CN102343289B - Preparation method for metal-based MFI type zeolite molecular sieve film - Google Patents
Preparation method for metal-based MFI type zeolite molecular sieve film Download PDFInfo
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- CN102343289B CN102343289B CN 201110163362 CN201110163362A CN102343289B CN 102343289 B CN102343289 B CN 102343289B CN 201110163362 CN201110163362 CN 201110163362 CN 201110163362 A CN201110163362 A CN 201110163362A CN 102343289 B CN102343289 B CN 102343289B
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Abstract
The invention discloses a preparation method for a metal-based MFI type zeolite molecular sieve film composite catalytic material. According to the method, a Silicalite-1 zeolite film crystal seed layer is prepared on a stainless steel carrier; metal nanoparticles are deposited on the crystal seed coating surface through an electrochemistry method; the MFI type zeolite molecular sieve film is secondarily grown on the crystal seed coating; the metal-based MFI type zeolite molecular sieve film is prepared through calcination. The electrodeposited metal nanoparticles are embedded in the crystal gaps in the crystal seed layer, the zeolite film prepared through the secondary hydrothermal synthesis has characteristics of continuity, compactness and no crack, and is solidly combined with the carrier so as to improve mechanical vibration resistance and heat conductivity of the coating. With the prepared metal-based zeolite molecular sieve film composite material through the method provided by the present invention, the transmission flux of the coating material to the material can be effectively improved, the problem of discontinuity of the zeolite molecular sieve film due to defects or calcination is solved, the combination strength of the zeolite molecular sieve film and the metal matrix is enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of zeolite molecular sieve film, be specially a kind of method that on metallic carrier, prepares high temperature resistant, fine and close flawless MFI type zeolite molecular sieve membrane coat.
Background technology
Research at metal surface synthetic catalyst film has caused extensive interest, the research of this class material not only can be widened its range of application, and it all may be better than pellet type catalyst aspect processing and the serviceability, can be used as catalytic distillation structure, also can be used as irregular shape catalyst, be used for that the requirement treating capacity is big, mass transfer and the fast catalytic process of heat transfer rate, be hopeful to be applied at some important chemical fields.Molecular sieve film catalyst is a kind of special inoranic membrane catalyst.As everyone knows, molecular sieve is a kind of catalyst of unique properties, but owing to its characteristic such as aperture, surface acidity and cation with modulation is widely used in fields such as petrochemical industry, fine chemistry industry and environmental protection.Shortcomings such as molecular sieve film catalyst has not only overcome traditional pellet type catalyst bed pressure drop height, and temperature and concentration gradient are big, but also have its unique shape selective catalysis function and good temperature resistance energy, thereby catalyst activity and selectivity improve greatly.Can be made into purified treatment, the Fischer-Tropsch synthesis that the integrated member catalyst is applied to vehicle exhaust as molecular screen membrane/porous metal composite material.Then have separation and catalysis dual-use function as membrane catalytic reactor, not only can cut down the consumption of energy, reduce operating procedure, and a certain component that can also remove selectively in the product improves reaction yield and the selectivity that is subjected to equilibrium-limited, and allow in same reactor, to carry out two reactions simultaneously, for its application in new catalytic process provides foundation.
During the last ten years, the preparation of zeolite molecular sieve film/metal carrier material and application have obtained very big progress, need study and solve but still exist some problems, for example: the even growth of (1) zeolite molecular sieve film is transmission (because anisotropy diffusion) that improves material and the assurance of controlling thermal stress (because anisotropic thermal expansion); (2) should avoid in the catalyst preparation process, and produce or increase inoranic membrane gap because of temperature-rise period; (3) reduce or eliminate because of two kinds of material coefficient of thermal expansion coefficients of metal and molecular sieve are different and produce in operation thermal stress, make zeolite molecular sieve rete unlikely coming off in temperature-rise period.Lousis proposes to prepare ZSM-5 zeolite coating (B.Lousis, P.Reuse, L.Kiwi-Minsker and A.Renken, Appl.Catal.A:General, 2001,201,103) with the growth in situ method on stainless steel grid carrier; Khoo Daw Deeng etc. are direct crystallization growth ZSM-5 molecular sieve on Lacunaris metal carrier, be used for nitrogen oxide, carbon monoxide and hydrocarbons remove (Khoo Daw Deeng, Abdul Rahman Mohamed, Subhash Bhatia.Process optimization studies of structured Cu-ZSM-5 zeolite catalyst for the removal of NO using design of experiments (DOE) .Chemical Engineering Journal 103 (2004) 147-157.) but the uniformity of the Metal Substrate zeolite molecular sieve membrane coat of these methods preparation, with the bond strength of metallic carrier, the thickness of molecular screen membrane and heat conductivity are difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of method that on metallic carrier, prepares even, continuous fine and close flawless zeolite molecular sieve membrane coat, reduce or eliminate the thermal stress that does not coexist and produce in applying because of metallic carrier and two kinds of material coefficient of thermal expansion coefficients of molecular screen membrane, with preparation in conjunction with firmly, the good gradient transition Metal Substrate MFI type zeolite molecular sieve film compound catalyze material of heat conductivity.
Technical solution of the present invention is: the Silicalite-1 zeolite membrane crystal seed layer that the precoating crystal seed method applies on the stainless steel carrier, the perhaps synthetic Silicalite-1 zeolite membrane crystal seed layer of original position hydro-thermal on the stainless steel carrier; Then on the crystal seed layer with the electrochemical deposition technique grappling growth in situ MFI type zeolite molecular sieve film thereon again behind the directed Silicalite-1 zeolite grain.Specific as follows:
A kind of preparation method of Metal Substrate MFI type zeolite molecular sieve film is characterized in that comprising the steps:
1. prepare MFI type zeolite membrane crystal seed transition zone on the stainless steel carrier;
2. seed coating layer surface electrochemistry depositing nano metal;
3. diauxic growth MFI type zeolite molecular sieve film on the seed coating layer;
4. make the metal-based nano molecular screen membrane through roasting.
1. step prepares Silicalite-1 zeolite membrane crystal seed transition zone on stainless steel carrier method is:
Method one: the precoating crystal seed method applies the zeolite membrane crystal seed layer
1.-a removes its surperficial grease with washing agent and washed with de-ionized water stainless steel carrier, puts into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out flushing, drying for standby;
Described washing agent is ethanol or acetone;
1.-b prepares seed coating layer liquid:
Earlier TPAOH is added in the deionized water, the 375rpm rotating speed stirs 30min, adds ethyl orthosilicate simultaneously in stirring then, continues to stir ageing 24h, and in 100 ℃ of crystallization 24h, it is standby that supersonic oscillations obtain seed coating layer liquid then;
The mol ratio of TPAOH, ethyl orthosilicate, deionized water is 9: 25: 480;
1.-c plants zeolite seed crystal in advance:
Will be 1.-a in stainless steel carrier in seed coating layer liquid, soak 2-4min, then with horizontal plane be inclined to 60 the degree angle 6m/s speed at the uniform velocity pull out, dry 4-12h naturally; Repeat to soak 1-3 time;
Method two: original position crystal seed method growth zeolite membrane crystal seed layer
1.-I removes its surperficial grease with washing agent and washed with de-ionized water stainless steel carrier, puts into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out flushing, drying for standby;
Described washing agent is ethanol or acetone;
1.-II is dissolved in TPAOH in the deionized water, 375rpm stir or ultrasound condition under, drip ethyl orthosilicate; Continue to stir ageing 5h, obtain the synthetic liquid of zeolite membrane;
1.-stainless steel carrier that III will be 1. handles among the I be immersed in fully step 1.-the resulting zeolite membrane of II synthesizes in the liquid 165 ℃ of crystallization 5.5h;
The mol ratio of described ethyl orthosilicate, TPAOH and deionized water is 1: 0.32: 165.
The method of the 2. described seed coating layer surface electrochemistry of step depositing nano metal comprises:
Add H in the aqueous solution of sulfate, nitrate or the acetate of metal cation, adding
3BO
3, obtaining electrodeposit liquid, the concentration that makes metal cation in the electrodeposit liquid is 0.5～0.8mol/L, H
3BO
3Concentration be 30～35g/L; With the platinized platinum is anode, and the stainless steel carrier that 1. step was handled is a negative electrode, in 25 ℃ of waters bath with thermostatic control, and electro-deposition 1-5min under the condition of deposition voltage 3-10V; Stainless steel carrier dry 12-24h under 100 ℃ of conditions after electro-deposition is finished;
Described metal cation is Ni
2+, Cu
2+, Mn
2+Or Co
2+
The method of diauxic growth MFI type zeolite molecular sieve film is on the 3. described seed coating layer of step:
3.-a TPAOH is dissolved in the deionized water, 375rpm stir or ultrasound condition under, add ethyl orthosilicate after; Continue to stir ageing 6h, obtain the synthetic liquid of zeolite membrane;
The mol ratio of described ethyl orthosilicate, TPAOH and deionized water is 1: 0.16: 110;
3.-stainless steel carrier that the b step was handled in 2. be immersed in fully step 3.-zeolite membrane that a obtains synthesizes in the liquid 175 ℃ of crystallization 24h.
The inventive method can prepare the zeolite molecular sieve film of other different metal bases, MFI, BEA, the isostructural zeolite molecular sieve film of A type as copper base, Metal Substrate such as Ni-based, use the inventive method and prepare various types of zeolite molecular sieve films, in strong heat release or strong endothermic catalytic reaction system, the like product of the zeolite molecular sieve film more synthetic than single zeolite molecular sieve and conventional method has more advantage.
In the intergranular crack, synthetic continuous, the fine and close nothing of zeolite membrane of secondary hydro-thermal is split scarce, with the carrier firm binding force, has improved the anti-mechanical oscillation performance and the heat-conductive characteristic of coating on the nano-metal particle embedding crystal seed layer of electro-deposition of the present invention.
The Metal Substrate zeolite molecular sieve film composite material that method provided by the present invention obtains is compared with other existing methods, have molecular screen membrane and combine characteristics firm, high temperature resistant and that heat conductivity is good with carrier, can effectively improve the propagated flux of coating material to material, solve zeolite molecular sieve film because the discontinuous problem that defective or roasting cause, strengthened the bond strength of zeolite molecular sieve film and metallic matrix.
Description of drawings
18 in the total invention accompanying drawing of the present invention, wherein:
Fig. 1 is the SEM figure of product M1;
Fig. 2 is the SEM figure of product M2;
Fig. 3 is the XRD figure of product M2;
Fig. 4 is the XRD figure of product M3;
Fig. 5 is the EDX figure of product M3;
Fig. 6 is the XRD figure of product M4;
Fig. 7 is the SEM figure of product M4;
Fig. 8 is the SEM figure of product M5;
Fig. 9 is the XRD figure of product M5;
Figure 10 is the EDX figure of product M5;
Figure 11 is the EDX figure of product M6;
Figure 12 is the SEM figure of product M7;
Figure 13 is the SEM figure of product M8;
Figure 14 is the XRD figure of product M8;
Figure 15 is the XRD figure of product M9;
Figure 16 is the SEM figure of product M9;
Figure 17 is the SEM figure of product M10;
Figure 18 is the XRD figure of product M10.
The specific embodiment
In order better to understand the present invention, below the invention will be further described with embodiment, but the present invention is not limited to these examples.
1: three kind of method of embodiment prepares the contrast of Metal Substrate molecular screen membrane composite firmness
Method one: original position hydro-thermal method direct growth MFI type molecular screen membrane
The TPAOH of template agent 1.5mL 2.214moL/L is dissolved in the 3.2g water, stirs.Under the stirring condition, slowly drip 2.0g TEOS then, stirring at room 6h obtains clarifying synthetic liquid.The stainless steel carrier of handling well is put on the polytetrafluoroethylene (PTFE) support, vertically put into and have teflon-lined stainless steel crystallizing kettle, then the above-mentioned synthetic liquid that makes is poured in the still, stainless steel carrier is flooded, at 175 ℃ of following hydro-thermal Synthetic 2 4h.After taking out still, anxious water cooling is taken out stainless steel carrier, wash repeatedly with deionized water, and cleaned by ultrasonic vibration, dry in the shade under the room temperature.Repeat above process once.The stainless steel carrier that drying is good is put in the Muffle furnace, the employing temperature programming (1 ℃/min) to 540 ℃, roasting 4h is to remove TPAOH (TPAOH) the template agent in the fenestra.Obtain sample M1.
Method two: precoating crystal seed method diauxic growth MFI type molecular screen membrane
The preparation of step 1. seed coating layer liquid
With TPAOH, ethyl orthosilicate, deionized water mixed in molar ratio according to 9: 25: 480.Earlier 1.5mL 2.214moL/L TPAOH is added 3.2g H
2Among the O, the 375rpm rotating speed stirs 30min, dropwise adds 2.0g TEOS simultaneously in stirring then.Continue to stir ageing 24h then.The synthetic liquid that ageing is good is slowly poured in the still, with the still good seal, puts into 100 ℃ baking oven crystallization 24h again.Then still is taken out from baking oven,, product taken out from still to place the beaker supersonic oscillations to obtain seed coating layer liquid standby with behind the cold water chilling.
The preparation of step 2. stainless steel electrode
End boring with stainless steel carrier (20x30mm) pulls out copper conductor, utilizes epoxy sealing lead exposed region, and stainless steel electrode is prepared as follow-up load crystal seed and electro-deposition zone in remaining zone.
The preliminary treatment of step 3. stainless steel electrode
Adopt 30 orders, 240 orders, 1000 order sand papering electro-deposition zones successively, use ethanol, washed with de-ionized water electro-deposition zone then, drying for standby under the room temperature.
Place the seed coating layer liquid of step 1 preparation to soak 2min step 2 and 3 stainless steel electrodes of handling, at the uniform velocity to pull out with horizontal plane 60 speed of spending angle 6m/s that are inclined to, drying at room temperature 6h obtains sample M2 then.
At CuSO
4Add H in the solution
3BO
3, make CuSO in the solution
4Concentration be 0.5mol/L, H
3BO
3Concentration be 30g/L, obtain required electric depositing solution.
The step 6. crystal seed layer depositing nano Cu that powers on
As negative electrode, platinum electrode is as anode with the stainless steel electrode of step 4 preparation, and the electric depositing solution of step 5 preparation places water bath with thermostatic control to keep 25 ℃, is under the condition of 5V at voltage, electro-deposition 1min.Electro-deposition finishes back taking-up negative electrode stainless steel electrode and places 100 ℃ of drying for standby, obtains sample M3.
With ethyl orthosilicate, TPAOH and deionized water mixed in molar ratio according to 1: 0.16: 110.Earlier 1.3mL concentration is added 34.96gH for 2.214moL/L TPAOH
2Among the O, under stirring of 375rpm rotating speed or the ultrasonication, dropwise add the TEOS of 3.74g.Continue then to stir ageing 6h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier of step 6 preparation is fixed on the polytetrafluoroethylene (PTFE) support, vertically put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence with stainless steel carrier, with the still good seal, put into 175 ℃ baking oven crystallization 24h again.Crystallization is taken out still after finishing from baking oven, behind the cold water chilling, stainless steel carrier is taken out from still, washes repeatedly through deionized water, and 100 ℃ of oven dry obtain sample M4.
Method three: original position crystal seed method diauxic growth MFI type molecular screen membrane
Step 1: the preliminary treatment of stainless steel carrier
Use 30 orders, 240 orders, 1000 order model sand papering stainless steel surfaces respectively, remove its surperficial grease with ethanol and washed with de-ionized water again, put into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out flushing, drying for standby;
Step 2: the synthetic Silicalite-1 zeolite membrane crystal seed transition zone of original position hydro-thermal on the stainless steel carrier
In conical flask, with TEOS, TPAOH and H
2O presses TEOS: TPAOH: H
2O=1: 0.32: 165 ratio is mixed.Earlier 1.73mL2.214moL/L TPAOH is added 34.56gH
2Among the O, under stirring or ultrasonication under the 375rpm rotating speed, dropwise add 2.5gTEOS.Continue then to stir ageing 5h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier of handling has vertically been put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence,, put into 165 ℃ baking oven crystallization 5.5h again with the still good seal with stainless steel carrier.Then still is taken out from baking oven, behind the cold water chilling, stainless steel carrier is taken out from still, after deionized water washes repeatedly,, obtain sample M5 in 100 ℃ of oven dry.
At CuSO
4Add H in the solution
3BO
3, make CuSO in the solution
4Concentration be 0.5mol/L, H
3BO
3Concentration be 30g/L, obtain required electric depositing solution.
With behind the stainless steel carrier removed template method of step 2 preparation as negative electrode, platinum electrode is as anode, the electric depositing solution of step 3 preparation places water bath with thermostatic control to keep 25 ℃, under the condition of deposition voltage 5V, electro-deposition 1min.Electro-deposition finishes the back and takes out 100 ℃ of drying for standby of negative electrode stainless steel carrier, obtains sample M6.
With ethyl orthosilicate, TPAOH and deionized water mixed in molar ratio according to 1: 0.16: 110.Earlier 1.3mL concentration is added 34.96gH for 2.214moL/L TPAOH
2Among the O, under stirring of 375rpm rotating speed or the ultrasonication, dropwise add the TEOS of 3.74g.Continue then to stir ageing 6h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier of step 4 preparation has been put in the teflon-lined stainless steel crystallizing kettle, and then that ageing is good synthetic liquid is slowly poured in the still, with the complete submergence of stainless steel carrier, with the still good seal, puts into 175 ℃ baking oven crystallization 24h.Crystallization is taken out still after finishing from baking oven, behind the cold water chilling, stainless steel carrier is taken out from still, washes repeatedly through deionized water, and 100 ℃ of oven dry obtain sample M7.
MFI type zeolite molecular sieve film to three kinds of method preparations, by mechanical vibration method (vibration 30min weighs in the ultrasound bath) and thermal shock method (400 ℃ of calcining 30min, take out then and put into cold water immediately, after placing 10min, dry its weight that claims) analyzed the combine firmness of molecular screen membrane with stainless steel carrier, characterize by XRD, SEM, EDX, analyzed molecular screen membrane thing phase, pattern and element and formed.By thermal shock test and mechanical oscillation test, the weight-loss ratio of three kinds of method molecular screen membranes is respectively: 37.48%, 27.36%; 7.03%, 5.67%; 3.73%, 2.28%.Compare the method one of conventional molecular screen membrane growth as can be seen, the introducing of method two, three zeolite seed crystal top layer electro-deposition nano metal steps effectively raises the firmness that combines of molecular screen membrane and stainless steel carrier.
In the method two, three, the carrier surface after the different step processing is carried out XRD, SEM and EDX sign.XRD shows that coating is a Silicalite-1 zeolite seed crystal layer after the coating electro-deposition, and there is copper in the surface, and EDX test shows crystal seed layer area load has copper.It is the Silicalite-1 zeolite membrane that XRD is presented at the synthetic rete of secondary hydro-thermal, SEM schemes to show, the synthetic Silicalite-1 zeolite membrane laminar surface molecular sieve of secondary hydro-thermal is the symbiosis of cuboid or a plurality of cuboids, the surface crystal level of coverage is complete, crystallite dimension is between 3～6 μ m, and the general commissure of surface crystal is grown.EDX test shows surface does not have Cu, only from Si, the Al of Silicalite-1 zeolite, has proved that the synthetic Silicalite-1 zeolite rete of secondary hydro-thermal is continuous, the densification nothing is split scarce.
Embodiment 2: Metal Substrate MFI type zeolite molecular sieve film compound catalyze material is applied in the low-concentration methane catalytic combustion
Step 1: the preliminary treatment of stainless steel carrier
Use 30 orders, 240 orders, 1000 order model sand papering stainless steel surfaces respectively, remove its surperficial grease with ethanol and washed with de-ionized water again, put into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out flushing, drying for standby;
Step 2: the original position hydrothermal synthesis method prepares Silicalite-1 zeolite membrane crystal seed transition zone on the stainless steel carrier
In conical flask, with TEOS, TPAOH and H
2O presses TEOS: TPAOH: H
2O=1: 0.32: 165 ratio is mixed.Earlier 1.734mL concentration is added 34.56gH for 2.214moL/L TPAOH
2Among the O, under stirring of 375rpm rotating speed or the ultrasonication, dropwise add the TEOS of 2.5g.Continue then to stir ageing 5h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier that step 1 was handled is fixed on the polytetrafluoroethylene (PTFE) support, vertically put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence with stainless steel substrates, with the still good seal, put into 165 ℃ baking oven crystallization 5.5h again.Then still is taken out from baking oven,, stainless steel substrates is taken out from still with behind the cold water chilling, after deionized water washes repeatedly in 100 ℃ of oven dry.
At Mn (NO
3)
2Add H in the solution
3BO
3, make Mn (NO in the solution
3)
2Concentration be 0.8mol/L, H
3BO
3Concentration be 35g/L, obtain required electric depositing solution.
With behind the stainless steel substrates removed template method of step 2 preparation as negative electrode, platinum electrode is as anode, the electric depositing solution of step 3 preparation places water bath with thermostatic control to keep 25 ℃, under the condition of voltage 5V, electro-deposition 1min.Electro-deposition finishes the back and takes out 100 ℃ of drying for standby of negative electrode stainless steel substrates.
With ethyl orthosilicate, TPAOH and deionized water mixed in molar ratio according to 1: 0.16: 110.Earlier 1.3mL concentration is added 34.96gH for 2.214moL/L TPAOH
2Among the O, the 375rpm rotating speed stir or ultrasonication under, dropwise add the TEOS of 3.74g after, continue to stir ageing 6h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier of step 4 preparation has been put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence,, put into 175 ℃ baking oven crystallization 24h again with the still good seal with stainless steel carrier.Crystallization is taken out still after finishing from baking oven, behind the cold water chilling, stainless steel substrates is taken out from still, washes 100 ℃ of oven dry repeatedly through deionized water.
Step 6: load active component La on Metal Substrate Silicalite-1 zeolite membrane composite
0.7S
0.3MnO
3
The print that step 5 is obtained carries out the roasting removed template method with following roasting technique.Roasting technique is: Muffle furnace is raised to 260 ℃ with the heating rate of 1 ℃/min from 30 ℃, kept 1 hour at 260 ℃, still be warmed up to 550 ℃ then with the heating rate of 1 ℃/min, rate of temperature fall with 1 ℃/min dropped to 30 ℃ from 550 ℃ to constant temperature subsequently to remove the agent of tetrapropyl ammonium template fully in 4 hours under this temperature.With lanthanum nitrate, strontium nitrate, manganese nitrate mixed in molar ratio by 0.7: 0.3: 1, add the citric acid of 1.5 times of metal ion total amounts and 1.3 times water then, mix stirring at room 2h.Evaporating solvent in 80 ℃ water bath with thermostatic control, with the thick liquid that becomes sticky as coating liquid.
Adopt the dip-coating method to apply La then
0.7S
0.3MnO
3Active component.Take out the stainless steel carrier of above-mentioned removed template method left standstill 3min in active component coating liquid after, 120 ℃ of dryings repeat to leave standstill twice, 800 ℃ of calcination 1h, remove the material of the loose show bubble of carrier surface.Said process is triplicate again, to reach required gain in weight, at last respectively at 800 ℃, 900 ℃ calcination 5h.Obtain sample M8.
Carrier surface after the different step processing is carried out XRD, SEM to be characterized.Coating is a Silicalite-1 zeolite seed crystal layer behind the XRD demonstration coating electro-deposition manganese.It is the Silicalite-1 zeolite membrane that XRD is presented at the synthetic rete of secondary hydro-thermal, the SEM photo shows, the synthetic Silicalite-1 zeolite membrane laminar surface molecular sieve of secondary hydro-thermal is the symbiosis of cuboid or a plurality of cuboids, and the surface crystal level of coverage is complete, general commissure growth.
The load active component sample is carried out XRD, SEM to be characterized.From XRD figure, observe the perovskite characteristic peak that active component has formed the well-crystallized, and do not have MFI type zeolite molecular sieve film peak, illustrate that active component almost all covers molecular screen membrane.SEM figure continues load active component as can be seen on Metal Substrate MFI type zeolite molecular sieve film compound catalyze material, active component particle load capacity thereon is big, and particle size is even, disperses more complete.
The sample for preparing is used in the low-concentration methane catalytic combustion, and reaction gas consists of 2% methane, 98% air, and gas space velocity adopts 24200mL/cat-g (catalyst activity constituent mass) h respectively.Range of reaction temperature 350-780 ℃.Reactant and product are by the gas chromatograph on-line analysis.Reaction draws, methane conversion surpasses 10% in the time of 350 ℃, 700 ℃ of methane reach 100% the conversion of finishing, and preparing the integer catalyzer initiation temperature than other method has all had significantly reduction with complete conversion temperature, has showed the active and high temperature active stability of extraordinary low temperature ignition.
Embodiment 3: Metal Substrate molecular screen membrane compound catalyze material is applied in the Fischer-Tropsch synthesis
Step 1: the preliminary treatment of stainless steel carrier
The shaped back of stainless steel carrier is washed to remove grease with acetone, rinse well with deionized water again, put into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out flushing, drying for standby.
Step 2: the synthetic Silicalite-1 zeolite membrane crystal seed transition zone of original position hydro-thermal on the stainless steel carrier
In conical flask, with TEOS, TPAOH and H
2O presses TEOS: TPAOH: H
2O=1: 0.32: 165 ratio is mixed.Earlier 1.734mL concentration is added 34.56gH for 2.214moL/L TPAOH
2Among the O, under stirring of 375rpm rotating speed or the ultrasonication, dropwise add the TEOS of 2.5g.Continue then to stir ageing 5h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier that step 1 was handled is fixed on the polytetrafluoroethylene (PTFE) support, vertically put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence with stainless steel substrates, with the still good seal, put into 165 ℃ baking oven crystallization 5.5h again.Then still is taken out from baking oven,, stainless steel substrates is taken out from still with behind the cold water chilling, after deionized water washes repeatedly in 100 ℃ of oven dry.
At CoSO
4Add H in the solution
3BO
3, make CoSO in the solution
4Concentration be 0.5mol/L, H
3BO
3Concentration be 30g/L, obtain required electric depositing solution.
With behind the stainless steel carrier removed template method of step 2 preparation as negative electrode, platinum electrode is as anode, the electric depositing solution of step 3 preparation places water bath with thermostatic control to keep 25 ℃, under voltage 3V condition, electro-deposition 1min.Electro-deposition finishes back taking-up negative electrode stainless steel carrier and places 100 ℃ of drying for standby, obtains sample M9.
With ethyl orthosilicate, TPAOH and deionized water mixed in molar ratio according to 1: 0.16: 110.Earlier 1.3mL concentration is added 34.96gH for 2.214moL/L TPAOH
2Among the O, under stirring of 375rpm rotating speed or the ultrasonication, dropwise add the TEOS of 3.74g.Continue to stir ageing 6h, to obtain the synthetic liquid of zeolite membrane.The stainless steel carrier of step 4 preparation has been put in the teflon-lined stainless steel crystallizing kettle, then that ageing is good synthetic liquid is slowly poured in the still, till complete submergence,, put into 175 ℃ baking oven crystallization 24h again with the still good seal with stainless steel carrier.Crystallization is taken out still after finishing from baking oven, behind the cold water chilling, stainless steel substrates is taken out from still, washes 100 ℃ of oven dry repeatedly through deionized water.
Step 6: load active component cobalt on Metal Substrate Silicalite-1 zeolite membrane composite
The print that obtains is carried out the roasting removed template method with following roasting technique.Roasting technique is: Muffle furnace is raised to 260 ℃ with the heating rate of 1 ℃/min from 30 ℃, kept 1 hour at 260 ℃, still be warmed up to 550 ℃ then with the heating rate of 1 ℃/min, rate of temperature fall with 1 ℃/min dropped to 30 ℃ from 550 ℃ to constant temperature subsequently to remove the agent of tetrapropyl ammonium template fully in 4 hours under this temperature.Cobalt nitrate solution with equi-volume impregnating preparation 0.6moL/L is added drop-wise to dropper on the zeolite membrane on stainless steel carrier surface, puts into to put in the Muffle furnace behind the oven dry 12h in 100 ℃ of baking ovens when at room temperature being dried to surperficial dripless to obtain sample M10 at 400 ℃ of following roasting 6h.
Carrier surface after the different step processing is carried out XRD, SEM to be characterized.Coating is a Dilicalite-1 zeolite seed crystal layer behind the XRD demonstration coating electro-deposition cobalt, and there is cobalt in the surface.It is the Silicalite-1 zeolite membrane that XRD is presented at the synthetic rete of secondary hydro-thermal, the SEM photo shows, the synthetic Silicalite-1 zeolite membrane laminar surface molecular sieve of secondary hydro-thermal is the symbiosis of cuboid or a plurality of cuboids, the surface crystal level of coverage is complete, 3～6 μ ms between, grow substantially by the general commissure of surface crystal for crystallite dimension.
The sample for preparing is used Fischer-Tropsch synthesize, earlier at 420 ℃ of temperature, normal pressure, H
2=30ml/min is reduction 10h down, afterwards 240 ℃ of temperature, and 2.0Mpa, CO=10ml/min, H
2=20ml/min is reaction 50h down, and stability is better, diesel oil distillate (C in the liquid product
12-C
18) account for 81.69%, gasoline fraction (C
5-11) account for 15.72%, account for about 95% of whole product, what obtain is the liquid product of high added value.
Claims (1)
1. the preparation method of a Metal Substrate MFI type zeolite molecular sieve film is characterized in that comprising the steps:
1. prepare Silicalite-1 zeolite membrane crystal seed layer on the stainless steel carrier;
2. seed coating layer surface electrochemistry depositing nano metal;
3. diauxic growth MFI type zeolite molecular sieve film on the seed coating layer;
4. make Metal Substrate MFI type zeolite molecular sieve film through roasting;
The method of the 2. described seed coating layer surface electrochemistry of step depositing nano metal is:
In the aqueous solution of sulfate, nitrate or the acetate of metal cation, add H
3BO
3, obtaining electrodeposit liquid, the concentration that makes metal cation in the electrodeposit liquid is 0.5～0.8mol/L, H
3BO
3Concentration be 30～35g/L; With the platinized platinum is anode, and the stainless steel carrier that 1. step was handled is a negative electrode, in 25 ℃ of waters bath with thermostatic control, and electro-deposition 1-5min under the condition of deposition voltage 3-10V; Carrier dry 12-24h under 100 ℃ of conditions after electro-deposition is finished;
Described metal cation is Ni
2+, Cu
2+, Mn
2+Or Co
2+;
1. described step prepares Silicalite-1 zeolite membrane crystal seed transition zone on stainless steel carrier method has following two kinds, is respectively:
Method one: 1.-a is with washing agent and washed with de-ionized water stainless steel carrier, puts into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out stainless steel carrier through flushing, drying, and is standby;
Described washing agent is ethanol or acetone;
1.-b prepares seed coating layer liquid:
TPAOH is added in the deionized water, after the 375rpm rotating speed stirs 30min, add ethyl orthosilicate while stirring after, continue to stir ageing 24h; Synthetic liquid after the ageing is 100 ℃ of crystallization 24h in still, and supersonic oscillations obtain seed coating layer liquid then;
The mol ratio of described TPAOH, ethyl orthosilicate and deionized water is 9:25:480;
1.-c plants zeolite seed crystal in advance:
Will be 1.-a in stainless steel carrier in seed coating layer liquid, soak 2-4min, then with horizontal plane be inclined to 60 the degree angle 6m/s speed at the uniform velocity pull out, dry 4-12h naturally; Repeat aforesaid operations 1-3 time;
Method two: 1.-I is with washing agent and washed with de-ionized water stainless steel carrier, puts into the H of 30wt% concentration
2O
2The middle 30min that soaks takes out stainless steel carrier through flushing, drying, and is standby;
Described washing agent is ethanol or acetone;
1.-II is dissolved in TPAOH in the deionized water, 375rpm stir or ultrasound condition under, drip ethyl orthosilicate; Continue to stir ageing 5h, obtain the synthetic liquid of zeolite membrane;
1.-III will be 1.-stainless steel carrier handled in the I be immersed in fully step 1.-the synthetic liquid of zeolite membrane that II obtains in, 165 ℃ of crystallization 5.5h;
The mol ratio of described ethyl orthosilicate, TPAOH and deionized water is 1:0.32:165;
The method of diauxic growth MFI type zeolite molecular sieve film is on the 3. described seed coating layer of step:
3.-a TPAOH is dissolved in the deionized water, 375rpm stir or ultrasound condition under, add ethyl orthosilicate after; Continue to stir ageing 6h, obtain the synthetic liquid of zeolite membrane;
The mol ratio of described ethyl orthosilicate, TPAOH and deionized water is 1:0.16:110;
3.-stainless steel carrier that the b step was handled in 2. be immersed in fully step 3.-zeolite membrane that a obtains synthesizes in the liquid 175 ℃ of crystallization 24h.
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| CN103100415B (en) * | 2012-12-03 | 2015-06-10 | 北京化工大学 | Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application |
| CN104722327B (en) * | 2013-12-18 | 2018-05-22 | 武汉凯迪工程技术研究总院有限公司 | It is a kind of for metal base monolithic film catalyst of Fiscber-Tropscb synthesis and preparation method thereof |
| CN103818089B (en) * | 2014-03-03 | 2017-02-15 | 河南中烟工业有限责任公司 | Preparation method of metal anti-corrosion coating |
| CN105502431B (en) * | 2015-12-03 | 2018-06-26 | 吉林化工学院 | A kind of preparation method of MFI-LTA molecular sieves individual layer composite membrane |
| CN109647496A (en) * | 2018-11-09 | 2019-04-19 | 南京工业大学 | A kind of multicomponent catalysis material of Zeolite modifying glass fibre and its preparation method and application |
| CN113881932B (en) * | 2021-09-18 | 2022-07-19 | 浙江大学 | Low-temperature rapid preparation method of hydrophobic high-orientation all-silicon zeolite protective film |
| CN115591574A (en) * | 2022-10-08 | 2023-01-13 | 扬州晨化新材料股份有限公司（Cn） | Porous alumina-supported metal copper catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843629A (en) * | 2006-04-18 | 2006-10-11 | 天津大学 | Method for preparing catalyst with micron-grade zeolite molecular sieve coated on carrier |
| CN101696018A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Method for synthesizing silicalite-1 zeolite membranes |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843629A (en) * | 2006-04-18 | 2006-10-11 | 天津大学 | Method for preparing catalyst with micron-grade zeolite molecular sieve coated on carrier |
| CN101696018A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Method for synthesizing silicalite-1 zeolite membranes |
Non-Patent Citations (2)
| Title |
|---|
| MFI型沸石膜构件催化剂制备方法研究;刘志禹;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20101015(第10期);正文20-45页 * |
| 刘志禹.MFI型沸石膜构件催化剂制备方法研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2010,(第10期),正文20-45页. |
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