ostir 3h in scope under C, the conversion ratio of dinaphthyl methane is 98%.Main effectively product comprises naphthalene and methyl naphthalene, and the selective of both one way is 100%.By comparing with the catalyst that conventional method thermal decomposition obtains, super acidic catalyst prepared by this method 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, the preparation of catalyst:
(1) be 1g by weight, weight concentration is the NaHCO of 8 ‰
3with the abundant mix and blend of CNT that weight is 500g, 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 DEG C of static roastings.
(2) the above-mentioned load Na catalyst carrier prepared of 200g is placed in the flask in microwave reactor, in 100W power microwave irradiates, in nitrogen stream, the temperature of carry out microwave radiation heating is under 30 DEG C of conditions, in flask, dropwise add that gross weight is 500g, volume ratio is the SbCl of 1:4
5and F
3cSO
3si (CH
3)
3mixed solution, system fully stirs, flood and keep after 15 minutes obtain (load) SbCl
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under hydrogen stream protection, above-mentioned load SbCl is filtered by the bottle,suction with organic film
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of super acidic catalyst solid precursor, obtains dipping SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor and remaining SbCl
5and F
3cSO
3si (CH
3)
3mixed solution.The residue SbCl obtained
5and F
3cSO
3si (CH
3)
3the impregnating agent that mixed solution can be used as in step (2) recycles.
(4) by the dipping SbCl of above-mentioned acquisition
5and F
3cSO
3si (CH
3)
3the 50g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, keeps the temperature of carry out microwave radiation heating at 350 DEG C in the hydrogen gas stream, and static roasting obtained solid super acid catalyst blank after 100 minutes.
(5) with in step (4) 2 times obtain solid super acid catalyst blank for raw material; repeatedly operate 3-5 time according to step (2), (3) and (4) step; complete whole preparation process of solid super acid catalyst, under hydrogen shield, take out solid super acid catalyst and airtight, for subsequent use.
2, the performance indications of catalyst and catalytic effect:
In supported solid superacid acid catalyst, the mass content of effective element is respectively: 2.0%O, 4.2%F, 0.2%Si, 0.1%S, 0.3%Cl, 0.6%Sb, and specific area is 492.0m
2/ g, total pore volume is 0.39cm
3/ g, average pore size 3.12nm, the Ho acidity of catalyst super acids is-10.89.Add raw material dinaphthyl methane 1g in the reactor, the absolute magnitude of catalyst is 0.6g, and initial pressure is 5MPa, keeps reaction temperature 290
ostir 3h in scope under C, the conversion ratio of dinaphthyl methane is 97%.Main effectively product comprises naphthalene and methyl naphthalene, and the selective of both one way is 100%.By comparing with the catalyst that conventional method thermal decomposition obtains, super acidic catalyst prepared by this method 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, the preparation of catalyst:
(1) be 1g by weight, weight concentration is the NaHCO of 4 ‰
3with the abundant mix and blend of CNT that weight is 500g, 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 DEG C of static roastings.
(2) the above-mentioned load Na catalyst carrier prepared of 150g is placed in the flask in microwave reactor, in 120W power microwave irradiates, in nitrogen stream, the temperature of carry out microwave radiation heating is under 40 DEG C of conditions, in flask, dropwise add that gross weight is 600g, volume ratio is the SbCl of 1:1
5and F
3cSO
3si (CH
3)
3mixed solution, system fully stirs, flood and keep after 20 minutes obtain (load) SbCl
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution.
(3) under hydrogen stream protection, above-mentioned load SbCl is filtered by the bottle,suction with organic film
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of super acidic catalyst solid precursor, obtains dipping SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor and remaining SbCl
5and F
3cSO
3si (CH
3)
3mixed solution.The residue SbCl obtained
5and F
3cSO
3si (CH
3)
3the impregnating agent that mixed solution can be used as in step (2) recycles.
(4) by the dipping SbCl of above-mentioned acquisition
5and F
3cSO
3si (CH
3)
3the 100g solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 500W power, keeps the temperature of carry out microwave radiation heating at 400 DEG C in the hydrogen gas stream, and static roasting obtained solid super acid catalyst blank after 120 minutes.
(5) with in step (4) 1 time obtain solid super acid catalyst blank for raw material; repeatedly operate 3-5 time according to step (2), (3) and (4) step; complete whole preparation process of solid super acid catalyst, under hydrogen shield, take out solid super acid catalyst and airtight, for subsequent use.
2, the performance indications of catalyst and catalytic effect:
In solid super acid catalyst, the mass content of effective element is respectively: 1.7%O, 4.0%F, 0.2%Si, 0.1%S, 0.5%Cl, 1.1%Sb, specific area is 477.6m2/g, total pore volume is 0.43cm3/g, average pore size 54.00, and the Ho acidity of catalyst super acids is-11.4.Add raw material Lingwu ub-bituminous coal 1g in the reactor, the absolute magnitude of catalyst is 0.5g, and initial pressure is 5MPa, keeps reaction temperature 280
ostir 4h in scope under C, the efficiency of Lingwu ub-bituminous coal catalytic hydrogenation is about 45%, and main effectively product comprises naphthalene and methyl naphthalene, phenyl ring class one ring product, naphthalene nucleus class two ring product and other three-membered ring products such as part anthracene and phenanthrene.By comparing with the catalyst that conventional method thermal decomposition obtains, super acidic catalyst prepared by this method has higher bridged bond catalytic hydrogenation lytic effect.
Claims (1)
1. microwave method directly prepares a method for supported solid superacid acid catalyst, it is characterized in that: preparation method is:
(1) be the NaHCO of 1:500 by weight ratio
3mix and blend abundant with CNT, NaHCO
3weight concentration be 1 ‰ to 1%; And mixed material is positioned in the microwave reactor of 300W to 320W power, in nitrogen stream, keep the temperature of carry out microwave radiation heating at 200 DEG C to 220 DEG C, static roasting obtains load Na catalyst carrier after 10 minutes to 20 minutes;
(2) the above-mentioned load Na catalyst carrier prepared of 10g to 500g is placed in the flask in microwave reactor, under 100W to 120W power microwave irradiates, in nitrogen gas atmosphere, the temperature of carry out microwave radiation heating is at 30 DEG C to 50 DEG C, in flask, dropwise add the Antimony pentachloride (SbCl that gross weight is 100g to 1000g, volume ratio is 1:1 to 1:5
5) and Trimethylsilyl trifluoromethanesulfonate (F
3cSO
3si (CH
3)
3) mixed solution, system fully stirs, flood and keep after 10 minutes to 20 minutes obtain dipping SbCl
5and F
3cSO
3si (CH
3)
3the suspension mixed liquor of the super acidic catalyst solid precursor of mixed solution;
(3) under hydrogen stream protection, filter above-mentioned suspension mixed liquor by the bottle,suction with organic film, obtain dipping SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor and remaining SbCl
5and F
3cSO
3si (CH
3)
3mixed solution; The residue SbCl obtained
5and F
3cSO
3si (CH
3)
3the hybrid infusion agent that mixed solution can be used as in step (2) recycles;
(4) above-mentioned acquisition 10g to 100g is flooded SbCl
5and F
3cSO
3si (CH
3)
3the solid precursor of the super acidic catalyst of mixed liquor is positioned in the microwave reactor of 400W to 500W power, keep the temperature of carry out microwave radiation heating at 350 DEG C to 400 DEG C in the hydrogen gas stream, static roasting obtains solid super acid catalyst blank after 60 minutes to 120 minutes;
(5) with the solid super acid catalyst blank repeatedly obtained in step (4) for raw material; repeatedly operate 1-5 time according to step (2), (3) and (4) step; complete whole preparation process of solid super acid catalyst, under hydrogen shield, take out solid super acid catalyst and airtight, for subsequent use.
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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 |
| CN101264450A (en) * | 2008-04-28 | 2008-09-17 | 中国矿业大学 | Preparation of full microwave radiation method sulfur-tolerant type molybdenum base catalyst |
| 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 |
| CN101703949A (en) * | 2009-09-11 | 2010-05-12 | 广东工业大学 | Method for preparing solid acid catalyst by microwave solid phase method and application thereof |
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Patent Citations (6)
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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 |
| CN101264450A (en) * | 2008-04-28 | 2008-09-17 | 中国矿业大学 | Preparation of full microwave radiation method sulfur-tolerant type molybdenum base catalyst |
| 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 |
| CN101703949A (en) * | 2009-09-11 | 2010-05-12 | 广东工业大学 | Method for preparing solid acid catalyst by microwave solid phase method and application thereof |
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