CN104258897B - Core-shell type molecular sieve coated catalysts and preparation method thereof - Google Patents
Core-shell type molecular sieve coated catalysts and preparation method thereof Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of core-shell type molecular sieve coated catalysts, described catalyst includes the kernel carrier containing catalytic hydrogenation activity component, and formation having on described kernel carrier selects the molecular sieve shell of shape or isomerization ability；Described preparation method includes the kernel carrier containing catalytic hydrogenation activity component utilizes alkaline solution carry out etch and the step that surfactant soaks；And on the kernel carrier of above-mentioned process, forming the step of molecular sieve shell.The catalyst obtained by preparation method of the present invention can realize the coupling reaction and separation receiving in minute yardstick, can be used for multiple hydrogenation and isomerization reaction, improve existing hygrogenating isomerization reaction technological process, reduce operating cost, improve production efficiency, it is achieved the efficient coupling of Reaction Separation technique；And this catalyst can for developing the Reaction Separation technique offer theoretical direction and technical foundation with independent intellectual property right.
Description
Technical field
The present invention relates to the technical field of petrochemical industry, it is more particularly related to a kind of core-shell type molecular sieve coated catalysts and preparation method thereof.
Background technology
Core-shell material is generally made up of the nucleation material at center and the shell two parts being coated on outside.Core is formed by physically or chemically acting on being connected with each other by two kinds of different materials with shell, and nucleocapsid two sections of material can be the components such as macromolecule, inorganic matter and metal respectively.It is coated on the Shell Materials outside nucleation material both can pass through change over the electric charge on nuclear material surface and then change over the surface nature of nuclear material, thus giving the functions such as particle is optical, electrical, magnetic, catalysis, can also pass through to change over the transparent performance on nuclear material surface, improve its stability and prevent itself and external agency from physically or chemically effect etc. occurring.Simultaneously as core-shell material combines the advantage of two or more materials, thus the multifunction of material can be realized.
When employing molecular sieve is coated on particulate vector or catalyst surface forms the composite catalyst with nucleocapsid structure, different from conventional film reactor, after cladding molecular sieve, single catalyst granules is a mini-size membrane reactor.Due to the sieving actoion of molecular screen membrane, only could pass through entrance catalyst kernel with the reactant of molecular sieve pore passage sizableness or less and product, realize separating and reacting the coupling of two processes simultaneously；Be sized generally below the catalytic active species in catalysis toxicity species and catalyst nucleus due to molecular sieve pore passage, " fence " effect of molecular screen membrane can stop the inactivation of catalyst and the loss of active component to a great extent；Additionally, the separation of molecular sieve itself, catalytic action can couple with the catalytic action of catalyst nucleus, between nucleocapsid catalyst, there is synergism；But nucleocapsid structure is likely to the reduction causing catalytic efficiency.
Chinese patent CN101530797 describes a kind of catalyst with core-casing structure and preparation method thereof, namely selects containing SnO2Metal-oxide as nucleation material, noble metal film layer is distributed in nucleation material surface.The catalyst with core-casing structure prepared by the method can improve precious metal catalyst activity while saving noble metal dosage, it is possible to reacts for Oxidation of Carbon Monoxide, oxygen electroreduction etc..Chinese patent CN102040448A describes a kind of method of preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell, adopt the complex nucleus shell structure molecular sieve catalytic methanol/dimethyl ether raw material being made up of HZSM-5 molecular sieve and mesopore molecular sieve, product Propylene Selectivity is high, and catalyst activity is stable.Chinese patent CN102463136A provides the MFI molecular sieve of a kind of nucleocapsid structure, with micron-sized Silicalite-1 molecular sieve for nuclear phase, with ZSM-5 molecular sieve nanometer layer for shell phase, by infusion process, active metal load is prepared on Silicalite-1 molecular sieve the core-shell molecular sieve of composite molecular screen.Described core-shell molecular sieve, for alkylating aromatic hydrocarbon in field of petrochemical industry, aromatics isomerization and the aspect such as methane aromatizing and alkane hydroisomerizing, especially has good catalytic performance in alkylation of toluene methanol.
Collier etc. (CollierP, GolunskiS, MaldeC, BreenJ, Burch.J.Am.Chem.Soc.2003,125,12414-12415) are at Fe/SiO2For the selective oxidation of butane and Co after particle catalyst surface catalytic growth cladding 4A molecular sieve.When 200 DEG C, still ensure that CO complete oxidation.Tsubaki etc. (BaoJ, HeJ, ZhangY, YoneyamaY, TsubakiN.Angew.Chem.Int.Ed.2008,47,353-356) develop the Co/Al of H-beta molecular sieve membrane cladding2O3.Catalyst is used for F-T synthesis reaction, and experiment finds that in reaction, the generation of C12+ hydrocarbon products is completely suppressed, significantly reduces the selectivity of byproduct methane simultaneously.Yang etc. (YangGH, TsubakiN, ShamotoJ, YoneyamaY, ZhangY.J.Am.Chem.Soc.2010,132,8129-8136) are with Cu-ZnO-Al2O3Ternary catalyst particles is core, prepares the H-ZSM5 molecular screen membrane shell of densification at catalyst surface.Prepare dimethyl ether for synthesis gas, generate almost without by-product carbinol.(the ZhongYJ such as Zhong, ChenL, LuoMF, XieYL, ZhuWD.ChemCommun, 2006,2911-2912) on the Pt/ γ-Al2O3 catalyst granules that mean diameter is 1.5mm, it is coated with 4A molecular screen membrane, using it for the selective oxidation of normal butane and CO, due to the molecule sieve effect of 4A molecular sieve, the conversion ratio of normal butane significantly reduces.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, it is an object of the invention to provide a kind of core-shell type molecular sieve coated catalysts and preparation method thereof.The technological means adopted for this present invention is to be coated on the inner nuclear material with Hydrogenation by the molecular sieve with selective isomerization function, nucleocapsid structure is utilized Hydrogenation and the selective isomerization performance of conventional catalyst to be combined, improve the activity and selectivity of catalyst, this catalyst can realize the coupling reaction and separation receiving in minute yardstick, can be used for multiple hydrogenation and isomerization reaction, improve existing hygrogenating isomerization reaction technological process, reduce operating cost, improve production efficiency；And this catalyst can for developing the Reaction Separation technique offer theoretical direction and technical foundation with independent intellectual property right.
In order to realize foregoing invention purpose, the technical solution adopted in the present invention is as follows:
The preparation method of a kind of core-shell type molecular sieve coated catalysts, described catalyst includes the kernel carrier containing catalytic hydrogenation activity component, and formation having on described kernel carrier selects the molecular sieve shell of shape or isomerization ability；It is characterized in that: described preparation method includes the kernel carrier containing catalytic hydrogenation activity component utilizes alkaline solution carry out etch and the step that surfactant soaks；And on the kernel carrier of above-mentioned process, forming the step of molecular sieve shell.
Wherein, described alkaline solution is potassium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, ethamine, diethylamine, triethylamine, ethylenediamine, propylamine, di-n-propylamine, tripropyl amine (TPA), tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetramethylammonium hydroxide, trimethyl ammonium hydroxide or benzyltrimethylammonium hydroxide and one or more mixture by a certain percentage in ammonium salt.
Wherein, the temperature of alkaline solution etch is 20-200 DEG C, and the time of etch is 0.5-24 hour.
Wherein, described surfactant is polymethacrylates or PDDA.
Wherein, described kernel carrier is selected from graphite, white carbon black, activated carbon, carbon fiber, CNT, porous polymer, Al2O3、MgO、ZnO、SiO2、SnO2、TiO2Or ZrO2In one or more.
Wherein, described molecular sieve shell is one or both in ZSM-5, Silicalite-1 or mordenite molecular sieve.
Wherein, described hydrogenation active component is the mixture by a certain percentage of one or more in Pt, Pd, Ni, Cu, Rh, Fe, Co, Ag, Mo, Zn, Cr, W or Au, with active metal component computational load amount for 0.001-30wt%；And the predecessor of described hydrogenation active component is sulfate, nitrate, phosphate, acetate, complex, halogenide, carbonyl compound or halogen acids.
Specifically, method of the present invention, comprise the following steps:
(1) predecessor containing hydrogenation active component be impregnated in kernel carrier, be then dried calcination process；
(2) the kernel carrier processed through step (1) is placed in alkaline solution etch a period of time, then utilizes surfactant to soak；
(3) the kernel carrier processed through step (2) is placed in the solution containing molecular sieve crystal seed and adsorbs；The material having adsorbed crystal seed is dried, roasting；
(4) material processed through step (3) is carried out crystallization and dried.
Wherein, in step (3), the described solution concentration containing molecular sieve crystal seed is 0.01%-50%, and described molecular sieve seed sized is 10nm-5 μm.
Wherein, in step (4), crystallization temperature is 80-250 DEG C, and the time is 2-120 hour；Crystallization solution is TPAOH, TEOS and H2The mixed solution of O.
Compared with prior art, the multifunction catalyst receiving minute yardstick coupling reaction and separation of the present invention, there is beneficial effect highlighted below:
1. introduce the molecular sieve shell with Shape-selective, " fence " effect can be played, some component in mixture material is carried out hydrogenation reaction, activity of hydrocatalyst component can be avoided to be polluted by the Cucumber in raw material simultaneously, improves the stability of catalyst by selective.
2. by the kernel carrier of load being carried out alkali etch and the process of described surfactant, can obtain being perpendicular to the orthotropic molecular sieve shell structure of kernel carrier surface, not only achieve and isomerization reaction is coupled with hydrogenation reaction, and compared with tradition bifunctional catalyst, core-shell catalyst hydrogenation and the degree of depth of isomerization reaction, selectivity and catalytic performance are all obviously improved.
3. the character of the thickness and shell layer surface by regulating catalyst Shell Materials, gets final product the combination property of regulating catalyst, and then realizes the controlled synthesis to catalyst function.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph (SEM) of the catalyst section of embodiment 1 preparation.
Fig. 2 is the electron scanning micrograph (SEM) of the catalyst shell molecular sieve surface of embodiment 2 preparation.
Fig. 3 is the X ray diffracting spectrum (XRD) of the catalyst shell molecular sieve of embodiment 2 preparation.
Fig. 4 is the surface (a) of nucleocapsid catalyst of embodiment 3 preparation, surface enlarged drawing (b), sectional drawing (c) and section amplification figure (d).
Detailed description of the invention
Below with reference to specific embodiment, Catalysts and its preparation method of the present invention is further elaborated, to help those skilled in the art that the inventive concept of the present invention, technical scheme are had more complete, accurate and deep understanding；It is to be noted in embodiment that the description about technological process and parameter etc. is all illustrative of, and do not imply that the restriction to invention protection domain.Test method described in example below, if no special instructions, is conventional method；Described instrument and material, if no special instructions, all commercially obtain.
By the core-shell type molecular sieve coated catalysts that method of the present invention prepares, including the kernel carrier containing catalytic hydrogenation activity component, described kernel carrier is formed with the molecular sieve shell selecting shape or isomerization ability；Wherein said molecular sieve shell is one or both in ZSM-5, Silicalite-1 or mordenite molecular sieve, described molecular sieve shell is the staggered symbiotic structure of column, and the angle of the staggered symbiotic structure of described column and kernel carrier surface normal is 0～5 °.Described molecular sieve shell is 10～100% in the coverage of described kernel carrier surface, it is therefore preferable to 50～100%；And the thickness of described molecular sieve shell is 1～50 μm, it is therefore preferable to 5～50 μm.As required, described kernel carrier is selected from graphite, white carbon black, activated carbon, carbon fiber, CNT, porous polymer, Al2O3、MgO、ZnO、SiO2、SnO2、TiO2Or ZrO2In one or more.Described kernel carrier is generally micron level.It addition, described kernel carrier can also be molecular sieve, and described molecular sieve is not ZSM-5, Silicalite-1 or mordenite molecular sieve.Wherein said hydrogenation active component is the mixture by a certain percentage of one or more in Pt, Pd, Ni, Cu, Rh, Fe, Co, Ag, Mo, Zn, Cr, W or Au, with active metal component computational load amount for 0.001-30wt%；And the predecessor of described hydrogenation active component is sulfate, nitrate, phosphate, acetate, complex, halogenide, carbonyl compound or halogen acids.The known method that described dipping method is this area does not repeat them here.In the present invention, by the kernel carrier of load being carried out the process of alkali etch and surfactant, the molecular sieve shell structurre of oriented growth can be obtained, especially can obtain being basically perpendicular to kernel carrier surface orthotropic molecular sieve shell structure (angle of the staggered symbiotic structure of described column and kernel carrier surface normal is 0～5 °), not only achieve and isomerization reaction is coupled with hydrogenation reaction, and compared with tradition bifunctional catalyst, the degree of depth of core-shell catalyst hydrogenation and isomerization reaction, selectivity and catalytic performance all increase.
Embodiment 1
Under room temperature, adopt conventional infusion process that 10ml5wt% nickel nitrate aqueous solution be impregnated in 2gSiO2On, stand 30min；The SiO that will have impregnated2It is placed in 60 DEG C of baking oven inner drying 2h, is subsequently placed in Muffle furnace in 500 DEG C of roasting 2h；By the SiO after cooling2It is placed in 10ml1wt%KOH solution, puts into hydrothermal reaction kettle, in 60 DEG C of baking ovens, process 2h；By the SiO after cooling2It is placed in the polymethacrylates aqueous solution of 6wt% and soaks 2h, then wash 3 times with weak ammonia, be placed in 60 DEG C of baking oven inner drying 2h；The SiO processed2It is placed in containing in the seed-solution of the Silicalite-1 that 15wt% yardstick is 50-100nm, after absorption 3h, with deionized water wash 3 times, is subsequently placed in 60 DEG C of baking ovens and processes 2h, in 500 DEG C of roasting 2h in Muffle furnace；After roasting, thing is placed in and consists of (TPAOH:TEOS:H2O=1:30:4500) in solution, put into crystallizing kettle at 100 DEG C, to react 8h obtain product, through deionized water wash 5 times, it is subsequently placed in 60 DEG C of baking ovens and processes 2h, namely obtaining product in Muffle furnace after 500 DEG C of roasting 2h, Fig. 1 is the electron scanning micrograph of the nucleocapsid catalyst section prepared, photo can be seen that under the reaction conditions, catalyst shell molecular screen membrane is continuous, homogeneous, fine and close, and film thickness is at 15-20 μm.
Embodiment 2
Under room temperature, adopt evacuation infusion process that 10ml0.1wt% chloroplatinic acid aqueous solution be impregnated in 2gAl2O3On, stand 30min；The Al that will have impregnated2O3It is placed in 60 DEG C of baking oven inner drying 2h, is subsequently placed in Muffle furnace in 500 DEG C of roasting 2h；Al2O3 after cooling is placed in 10ml1wt%NaOH solution, puts into hydrothermal reaction kettle, in 60 DEG C of baking ovens, process 2h；By the Al after cooling2O3It is placed in the PDDA aqueous solution of 2.4wt% and soaks 2h, then wash 3 times with weak ammonia, be placed in 60 DEG C of baking oven inner drying 2h；The Al processed2O3It is placed in the solution containing 15wt%ZSM-5 crystal seed, after absorption 3h, with deionized water wash 3 times, is subsequently placed in 60 DEG C of baking ovens and processes 2h, in 500 DEG C of roasting 2h in Muffle furnace；Product after roasting is placed in and consists of (NaOH:TPAOH:TEOS:H2O:Al2(SO4)3=1:15:60:5500:2) solution in, put into crystallizing kettle at 180 DEG C, to react 48h obtain product, through deionized water wash 3 times, product is obtained after being placed in 60 DEG C of baking oven inner drying 2h, Fig. 2 is the electron scanning micrograph on the nucleocapsid catalyst surface prepared, being can be seen that the staggered degree of intergrowth of catalyst shell molecular screen membrane is high by photo, compactness is good.Fig. 3 is the X ray diffracting spectrum of shell molecular sieve, and as seen from the figure, shell structurre is MFI-type molecular sieve film.
Embodiment 3
Under room temperature, adopt conventional infusion process to impregnated on 2gY type molecular sieve by 10ml0.2wt% Palladous chloride. and 0.05wt% chloroplatinic acid aqueous solution, stand 30min；The molecular sieve impregnated is placed in 60 DEG C of baking oven inner drying 2h, is subsequently placed in Muffle furnace in 500 DEG C of roasting 2h；Molecular sieve after cooling is placed in 10ml1wt% TPAOH solution, puts into hydrothermal reaction kettle, in 60 DEG C of baking ovens, process 2h；Molecular sieve after cooling is placed in the PDDA aqueous solution of 0.8wt% and soaks 2h, then washs 3 times with weak ammonia, be placed in 60 DEG C of baking oven inner drying 2h；The molecular sieve processed is placed in the solution containing 30wt%Silicalite-1 crystal seed, after absorption 2h, with deionized water wash 3 times, is subsequently placed in 60 DEG C of baking ovens and processes 2h, in 500 DEG C of roasting 2h in Muffle furnace；Product after roasting is placed in the solution consisting of (TPAOH:TEOS:H2O=1:20:5500), puts into crystallizing kettle and reacts 48h at 170 DEG C and obtain product, through deionized water wash 3 times, obtains product after being placed in 60 DEG C of baking oven inner drying 2h.The surface of the nucleocapsid catalyst that (a), (b), (c), (d) respectively prepare, surface amplification, section and section magnified sweep electron micrograph in Fig. 4, can be seen that by photo to prepare gained catalyst shell molecular screen membrane continuous, homogeneous, fine and close, film thickness is at 10-20 μm, and the staggered degree of intergrowth of molecular screen membrane is high, compactness is good.
Catalytic performance is tested
Adopt fixed bed reactors, reactor inside diameterMillimeter, length 1000 millimeters, stainless steel.Beds equal filled stone sand up and down plays air flow method and supporting role, one in the catalyst that in reactor, filling embodiment 1-3 and CN102463136A embodiment prepare, reaction condition is: reaction temperature is 400 DEG C, reaction pressure 5.0MPa, hydrogen-hydrocarbon ratio (V/V) is 500, and liquid quality air speed is 4h-1.Mixed xylenes raw material passes through beds after mixing with hydrogen, carries out selection isomerization and the selective hydrogenation of mixed xylenes, generates Isosorbide-5-Nitrae-dimethyl cyclohexane.In described mixed xylenes raw material, xylol (PX) accounts for 20wt%, and o-Dimethylbenzene (OX) accounts for 20wt%, and meta-xylene (MX) accounts for 45wt%, and ethylbenzene (EB) accounts for 15wt%；When adopting the catalyst that the embodiment of the present application 1～3 prepares, the recovery rate of Isosorbide-5-Nitrae-dimethyl cyclohexane reaches 85～90wt%；And when adopting the catalyst that CN102463136A embodiment prepares, the productivity of Isosorbide-5-Nitrae-dimethyl cyclohexane is only capable of reaching 30～40wt%.By the kernel carrier of load being carried out alkali etch and the process of described surfactant, the catalyst being perpendicular to the orthotropic molecular sieve shell structure of kernel carrier surface obtained, compared with tradition bifunctional catalyst, selectivity isomerizing hydrogenation performance is greatly improved.
For the ordinary skill in the art; the present invention is simply exemplarily described by specific embodiment in conjunction with accompanying drawing; the obvious present invention implements and is not subject to the restrictions described above; as long as have employed the improvement of the various unsubstantialities that the design of the method for the present invention carries out with technical scheme; or the not improved design by the present invention and technical scheme directly apply to other occasion, all within protection scope of the present invention.
Claims (3)
1. a preparation method for core-shell type molecular sieve coated catalysts, described catalyst includes the kernel carrier containing catalytic hydrogenation activity component, and formation having on described kernel carrier selects the molecular sieve shell of shape or isomerization ability；It is characterized in that: described preparation method includes the kernel carrier containing catalytic hydrogenation activity component utilizes alkaline solution carry out etch and the step that surfactant soaks；And on the kernel carrier of above-mentioned process, forming the step of molecular sieve shell；Wherein, described molecular sieve shell is the one in ZSM-5, Silicalite-1 or mordenite molecular sieve；Described surfactant is polymethacrylates or PDDA；Described alkaline solution is one or more mixture by a certain percentage in potassium hydroxide, sodium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetramethylammonium hydroxide, trimethyl ammonium hydroxide or benzyltrimethylammonium hydroxide；The temperature of described alkaline solution etch is 20-200 DEG C, and the time of etch is 0.5-24 hour；Described kernel carrier is selected from graphite, white carbon black, activated carbon, carbon fiber, CNT, porous polymer, Al2O3、MgO、ZnO、SiO2、SnO2、TiO2Or ZrO2In one or more；Described hydrogenation active component is the mixture by a certain percentage of one or more in Pt, Pd, Ni, Cu, Rh, Fe, Co, Ag, Mo, Zn, Cr, W or Au, with active metal component computational load amount for 0.001-30wt%；And the predecessor of described hydrogenation active component is sulfate, nitrate, phosphate, acetate, complex, halogenide or carbonyl compound.
2. the preparation method of core-shell type molecular sieve coated catalysts according to claim 1, it is characterised in that: described preparation method comprises the following steps:
(1) predecessor containing hydrogenation active component be impregnated in kernel carrier, be then dried calcination process；
(2) the kernel carrier processed through step (1) is placed in alkaline solution etch a period of time, then utilizes surfactant to soak；
(3) the kernel carrier processed through step (2) is placed in the solution containing molecular sieve crystal seed and adsorbs；The material having adsorbed crystal seed is dried, roasting；
(4) material processed through step (3) is carried out crystallization and dried.
3. the preparation method of core-shell type molecular sieve coated catalysts according to claim 2, it is characterised in that: in step (3), the described solution concentration containing molecular sieve crystal seed is 0.01%-50%, and described molecular sieve seed sized is 10nm-5 μm；In step (4), crystallization temperature is 80-250 DEG C, and the time is 2-120 hour；Crystallization solution is TPAOH, TEOS and H2The mixed solution of O.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN103349997A (en) * | 2013-07-14 | 2013-10-16 | 中建安装工程有限公司 | Composite membrane core-shell structure catalyst and preparation method of low carbon hydrocarbon through CO2 hydrogenation adopting same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121102A (en) * | 1994-07-15 | 1996-04-24 | 国际壳牌研究有限公司 | Process for the conversion of a hydrocarbonaceous feedstock |
-
2014
- 2014-07-24 CN CN201410355792.4A patent/CN104258897B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN103349997A (en) * | 2013-07-14 | 2013-10-16 | 中建安装工程有限公司 | Composite membrane core-shell structure catalyst and preparation method of low carbon hydrocarbon through CO2 hydrogenation adopting same |
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