CN109603891A - A kind of preparation method being combined to aniline reaction catalyst applied to one step amino of benzene - Google Patents
A kind of preparation method being combined to aniline reaction catalyst applied to one step amino of benzene Download PDFInfo
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- CN109603891A CN109603891A CN201811616885.2A CN201811616885A CN109603891A CN 109603891 A CN109603891 A CN 109603891A CN 201811616885 A CN201811616885 A CN 201811616885A CN 109603891 A CN109603891 A CN 109603891A
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- molecular sieve
- benzene
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- aniline
- catalyst
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 114
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007809 chemical reaction catalyst Substances 0.000 title claims description 5
- MREOOEFUTWFQOC-UHFFFAOYSA-M potassium;5-chloro-4-hydroxy-1h-pyridin-2-one;4,6-dioxo-1h-1,3,5-triazine-2-carboxylate;5-fluoro-1-(oxolan-2-yl)pyrimidine-2,4-dione Chemical compound [K+].OC1=CC(=O)NC=C1Cl.[O-]C(=O)C1=NC(=O)NC(=O)N1.O=C1NC(=O)C(F)=CN1C1OCCC1 MREOOEFUTWFQOC-UHFFFAOYSA-M 0.000 claims abstract description 85
- 239000002808 molecular sieve Substances 0.000 claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005253 cladding Methods 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005751 Copper oxide Substances 0.000 claims abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000004176 ammonification Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- COUNCWOLUGAQQG-UHFFFAOYSA-N copper;hydrogen peroxide Chemical compound [Cu].OO COUNCWOLUGAQQG-UHFFFAOYSA-N 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FFEVHTMMGXLTCX-UHFFFAOYSA-N iron nitrobenzene Chemical compound [Fe].[N+](=O)([O-])C1=CC=CC=C1 FFEVHTMMGXLTCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
Abstract
It is combined to the application on aniline the present invention relates to a kind of preparation method of TS-1 (x) molecular sieve of hud typed Cu/MCM-41 cladding and its in one step amino of benzene, belongs to heterogeneous catalysis technical field.TS-1 molecular sieve, which coats one layer on its surface by the method for self assembly, has order mesoporous MCM-41 shell, using the method carried metal copper oxide active component of incipient impregnation, and is applied to one step amino of benzene and is combined in the reaction of aniline.TS-1 (x) molecular sieve for the Cu/MCM-41 cladding that the present invention synthesizes, using TS-1 as core, MCM-41 is that shell realizes micro porous molecular sieve and mesopore molecular sieve is mutually compound, it presents good catalytic effect in the reaction of one step ammonification of benzene synthesis aniline, the maximum yield of aniline is up to 1.67%, selectivity is 94.89%, which is combined to catalyst in aniline for design one step amino of benzene and provides theoretical direction.
Description
Technical field
The invention belongs to Green Chemistry and field of heterogeneous catalysis, and in particular to a kind of hud typed titanium silicon of supported copper point
The preparation method of son sieve and its method that catalysis one step amino of benzene is combined to aniline under the conditions of low-temperature atmosphere-pressure.
Background technique
Aniline is a kind of important Organic Chemicals.Chemical products as made from it and intermediate have more than 300 kinds.Aniline
It is mainly used for the production of MDI, another big purposes of aniline is used as rubber processing chemicals and intermediate, and such as vulcanization accelerator resists
Oxygen agent, antiozonant and stabilizer.Aniline is also the important intermediate of dyestuff (mainly azoic dye) and pigment.Aniline work
Industry production method mainly has nitrobenzene iron powder reducing method, Catalytic Hydrogenation of Nitrobenzene method and phenol or 3 kinds of chlorobenzene ammoniation process.But
These methods all have the shortcomings that many itself, as used corrosive raw materials, the complex process equipment that uses, original in production process
Material utilization rate is low, severe reaction conditions, the production cycle is long, by-product is more and causes relevant environmental problem etc., does not meet green
The needs of color synthesis chemistry ideas and the strategy of sustainable development.Therefore people are exploring always aniline synthesis side efficiently, green
Method.By activating the c h bond of benzene, directly the research that amino introduces phenyl ring is received significant attention in recent years.By the direct ammonification of benzene
Synthesize aniline, multistep reaction become into single step reaction, it will be apparent that improve the atom utilization of reaction, and by-product be hydrogen or
Water environmental sound.The main method of the one-step synthesis of aniline has high temperature and high pressure method and low-temperature atmosphere-pressure method at present.Low-temperature atmosphere-pressure method
Usually temperature is lower than being reacted under conditions of 100 DEG C under normal pressure, and this method is due to reaction temperature and pressure is lower and peace
The features such as performance is good entirely becomes the research hotspot that one step of benzene prepares aniline in recent years.
Guo Bin etc. [Green Chem., 2012,14,1880-1883] report with the molecular sieve carried Ti, Ce of TS-1, V,
Co, Ni, Fe, Cu metal are catalyst, and hydrogen peroxide is oxidant, and ammonium hydroxide is aminating agent, is combined to aniline by one step amino of benzene.This
Although method can the conversion ratio of synthesis aniline but its benzene be lower (1.05%) in next step in low-temperature atmosphere-pressure, and has by-product phenol
It generates.
Opening dragon waits [patent publication No.: CN104844460, a kind of method of benzene direct aminatin aniline] using benzene as raw material,
Using V-MCM-41 as catalyst, azanol is aminating agent, and using acetic acid as solvent, 2h, the choosing of available aniline are reacted at 70 DEG C
Selecting property is 100%, and the yield of aniline is 77.5%.Although this reacts the selection for realizing higher benzene conversion ratio and aniline
Property, but the unstable easy decomposition of azanol and expensive limit the prospects for commercial application of this method.
Summary of the invention
The purpose of the present invention is lower for the conversion ratio for being combined to aniline using ammonium hydroxide as the one step amino of benzene in ammonia source at present
The state of the art, propose a kind of TS-1 (x) molecular sieve of the Cu/MCM-41 cladding of hud typed supported copper preparation method and its
It is combined to the application on aniline in one step amino of benzene, such hud typed Titanium Sieve Molecular Sieve is using ammonium hydroxide as the one step amino of benzene in ammonia source
It is combined to present the conversion ratio of preferable benzene and the selectivity of aniline in the reaction of aniline.
Using the TS-1 molecular sieve with MFI topological structure as core, the MCM-41 with hexagonal mesoporous structure is shell preparation
The TS-1 (x) of hud typed composite molecular screen MCM-41 cladding；Support type is obtained using equi-volume impregnating carried metal CuO
TS-1 (x) molecular sieve of Cu/MCM-41 cladding, the i.e. catalyst of one step ammonification of benzene synthesis aniline.
TS-1 (x) molecular sieve of the hud typed Cu/MCM-41 cladding, with the TS-1 molecular sieve with MFI topological structure
For core, the MCM-41 with hexagonal mesoporous structure is shell；The silicon titanium ratio of the nuclear phase TS-1 molecular sieve is (SiO2/TiO2) it is 30-
100:1, shell MCM-41 molecular sieve be pure silicon molecular sieve, shell with a thickness of 5-50nm, the load capacity of metal copper oxide is
0.5-5wt%.Its specific method for preparing catalyst is as follows:
(1) by template (T), silicon source, titanium source, isopropanol and deionized water T:SiO in molar ratio2:TiO2:IPA:H2O is
0.18:1:0.01-0.033:1.5:40 is configured to gel mixture, and alcohol 2-6h is caught up at 80 DEG C, then at 160-180 DEG C
Hydrothermal crystallizing 2-7 days, 6h removed template method is roasted after washed, dry at 550 DEG C up to TS-1 molecular sieve.Template (T)
For tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide it is one such or it is a variety of mix in any proportion,
Silicon source used is TEOS, titanium source TBOT；
(2) it disperses (1) resulting TS-1 molecular sieve in deionized water and is ultrasonically treated 30min, and by the CTAB of 1-5g
It is soluble in water, CTAB solution and TS-1 suspension are mixed and stir 12-36h at room temperature, extremely with ammonium hydroxide adjustment suspension PH
10-11 or so is added dropwise the TEOS of 0.5-10mL under the conditions of 40 DEG C, and hydrolyzes 2h, hydrothermal crystallizing under the conditions of 100-130 DEG C
1-4 days.TS-1 (x) molecular sieve that 6h removed template method coats up to MCM-41, x table are roasted after washed, dry at 550 DEG C
Show TEOS additional amount.
(3) TS-1 (x) molecular sieve of (2) resulting MCM-41 cladding is carried out by copper activity component using equi-volume impregnating
Load, take the TS-1 (x) of a certain amount of MCM-41 cladding to be impregnated in isometric Gerhardite solution, stir at room temperature
Mix still aging 12h after 4h, it is dry after under 550 DEG C of air atmospheres roasting 6h obtain TS-1 (x) molecular sieve of Cu/MCM-41 cladding,
Wherein the load capacity of metal copper oxide is 0.5-5wt%.
A kind of usage of catalyst being combined to aniline for one step amino of benzene of the invention, step and condition are as follows:
Prepared catalyst and benzene feedstock are fitted into the single necked round bottom flask with condensation reflux unit first, passed through
Raw material ammonia water, hydrogen peroxide and deionized water are slowly added into reaction unit by peristaltic pump under ice water mixing condition, heating
To 50-80 DEG C, 2-5h is reacted under agitation, is cooled to room temperature after reaction with ice water, divided catalyst by centrifugation
From with methanol by reaction solution constant volume, using HPLC to reaction solution progress quantitative analysis, HPLC is furnished with Hypersil BDS C18 column
(4.6mm × 250mm, 5 μm) and ultravioletvisible absorption detector.
Beneficial effects of the present invention: the present invention provides a kind of preparation method of hud typed Titanium Sieve Molecular Sieve and its in benzene one
Step amino is combined to the usage on aniline.The present invention has synthesized Cu/MCM-41 packet by the method for self assembly and incipient impregnation
TS-1 (x) molecular sieve catalyst covered acts on the aqueous solution of TS-1 molecular sieve and CTAB to TS-1 points by electrostatic self-assembled
Son sieve carries out surface and is modified, and adjusts the shell thickness of core-shell type molecular sieve by changing the additional amount of TEOS, then will be hud typed
Molecular sieve and isometric metal front liquid solution, which are mixed, obtains the core-shell catalyst of metal load type by drying and calcining,
By the concentration of modulation metal front liquid solution, to adjust the content of metal active constituent.Traditional its duct of TS-1 molecular sieve
Diameter is about 0.55nm, and the molecular dynamics diameter of benzene is about 0.58nm, therefore diffusion of the benzene molecular in duct is restricted
Benzene feedstock is mainly reacted in molecular sieve surface, and hydrogen peroxide and amino molecule can freely pass in and out duct is formed inside duct
The intermediate azanol of reaction, intermediate azanol are reacted by being diffused into molecular sieve surface with benzene, and intermediate azanol is diffused into
Easily decomposing in solution causes the conversion ratio of reaction low.Hud typed Titanium Sieve Molecular Sieve load copper dioxide catalyst of the invention passes through
One layer of MCM-41 shell is coated in TS-1 molecular sieve surface, so that reaction intermediate azanol and benzene molecular are in the hole of shell MCM-41
It is reacted in road, avoids the decomposition of azanol, and cover the B of TS-1 molecular sieve surface by MCM-41 molecular sieve
Acid activity position directly reacts with hydrogen peroxide so as to avoid benzene generates by-product phenol, and the catalyst is in one step amination of benzene
Synthesis aniline presents good catalytic activity and higher product selectivity, and the selectivity of available aniline is
94.89%, the yield of aniline is 1.67%.
Detailed description of the invention
Fig. 1: TS-1 (2) TEM photo of hud typed Titanium Sieve Molecular Sieve Cu/MCM-41 cladding described in embodiment 1
Fig. 2: TS-1 (3) TEM photo of hud typed Titanium Sieve Molecular Sieve Cu/MCM-41 cladding described in embodiment 2
It forms it will be seen from figure 1 that MCM-41 molecular sieve is successfully coated on stratum nucleare TS-1 molecular sieve surface with core
The molecular sieve of shell structure.
Figure it is seen that by change TEOS the adjustable core-shell type molecular sieve of additional amount shell thickness to
Change shell proportion.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1:
It will be uniformly mixed at 50 DEG C of deionized water of the TPAOH of 14.692g and 21.444g, 20.830g be added dropwise
TEOS keep 50 DEG C of hydrolysis 30min, the TBOT of 0.844g is dissolved in the IPA of 9g be added dropwise to after mixing it is above-mentioned molten
50 DEG C of hydrolysis 30min are kept in glue, temperature is risen to 80 DEG C and catches up with alcohol 4h, are supplied after the deionized water of equivalent under the conditions of 170 DEG C
Hydrothermal crystallizing 48h.6h, which is calcined, after centrifugation, washing, drying, under 550 DEG C of air atmospheres obtains TS-1 molecular sieve.Take resulting TS-1
The CTAB of 2.2g is dissolved in 40mL water and mixing with above-mentioned TS-1 suspension by molecular sieve 0.5g ultrasonic disperse 30min in 10mL water
It is stirred at room temperature after uniformly for 24 hours, adjusts suspension PH10-11 or so with ammonium hydroxide, be slowly added to 2mL TEOS, hydrolyzed at 40 DEG C
2h.120 DEG C of hydrothermal crystallizing 48h calcine the TS-1 (x) that 6h obtains MCM-41 cladding after being filtered, washed, drying at 550 DEG C
Molecular sieve is denoted as the TS-1 (2) of MCM-41 cladding.MCM-41 TS-1 (2) molecular sieve coated is impregnated in three isometric hydrations
In copper nitrate solution, still aging 12h after 4h is stirred at room temperature, and roasting 6h obtains Cu/MCM-41 under 550 DEG C of air atmospheres after drying
TS-1 (2) molecular sieve of cladding, the theoretical negative carrying capacity of copper oxide are 2.5%.
Embodiment 2:
It will be uniformly mixed at 50 DEG C of deionized water of the TPAOH of 14.692g and 21.444g, 20.830g be added dropwise
TEOS keep 50 DEG C of hydrolysis 30min, the TBOT of 1.125g is dissolved in the IPA of 9g be added dropwise to after mixing it is above-mentioned molten
50 DEG C of hydrolysis 30min are kept in glue, temperature is risen to 80 DEG C and catches up with alcohol 4h, are supplied after the deionized water of equivalent under the conditions of 170 DEG C
Hydrothermal crystallizing 48h.6h, which is calcined, after centrifugation, washing, drying, under 550 DEG C of air atmospheres obtains TS-1 molecular sieve.Take resulting TS-1
The CTAB of 2.2g is dissolved in 40mL water and mixing with above-mentioned TS-1 suspension by molecular sieve 0.5g ultrasonic disperse 30min in 10mL water
It is stirred at room temperature after uniformly for 24 hours, adjusts suspension PH10-11 or so with ammonium hydroxide, be slowly added to 3mL TEOS, hydrolyzed at 40 DEG C
2h.120 DEG C of hydrothermal crystallizing 48h calcine the TS-1 (x) that 6h obtains MCM-41 cladding after being filtered, washed, drying at 550 DEG C
Molecular sieve is denoted as the TS-1 (3) of MCM-41 cladding.MCM-41 TS-1 (3) molecular sieve coated is impregnated in three isometric hydrations
In copper nitrate solution, still aging 12h after 4h is stirred at room temperature, and roasting 6h obtains Cu/MCM-41 under 550 DEG C of air atmospheres after drying
TS-1 (3) molecular sieve of cladding, the theoretical negative carrying capacity of copper oxide are 5%.
Embodiment 3:
It will be uniformly mixed at 50 DEG C of deionized water of the TPAOH of 14.692g and 21.444g, 20.830g be added dropwise
TEOS keep 50 DEG C of hydrolysis 30min, the TBOT of 0.844g is dissolved in the IPA of 9g be added dropwise to after mixing it is above-mentioned molten
50 DEG C of hydrolysis 30min are kept in glue, temperature is risen to 80 DEG C and catches up with alcohol 4h, are supplied after the deionized water of equivalent under the conditions of 170 DEG C
Hydrothermal crystallizing 48h.6h, which is calcined, after centrifugation, washing, drying, under 550 DEG C of air atmospheres obtains TS-1 molecular sieve.By TS-1 molecular sieve
It is impregnated in isometric Gerhardite solution, stirs still aging 12h after 4h, 550 DEG C of air atmospheres after drying at room temperature
It encloses lower roasting 6h and obtains Cu/TS-1 molecular sieve, the theoretical negative carrying capacity of copper oxide is 1%.
Embodiment 4:
The TS-1 (2) of the cladding of 0.5g catalyst Cu/MCM-41 prepared by embodiment 1 and 0.224g benzene feedstock are packed into band
Have in the single necked round bottom flask of condensation reflux unit, by peristaltic pump by raw material 9.1g ammonium hydroxide, 2.054g hydrogen peroxide and
31.851g deionized water is slowly added into reaction unit under ice water mixing condition, is warming up to 60 DEG C, under agitation instead
4h is answered, is cooled to room temperature after reaction with ice water, is separated catalyst by being centrifuged, with methanol by reaction solution constant volume, is used
HPLC carries out quantitative analysis to reaction solution.
Embodiment 5:
The TS-1 (3) of the cladding of 0.5g catalyst Cu/MCM-41 prepared by embodiment 2 and 0.224g benzene feedstock are packed into band
Have in the single necked round bottom flask of condensation reflux unit, by peristaltic pump by raw material 9.1g ammonium hydroxide, 2.054g hydrogen peroxide and
31.851g deionized water is slowly added into reaction unit under ice water mixing condition, is warming up to 70 DEG C, under agitation instead
5h is answered, is cooled to room temperature after reaction with ice water, is separated catalyst by being centrifuged, with methanol by reaction solution constant volume, is used
HPLC carries out quantitative analysis to reaction solution.
Embodiment 6:
0.5g catalyst Cu/TS-1 prepared by embodiment 3 and 0.224g benzene feedstock are packed into and have condensation reflux unit
Single necked round bottom flask in, by peristaltic pump by raw material 9.1g ammonium hydroxide, 2.054g hydrogen peroxide and 31.851g deionized water in ice
It is slowly added into reaction unit under water mixing condition, is warming up to 50 DEG C, reacted 3h under agitation, use ice after reaction
It is water-cooled to room temperature, catalyst is separated by being centrifuged, with methanol by reaction solution constant volume, reaction solution is quantified using HPLC
Analysis.
Table 1 is core-shell catalyst and to apply Cu/TS-1 catalyst in example 3 in comparative example 1 and embodiment 2 and be used for
One step amino of benzene is combined to the catalysis reaction result of aniline reaction, by data in table it can be found that core-shell catalyst presents
Good catalytic effect, for the maximum yield of aniline up to 1.67%, selectivity is 94.89%.
Table 1
Claims (5)
1. a kind of preparation method for being combined to aniline reaction catalyst applied to one step amino of benzene, which is characterized in that with MFI
The TS-1 molecular sieve of topological structure is core, and the MCM-41 with hexagonal mesoporous structure is the hud typed composite molecular screen of shell preparation；
The molecular sieve catalyst of support type is obtained using equi-volume impregnating carried metal CuO.
2. a kind of preparation method that aniline reaction catalyst is combined to applied to one step amino of benzene as described in claim 1,
It is characterized by comprising the following steps:
(1) by template (T), silicon source, titanium source, isopropanol and deionized water T:SiO in molar ratio2:TiO2:IPA:H2O is
0.18:1:0.01-0.033:1.5:40 is configured to gel mixture, and alcohol 2-6h is caught up at 80 DEG C, then at 160-180 DEG C
Hydrothermal crystallizing 2-7 days, 6h removed template method is roasted after washed, dry at 550 DEG C up to TS-1 molecular sieve；
(2) it disperses (1) resulting TS-1 molecular sieve in deionized water and is ultrasonically treated 30min, and the CTAB of 1-5g is dissolved in
In water, CTAB solution and TS-1 suspension are mixed and stir 12-36h at room temperature, adjusts suspension PH to 10-11 with ammonium hydroxide
Or so, the TEOS of 0.5-10mL is added dropwise under the conditions of 40 DEG C, and hydrolyze 2h, hydrothermal crystallizing 1-4 under the conditions of 100-130 DEG C
It；TS-1 (x) molecular sieve that 6h removed template method coats up to MCM-41 is roasted after washed, dry at 550 DEG C, x is indicated
TEOS additional amount；
(3) TS-1 (x) molecular sieve of (2) resulting MCM-41 cladding is carried out by the negative of copper activity component using equi-volume impregnating
It carries, takes the TS-1 (x) of a certain amount of MCM-41 cladding to be impregnated in isometric Gerhardite solution, stir 4h at room temperature
Still aging 12h afterwards, roasting 6h obtains TS-1 (x) molecular sieve of Cu/MCM-41 cladding under 550 DEG C of air atmospheres after drying, wherein
The load capacity of metal copper oxide is 0.5-5wt%.
3. a kind of preparation method for being combined to aniline reaction catalyst applied to one step amino of benzene as claimed in claim 2, special
Sign is, template (T) is that tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide are one such or more
Kind mixes in any proportion, and silicon source used is TEOS, titanium source TBOT.
4. using the catalyst such as any the method preparation of claim 1-3, it is characterised in that: the nuclear phase TS-1 molecular sieve
Silicon titanium ratio be (SiO2/TiO2) be 30-100:1, shell MCM-41 molecular sieve be pure silicon molecular sieve, shell with a thickness of 5-
50nm, the load capacity of metal copper oxide are 0.5-5wt%.
5. the application of aniline reaction is combined in one step amino of benzene using catalyst as claimed in claim 4, it is characterised in that: step
It is rapid as follows:
Prepared catalyst and benzene feedstock are fitted into the single necked round bottom flask with condensation reflux unit first, pass through wriggling
Raw material ammonia water, hydrogen peroxide and deionized water are slowly added into reaction unit by pump under ice water mixing condition, are warming up to 50-
80 DEG C, 2-5h is reacted under agitation, is cooled to room temperature after reaction with ice water, separated catalyst by being centrifuged, use
Methanol carries out quantitative analysis to reaction solution by reaction solution constant volume, using HPLC, and HPLC is furnished with Hypersil BDS C18 column
(4.6mm × 250mm, 5 μm) and ultravioletvisible absorption detector.
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